JP2013136679A - Polyolefin-based resin extruded sheet and container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an extruded sheet having high rigidity, and excellent draw down property and deep drawability in the thermo-molding.SOLUTION: A cross-linked foam is obtained by cross-linking and foaming an ethylene-based polymer composition for foam molding. The ethylene-based polymer composition for foam molding contains 2.0-25 pts.wt. of foaming agent with respect to 100 pts.wt. ethylene/α-olefin copolymer which has 925-945 kg/mdensity and 1-20 g/10 min MFR (Melt Flow Rate), shows two peaks in a molecular weight measurement by a gel permeation chromatography, and has a ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 3.0-10.0 and a plurality of peaks in an elution temperature-elution amount curve obtained by a continuous temperature rising elution fractionation (TREF) technique.

Description

  The present invention relates to an extruded sheet comprising a composition of a polypropylene resin and a specific polyethylene resin, and a container comprising the same.

  Polypropylene resins are widely used as various molded products because they are inexpensive and excellent in physical properties. In particular, polypropylene resins are mainly used for plastic trays used as food packaging materials because of their excellent balance of rigidity, heat resistance, and price. The plastic tray is manufactured by a thermoforming method such as a so-called vacuum forming method or a pressure forming method in which a resin sheet obtained by extrusion molding is softened by applying heat, and a semi-molten resin is adhered to a mold. Conventional propylene-based resin for sheet has low viscosity at the time of melting and lacks melt tension, so there is uneven thickness of the molded product and drooping down of the resin when the sheet is thermoformed. It became a problem and it was difficult to apply to deep drawing products and large area products.

  Several studies have been made for the purpose of solving such problems, that is, improving the melt tension of polypropylene resins. For example, a method of adding high-pressure low-density polyethylene (LDPE) produced by a high-pressure radical polymerization method to a polypropylene resin is a typical technique (see, for example, Patent Documents 1 and 2). Further, a method for improving the melt processability of polypropylene by irradiating a linear polypropylene resin with high energy ionizing radiation such as electron beam or gamma ray in the presence of active oxygen to cause long chain branching (for example, patents) Reference 3), and a method of adding a core-shell graft copolymer obtained by graft copolymerization of a vinyl monomer to a rubber-like polymer to a polypropylene resin (for example, see Patent Document 4). .

  In addition, a new polyethylene-based resin having excellent thermal stability and excellent molding processability in a wide molding process temperature range has been proposed (see, for example, Patent Documents 5 and 6).

JP 52-136247 A JP 58-185634 A Japanese Patent Laid-Open No. 62-121704 JP-A-5-339433 JP 2004-346304 A (Claims) JP 2007-169339 A (Claims)

  However, in the methods proposed in Patent Documents 1 and 2, the effect is small when the amount of LDPE added is small, and when a large amount of LDPE is added, the rigidity, which is a major characteristic of polypropylene resins, is reduced. A new problem has occurred and the problem has not been solved. In addition, the method proposed in Patent Document 3 requires a facility for irradiating high-energy ionizing radiation, which is disadvantageous in terms of cost. The method proposed in Patent Document 4 has a problem that a large amount of core-shell graft copolymer must be added in order to improve the melt tension of the polypropylene resin. Therefore, it has been difficult to efficiently produce a foamed sheet having good product properties using polypropylene modified by these methods.

  In Patent Documents 4 and 5, a new polyethylene resin is proposed, and it is described that other resins are blended within a range not departing from the characteristics of the polyethylene resin. There is no description or suggestion regarding modification, improvement of function, and use in extruded sheets using polypropylene.

  Accordingly, an object of the present invention is to provide an extruded sheet of a polyolefin resin that is excellent in rigidity and deep drawability, and a container comprising the same.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have high rigidity when formed into an extruded sheet by blending a specific polyethylene-based resin with polypropylene resin, and deep drawability during thermoforming. As a result, it was found that a deep-drawn container having a good shape without uneven thickness was obtained, and the present invention was completed.

That is, the present invention has a polypropylene resin (1) and a density of 925 to 970 kg / m ³ , a melt flow rate (MFR) of 0.1 to 50 g / 10 minutes, and a molecular weight by gel permeation chromatography (GPC). The measurement shows two peaks, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 2.0 to 7.0, and the Mn when molecular weight fractionation is 100,000. The above fraction contains a polyethylene resin (2) having 0.15 or more long chain branches per 1000 carbon atoms in the main chain, and the weight ratio of the polypropylene resin (1) and the polyethylene resin (2) is 30/70. It is related with the extrusion sheet | seat and container which consist of a polypropylene-type resin composition which is -95/5.

  First, the polypropylene resin (1) used for the extruded sheet of the present invention will be described.

  The polypropylene resin (1) used in the extruded sheet of the present invention may be any one as long as it belongs to the category of polypropylene resins, for example, a homopolymer of propylene or propylene and other α-olefins up to 20% by weight. For example, a block or a random copolymer with ethylene, butene-1, 4-methylpentene-1, octene-1, etc. is mentioned, These resin may use 1 type (s) or 2 or more types together. And as this polypropylene resin (1), according to JISK7210, the polypropylene resin whose MFR measured by 230 degreeC and the load 2.16kg is 0.05-20g / 10min is preferable, Furthermore, 0.1-10g A polypropylene resin of / 10 minutes is preferred. When the MFR is 0.05 g / 10 min or more, the load on the extruder is small during the molding process, and the productivity is high. Moreover, when MFR is 20 g / 10min or less, the drawdown at the time of shaping | molding is small, and sheet | seat shaping | molding is easy.

  Next, the polyethylene resin (2) used for the extruded sheet of the present invention will be described. The polyethylene-based resin belongs to a category generally referred to as a polyethylene-based resin, and is particularly an ethylene homopolymer composed of a repeating unit derived from ethylene, or a repeating unit derived from ethylene and an α having 3 to 8 carbon atoms. An ethylene-α-olefin copolymer composed of repeating units derived from olefins is preferred.

The polyethylene resin (2) used for the extruded sheet of the present invention has a density measured in accordance with JIS K7676 in the range of 925 to 970 kg / m ³ , particularly preferably in the range of 930 to 960 kg / m ³ . Here, when the density exceeds 970 kg / m ³ , the obtained extruded sheet and container are excellent in rigidity but significantly inferior in impact strength. When the density is less than 925 kg / m ³ , the obtained foamed sheet and container are inferior in rigidity, making it difficult to apply to uses that require rigidity.

  The polyethylene resin (2) used in the extruded sheet of the present invention has an MFR at 190 ° C. and a load of 2160 g of 0.1 to 50 g / 10 minutes, and preferably 1 to 20 g / 10 minutes. Here, when MFR is less than 0.1 g / 10 minutes, the surface smoothness of the extrusion sheet shape | molded as a polyolefin-type resin composition falls. On the other hand, when it exceeds 50 g / 10 minutes, only a polyolefin resin composition inferior in drawdown property and deep drawability when thermoforming an extruded sheet can be obtained.

  The polyethylene resin (2) used for the extruded sheet of the present invention exhibits two peaks in the molecular weight measurement by GPC. The peak top molecular weight (Mp) is obtained by dividing the molecular weight distribution curve obtained by GPC measurement into two peaks by the method described later, and evaluating the top molecular weight of the high molecular weight side peak and the low molecular weight side peak. The case of 100,000 or more was assumed to have two Mp. When it was less than 100,000, the top molecular weight of the actually measured molecular weight distribution curve was defined as one Mp. When the molecular weight measurement by GPC has one peak, the extrusion load at the time of processing becomes high, the productivity is lowered, and the deep drawability when made into an extruded sheet is not sufficient, so a good container cannot be obtained. It is not preferable. The molecular weight distribution curve was divided as follows. The standard deviation is 0.30 with respect to LogM of the molecular weight distribution curve in which the weight ratio is plotted against LogM which is the logarithm of molecular weight obtained by GPC measurement, and an arbitrary average value (molecular weight at the peak top position) A composite curve is created by adding together two logarithmic distribution curves having) at an arbitrary ratio. Further, the average value and the ratio are obtained so that the deviation sum of squares of the weight ratio with respect to the same molecular weight (M) value of the actually measured molecular weight distribution curve and the composite curve becomes a minimum value. The minimum value of the deviation sum of squares was set to 0.5% or less with respect to the deviation sum of squares when the ratios of the respective peaks were all zero. When the average value and the ratio giving the minimum value of the deviation sum of squares were obtained, the molecular weight at the peak top of each logarithmic distribution curve obtained by dividing into two lognormal distribution curves was defined as Mp.

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) to Mn of the polyethylene resin (2) used in the extruded sheet of the present invention is 2.0 to 7.0, preferably 2.5 to 7.0, more preferably. Is 3.0-6.0. When Mw / Mn is less than 2.0, the surface smoothness of the extruded sheet formed as a polyolefin resin composition is lowered. Moreover, when Mw / Mn exceeds 7.0, a molding temperature range becomes narrow. Mw / Mn can be increased by reducing the amount of organic compound added during synthesis of the organically modified clay (B) described later, lowering the temperature during polymerization, and increasing the amount of olefin other than ethylene.

  The number of long chain branches having 6 or more carbon atoms in the fraction having a Mn of 100,000 or more obtained by molecular weight fractionation of the polyethylene resin (2) used in the extruded sheet of the present invention is 0.15 or more per 1000 carbon atoms of the main chain. It is. When the number of long-chain branches having 6 or more carbon atoms in the fraction with Mn of 100,000 or more is less than 0.15 per 1000 carbon atoms of the main chain, the deep drawability when formed into an extruded sheet is not sufficient, and thus good A large container is not obtained, which is not preferable. The number of long-chain branches of the fraction with Mn of 100,000 or more obtained by molecular weight fractionation is due to the decrease in the amount of organic compound added during synthesis of the organically modified clay (B) described later, and the amount of olefin other than ethylene during polymerization. Can be increased. Control is also possible by the type of ligand of the transition metal compound (A). For example, the Mn obtained by molecular weight fractionation is 100,000 or more when the ligand of the general formula (6) and further the general formula (8) is used rather than using the ligand of the general formula (5) only. The number of long-chain branches in the fraction becomes higher.

The number average molecular weight (Mn) measured by GPC of the polyethylene resin (2) used in the extruded sheet of the present invention is preferably 15,000 or more, more preferably 15,000 to 100,000, and particularly 15,000. ~ 50,000 is preferred. When Mn is 15,000 or more, the strength of the obtained extruded sheet and container is increased. Mn increases due to a decrease in the amount of hydrogen added during polymerization. Mn can be controlled by the type of ligand of the transition metal compound (A) described later. For example, Mn is higher when the ligand of the general formula (6) and further the general formula (8) is used than when the ligand of the general formula (5) alone is used.
The polyethylene resin (2) used in the extruded sheet of the present invention preferably has a long chain branch number of 6 or more carbon atoms of 0.02 or more per 1000 carbon atoms of the main chain. When the number of long chain branches is 0.02 or more per 1000 carbon atoms of the main chain, the drawdown property is good and a smooth extruded sheet is obtained.

  Moreover, it is desirable that the ratio of the fraction having Mn of 100,000 or more obtained by molecular weight fractionation is less than 40% of the whole polymer. When the ratio of the fraction of Mn obtained by molecular weight fractionation is 100,000 or more is less than 40% of the whole polymer, the extrusion load is reduced and the productivity is improved. Regarding the proportion of fractions with Mn of 100,000 or more obtained by molecular weight fractionation, the amount of organic compound added during the synthesis of organically modified clay (B), the amount of hydrogen added during polymerization, the olefin other than ethylene during polymerization It can be increased by increasing the amount added. Control is also possible by the type of ligand of the transition metal compound (A). For example, the Mn obtained by molecular weight fractionation is 100,000 or more when the ligand of the general formula (6) and further the general formula (8) is used rather than using the ligand of the general formula (5) only. The proportion of the fraction becomes higher.

The melt tension measured at 160 ° C. of the polyethylene resin (2) used for the extruded sheet of the present invention is preferably 20 mN or more, more preferably 30 mN or more. When the melt tension satisfies the above conditions, the deep drawability at the time of thermoforming the extruded sheet becomes good, and a deep-drawn container having a good shape without uneven thickness can be obtained. As described above, by using the polyethylene-based resin (2) having a specific molecular weight distribution and a long-chain branched structure in the present invention, an extruded sheet of a polyolefin-based resin excellent in rigidity and deep drawability, and a container made thereof are obtained.
The polyethylene resin (2) used in the extruded sheet of the present invention is
The following general formula (1)
M ¹ Q ¹ _a Q ² _b Q ³ _c Q ⁴ _d (1)
(In the formula, M ¹ is a titanium atom, a zirconium atom or a hafnium atom, and Q ¹ , Q ² , Q ³ and Q ⁴ are a cycloalkadienyl group, a substituted cycloalkadienyl group, a chelating ligand, Lewis base, hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylamino group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, the above One in which oxygen is introduced between carbon-carbon bonds of a hydrocarbon group having 1 to 20 carbon atoms, and a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms In the hydrocarbon group having 1 to 20 carbon atoms, a part of carbon is substituted with silicon, and these may be the same as or different from each other. Q ¹ , Q ² , Q ³ and Q ⁴ are And may be bonded via another atom or atomic group, and a, b, c and d each represent an integer of 0 to 4.)
The transition metal compound (A) represented by the formula (2) is a clay compound belonging to the smectite group hectorite.

(In the formula, R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and an alkyl having 1 to 30 carbon atoms. A silyl group, a hydrocarbon group having 1 to 30 carbon atoms in which oxygen is introduced between carbon bonds, and a part of the hydrocarbon group having 1 to 30 carbon atoms is an alkylamino group having 1 to 30 carbon atoms. those substituted with, that part of the carbon of the hydrocarbon groups of 1 to 30 carbon atoms substituted with silicon, and at least one of R1～R ³ is at number 21 or more carbon atoms, M ² is (It is an atom of Group 15 of the periodic table, and [A ⁻ ] is an anion.)
It can manufacture by carrying out ethylene polymerization using the catalyst for polyethylene-type resin manufacture which consists of the organic modified clay (B) modified | denatured with the organic compound represented by this, and the organoaluminum compound (C).

The transition metal compound (A) has the following general formula (1)
M ¹ Q ¹ _a Q ² _b Q ³ _c Q ⁴ _d (1)
(In the formula, M ¹ is a titanium atom, a zirconium atom or a hafnium atom, and Q ¹ , Q ² , Q ³ and Q ⁴ are a cycloalkadienyl group, a substituted cycloalkadienyl group, a chelating ligand, Lewis base, hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylamino group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, the above One in which oxygen is introduced between carbon-carbon bonds of a hydrocarbon group having 1 to 20 carbon atoms, and a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms In the hydrocarbon group having 1 to 20 carbon atoms, a part of carbon is substituted with silicon, and these may be the same as or different from each other. Q ¹ , Q ² , Q ³ and Q ⁴ are And may be bonded via another atom or atomic group, and a, b, c and d each represent an integer of 0 to 4.)
Preferably, the following general formula (3), general formula (4)

[Wherein, M ³ is a titanium atom, a zirconium atom or a hafnium atom, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, carbon An alkylamino group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms in which oxygen is introduced between carbon-carbon bonds, and the above 1 to 20 carbon atoms A part of the hydrocarbon group is substituted with an alkylamino group having 1 to 20 carbon atoms, a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with silicon, and R ⁴ , R ⁵ Are each independently the general formula (5), (6), (7) or (8)

(In the formula, each R ⁷ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or the above carbon number. What introduced oxygen between the carbon-carbon bond of 1-20 hydrocarbon group, What substituted a part of said C1-C20 hydrocarbon group by C1-C20 alkylamino group, The above (Some carbons of the hydrocarbon group having 1 to 20 carbon atoms are substituted with silicon.)
In a ligand coordinating to ^{M 3} represented, a sandwich structure is formed with ^{R 4} and ^{R 5 M 3, R 6} is the formula (9) or (10)

(In the formula, each R ⁸ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 alkylsilyl groups, those having oxygen introduced between the carbon-carbon bonds of the hydrocarbon group having 1 to 20 carbon atoms, and some of the hydrocarbon groups having 1 to 20 carbon atoms having 1 to 20 carbon atoms (Substituted by an alkylamino group, or by substituting part of carbon of the hydrocarbon group having 1 to 20 carbon atoms with silicon, and M ⁴ is a silicon atom, a germanium atom, or a tin atom.)
And R ⁴ and R ⁵ are cross-linked and n is an integer of 1 to 5. ]
The compound represented by these is used.

  Further, the following general formula (12) or general formula (13)

[Wherein, M ⁵ represents a transition metal atom of Groups 4 to ⁵ of the periodic table, m represents an integer of 1 to 2, R ^{11 to} R ¹⁶ may be the same as or different from each other, hydrogen Atoms and halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, alkylamino groups having 1 to 20 carbon atoms, alkylsilyl groups having 1 to 20 carbon atoms, and carbons and carbons of the above hydrocarbon groups having 1 to 20 carbon atoms. One in which oxygen is introduced between the bonds, one in which part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms, part of the hydrocarbon group having 1 to 20 carbon atoms In which two or more groups of R ^{11 to} R ¹⁶ , preferably adjacent groups, are connected to each other to contain an alicyclic ring, an aromatic ring, or a hetero atom such as a nitrogen atom. Hydrocarbon rings may be formed, and these rings further have a substituent. You may do it. p is a number that satisfies the valence of M ⁵ , and Y is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkylamino group having 1 to 20 carbon atoms. A group, an alkylsilyl group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms introduced with oxygen between carbon-carbon bonds, and a part of the hydrocarbon group having 1 to 20 carbon atoms. The one substituted with an alkylamino group having 1 to 20 carbon atoms, the one obtained by substituting a part of carbons of the hydrocarbon group having 1 to 20 carbon atoms with silicon, and when p is 2 or more, it is represented by Y. A plurality of groups may be the same as or different from each other, and a plurality of groups represented by Y may be bonded to each other to form a ring. ]

[Wherein R ¹⁷ is independently selected in each case from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano and combinations thereof, and optionally two R ^17, where R ¹⁷ is hydrogen, halo Or not cyano) may be joined together to form a divalent derivative thereof linked to the adjacent position of the cyclopentadienyl ring to form a bonded ring structure, and J forms a 錯 体 -complex with M ⁶ A neutral η4-bonded diene group having 30 or less non-hydrogen atoms, Q is —O—, —S—, —NR ¹⁸ —, —PR ¹⁸ —, and M6 is in the +2 formal oxidation state. Titanium or zirconium, Z is SiR ¹⁸ 2, CR ¹⁸ 2, SiR ¹⁸ ₂ SiR ¹⁸ ₂ , CR ¹⁸ ₂ CR ¹⁸ ₂ , CR ¹⁸ = CR ¹⁸ , CR ¹⁸ ₂ SiR ¹⁸ ₂ or GeR ¹⁸ ₂ Where R ¹⁸ is in each case independently a member selected from hydrogen or hydrocarbyl, silyl, alkyl halide, aryl halide and combinations thereof, and optionally two R ¹⁸ from Z or ^{R 18} from ^{R 18} and Q from Z (wherein ^{R 18} is not hydrogen) may form a ring system '
The compound represented by these can also be used.

Examples of the cycloalkadienyl group of Q ¹ , Q ² , Q ³ and Q ⁴ include a cyclopentadienyl group, an indenyl group, a fluorenyl group and the like. Examples of substituted cycloalkadienyl groups include 2-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2,4-dimethylcyclopentadienyl group, 2-phenylindenyl group, 2,4-diethylcyclo Pentadienyl group, 2-methoxycyclopentadienyl group, 2-dimethylaminocyclopentadienyl group, 2-trimethylsilylcyclopentadienyl group, 7-methylindenyl group, 7-ethylindenyl group, 7-phenyl Indenyl group, 2,7-dimethylindenyl group, 2-methoxy-7-methylindenyl group, 2-dimethylamino-7-methylindenyl group, 2-trimethylsilyl-7-methylindenyl group, 4,7 -Dimethylindenyl group, 4-methoxy-7-methylindenyl group, tetrahydroindenyl group, 7-methyl Trahydroindenyl group, 7-ethyltetrahydroindenyl group, 7-phenyltetrahydroindenyl group, 2,7-dimethyltetrahydroindenyl group, 2-dimethylamino-7-methyltetrahydroindenyl group, 2-trimethylsilyl-7 -A tetrahydroindenyl group, 4,5,6,7-tetramethyltetrahydroindenyl group, etc. can be illustrated. Examples of the chelating ligand include an ethylenediamine group, a bipyridine group, a phenanthroline group, and an acetylacetonate group. Examples of Lewis bases include amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine and pyridine, phosphines such as triethylphosphine and triphenylphosphine, thioethers such as tetrahydrothiophene, and benzoic acid. Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, n-butyl group, t-butyl group, and n-octyl group. Examples include a group, n-eicosyl group, phenyl group, benzyl group, o-toluyl group, m-toluyl group, p-toluyl group and the like. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, t-butoxy group, n-octoxy group and n-eoxy group. N-phenoxy group, 2-methylphenoxy group, 3-ethylphenoxy group, and the like. Examples of the alkylamino group having 1 to 20 carbon atoms include a methylamino group, a dimethylamino group, an ethylamino group, a methylethylamino group, and an n-propylamino group. Examples of the alkylsilyl group having 1 to 20 carbon atoms include methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, n-propylsilyl group, iso-propylsilyl group, and di (n-propylsilyl group). Group), di (iso-propylsilyl group), tri (n-propylsilyl group), tri (iso-propylsilyl group), n-butylsilyl group, iso-butylsilyl group, t-butylsilyl group, di (n-butylsilyl group) Group) and the like. As what introduce | transduced oxygen between carbon of carbon of the said C1-C20 hydrocarbon group, a methoxymethylene group, an ethoxymethylene group, etc. can be illustrated. As what substituted a part of said C1-C20 hydrocarbon group by the C1-C20 alkylamino group, a dimethylaminomethylene group, a diethylaminomethylene group, etc. can be illustrated. As what substituted a part of carbon of the said C1-C20 hydrocarbon group with silicon, a trimethylsilylmethylene group, a tert- butyldimethylsilylmethylene group, etc. can be illustrated.

  Specific examples of the transition metal compound (A) include the following compounds. As specific examples of the transition metal compound (A), those corresponding to the general formula (3) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl). ) Zirconium dichloride, those corresponding to general formula (4) include methylene bis (methylcyclopentadienyl) zirconium dichloride, methylene bis (butylcyclopentadienyl) zirconium dichloride, methylene bis (tetramethylcyclopentadienyl) zirconium dichloride, As a thing corresponding to General formula (12), bis (2-tert-butyl-5-phenylimino) zirconium dichloride, as a thing corresponding to General formula (13), (tert-butylamide) ( Zirconium compounds such as tramethyl-η5-cyclopentadienyl) dimethylsilanezirconium dichloride, compounds in which the zirconium atom is changed to titanium atom, hafnium atom, and dichloro form of the above transition metal compounds are dimethyl form, diethyl form, dihydro form, diphenyl form Examples of preferred transition metal compounds (A) include bis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, and dimethylsilane. Diyl (cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium di Examples thereof include, but are not limited to, chloride and isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride.

  The organically modified clay (B) has the following general formula (2)

(In the formula, R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and an alkyl having 1 to 30 carbon atoms. A silyl group, a hydrocarbon group having 1 to 30 carbon atoms in which oxygen is introduced between carbon bonds, and a part of the hydrocarbon group having 1 to 30 carbon atoms is an alkylamino group having 1 to 30 carbon atoms. those substituted with, a portion of the carbons of the hydrocarbon groups of 1 to 30 carbon atoms are those obtained by replacing silicon, and at least one of R1~R3 is at number 21 or more carbon atoms, M ² of the periodic table (It is a Group 15 atom, and [A ⁻ ] is an anion.)
As a specific example of the organic compound, the following can be exemplified.

In the general formula (2), examples of the hydrocarbon group having 1 to 30 carbon atoms of R ¹ , R ² and R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an allyl group, an n-butyl group, Isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, neopentyl, tert-pentyl, cyclopentyl, n- A hexyl group etc. can be illustrated.

  Examples of the alkoxy group having 1 to 30 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, and a phenoxy group.

  A C1-C30 alkylamino group is an amino group which has the said C1-C30 hydrocarbon group as a substituent, and is a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diisopropylamino group. , Diphenylamino group, methylphenylamino group and the like.

  The alkylsilyl group having 1 to 30 carbon atoms is a silyl group having the hydrocarbon group having 1 to 30 carbon atoms as a substituent, and includes a trimethylsilyl group, a tri-tert-butylsilyl group, a ditert-butylmethylsilyl group, a tert- Examples thereof include a butyldimethylsilyl group, a triphenylsilyl group, a diphenylmethylsilyl group, and a phenyldimethylsilyl group.

  As what introduce | transduced oxygen between carbon of carbon of the said C1-C30 hydrocarbon group, a methoxymethylene group, an ethoxymethylene group, etc. can be illustrated.

  As what substituted a part of said C1-C30 hydrocarbon group by the C1-C30 alkylamino group, a dimethylaminomethylene group, a diethylaminomethylene group, etc. can be illustrated.

  As what substituted a part of carbon of the said C1-C30 hydrocarbon group with silicon, a trimethylsilylmethylene group, a tert- butyldimethylsilylmethylene group, etc. can be illustrated.

At least one of R ¹ , R ² and R ³ is a hydrocarbon group having 21 or more carbon atoms represented by a behenyl group.

M ² is an atom of Group 15 of the periodic table, and can be exemplified by a nitrogen atom or a phosphorus atom. Specific examples of the organic compound represented by the general formula (2) when M ² is a nitrogen atom include N, N-dimethyl-behenylamine hydrochloride, N-methyl-N-ethyl-behenylamine hydrochloride, Examples include compounds such as N-methyl-Nn-propyl-behenylamine hydrochloride and the like, and compounds in which the hydrochloride salt of the above compound is replaced with hydrofluoride, hydrobromide, hydroiodide, or sulfate. However, the present invention is not limited to these.

Examples of the compound in which M ² is a phosphorus atom include compounds such as P, P-dimethyl-behenylphosphine hydrochloride, P, P-diethyl-behenylphosphine hydrochloride, P, P-dipropyl-behenylphosphine hydrochloride, Examples thereof include, but are not limited to, compounds in which hydrochloride is replaced with hydrofluoride, hydrobromide, hydroiodide, or sulfate.

[A ⁻ ] is an anion such as fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, oxalate ion, citrate ion, succinate ion, tetra Although fluoroborate ion or hexafluorophosphate ion can be used, it is not limited to these.

  The clay compound used for the organically modified clay (B) belongs to the smectite group hectorite.

  The organically modified clay modified with an organic compound introduces organic ions between the clay compound layers to form an ionic complex.

  In the organic compound modification treatment, it is preferable to perform the treatment by selecting the conditions of the clay compound concentration of 0.1 to 30% by weight and the treatment temperature of 0 to 150 ° C. Further, the organic compound may be prepared as a solid and dissolved in a solvent for use, or a solution of the organic compound may be prepared by a chemical reaction in the solvent and used as it is. Regarding the reaction amount ratio between the clay compound and the organic compound, it is preferable to use an organic compound having an equivalent amount or more with respect to exchangeable cations of the clay compound. As the treatment solvent, aliphatic hydrocarbons such as pentane, hexane or heptane, aromatic hydrocarbons such as benzene or toluene, alcohols such as ethyl alcohol or methyl alcohol, ethers such as ethyl ether or n-butyl ether, Halogenated hydrocarbons such as methylene chloride or chloroform, acetone, 1,4-dioxane, tetrahydrofuran, water or the like can be used, but preferably alcohols or water is used alone or as a component of a solvent. .

  Further, the particle size of the organically modified clay (B) used in the polymerization of the polyethylene resin (2) used in the present invention is not particularly limited. If it is too large, the catalyst is clogged in the middle when the catalyst is transferred with the slurry, so that the thickness is preferably 1 to 100 μm. The method for adjusting the particle size is not particularly limited, and large particles may be pulverized to an appropriate particle size, small particles may be granulated to an appropriate particle size, or pulverization and granulation may be combined. Also good. The particle size may be adjusted for unmodified clay or for modified organically modified clay.

  The method of pulverization and granulation is not particularly limited. For pulverization, impact mill, rotary mill, cascade mill, cutter mill, cage mill, impact pulverizer, conical mill, colloid mill, compound mill, jet mill, vibration mill, stamp mill , Tube mill, disk mill, tower mill, medium stirring mill, hammer mill, pin mill, fret mill, pebble mill, ball mill, ball mill, planetary mill, ring ball mill, ring roll mill, rod mill, roller mill, roll crusher etc. as granulation May be any method such as rolling granulation, fluidized bed granulation, stirring granulation, compression granulation, extrusion granulation, crush granulation, melt granulation, spray granulation and the like.

  The organoaluminum compound (C) is a constituent of the catalyst for producing the polyethylene resin (2) used in the present invention, and is used together with the transition metal compound (A) and the organically modified clay (B).

  The organoaluminum compound (C) has the following general formula (11)

(In the formula, R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁰ is each independently a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a chlorine atom.)
And a compound capable of alkylating a transition metal compound is preferable, and specific examples include alkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum.

  Transition metal compound (A) ((A) component) and organically modified clay (B) ((B) component) used in the polymerization of polyethylene resin (2) used in the present invention, and organoaluminum compound (C) (( The ratio of component C) is not limited, but is preferably the ratio shown below.

  The molar ratio of the component (A) to the component (C) per metal atom is in the range of (component A) :( component C) = 100: 1 to 1: 100000, particularly in the range of 1: 1 to 1: 10000. It is preferable that the weight ratio of the component (A) to the component (B) is (component A) :( component B) = 10: 1 to 1: 10000, particularly 3: 1 to 1: 1000. It is preferable. In particular, by combining one kind of component (A), component (B) and component (C), it is possible to produce a polyethylene resin (2) in which two peaks are observed in molecular weight measurement by GPC, By using this polyethylene resin (2), the foam sheet and container excellent in heat resistance and strength of the present invention can be obtained. Also, by combining one type of component (A), component (B) and component (C), two peaks are observed in the molecular weight measurement by GPC, having a number average molecular weight and molecular weight distribution in a specific range, and molecular weight fractionation. The component with Mn of 100,000 or more obtained by the above is a specific ratio, and the Mn obtained by molecular weight fractionation has a long chain branching with a specific or more in the component with 100,000 or more, so it has excellent heat resistance and strength. An ethylene copolymer capable of producing a foam sheet and a container is obtained.

  There is no restriction on the method for preparing a polyethylene resin production catalyst comprising the components (A), (B) and (C) used in the polymerization of the polyethylene resin (2) used in the present invention. Examples of the method include mixing in an inert solvent for each component or using a monomer for polymerization as a solvent. Moreover, there is no restriction | limiting also about the order which makes these components react, and the temperature and processing time which perform this process also have no restriction | limiting. It is also possible to prepare a catalyst for producing a polyethylene-based resin by using two or more types of component (B) and component (C).

  The catalyst used in the polymerization of the polyethylene resin (2) used in the present invention can be used in any of usual polymerization processes, that is, slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization, and bulk polymerization.

In the present invention, polymerization means not only homopolymerization of ethylene but also copolymerization with other olefins, and the polyethylene resin (2) obtained by these polymerizations includes not only homopolymers but also copolymers. Used.
The polymerization of ethylene in the polyethylene resin (2) used in the present invention can be carried out either in the gas phase or in the liquid phase. In particular, when the polymerization is carried out in the gas phase, the polyethylene resin (2 ) Can be produced efficiently and stably. Further, when the polymerization is performed in a liquid phase, the solvent used may be any organic solvent that is generally used, and specific examples include benzene, toluene, xylene, pentane, hexane, heptane, and the like. Olefins such as 1-butene, 1-octene and 1-hexene can also be used as a solvent.

  Other olefins used for copolymerization of the polyethylene resin (2) used in the polymerization of the polyethylene resin (2) used in the present invention with ethylene include propylene, 1-butene, 4-methyl-1-pentene, 1- Α-olefins such as hexene, 1-octene, styrene and styrene derivatives, butadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7-methyl- Examples thereof include conjugated and non-conjugated dienes such as 1,6-octadiene, and cyclic olefins such as cyclobutene. Further, three or more kinds of components can be mixed and polymerized, such as ethylene, propylene and styrene, ethylene, 1-hexene and styrene, ethylene, propylene, and ethylidene norbornene.

There are no particular restrictions on the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration in producing the polyethylene resin (2) used in the present invention, but the polymerization temperature is -100 to 300 ° C. The time is preferably 10 seconds to 20 hours, and the polymerization pressure is preferably from normal pressure to 3000 kg / cm ² G. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. The polyethylene resin (2) obtained after completion of the polymerization can be obtained by separating and recovering from the polymerization solvent by a conventionally known method and drying it.

  In the polyolefin resin composition comprising the polypropylene resin (1) and the polyethylene resin (2) used in the extruded sheet of the present invention, the weight ratio of the polypropylene resin (1) and the polyethylene resin (2) is 30/70. It is -95/5, More preferably, it is 50 / 50-95 / 5. When the ratio of the polyethylene resin (2) is less than 95/5, the melt tension of the resin composition becomes low, and the drawdown property and deep drawability when the extruded sheet is thermoformed are lowered. On the other hand, when the ratio of the polyethylene resin (2) exceeds 30/70, the rigidity is significantly lowered.

Any method may be used to obtain a polyolefin resin composition comprising the polypropylene resin (1) and the polyethylene resin (2). For example, the polypropylene resin (1) and the polyethylene resin (2) A method in which a composition previously mixed with a mixer represented by a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, etc. is put into a sheet molding machine, and a polypropylene resin (1) and a polyethylene resin (2) are simply used. Examples thereof include a method of melt-mixing in advance at a melt-kneading temperature of 100 to 300 ° C. with an extruder such as an axial screw extrusion granulator and a twin screw extrusion granulator.

  The polyolefin resin composition comprising the polypropylene resin (1) and the polyethylene resin (2) thus obtained has a melt tension measured at 190 ° C. of preferably 15 mN or more, more preferably 20 mN or more. . When the melt tension satisfies the above conditions, the drawdown property and deep drawability when thermoforming the extruded sheet are improved, and a container that does not become uneven even when deep drawn is obtained.

  The polyolefin-based resin composition used for the extruded sheet of the present invention is additive-free or, if necessary, an antioxidant, a weathering stabilizer, an antistatic agent, a lubricant, an antiblocking agent, an organic / inorganic pigment, etc. Additives used may be added. The method of mixing the above-mentioned additives into the resin is not particularly limited, but for example, a method of directly adding in the pellet granulation step after polymerization, or a high concentration master batch is prepared in advance, Examples thereof include a method of dry blending at the time of molding.

  An inorganic filler may be added to the polyolefin resin composition used in the extruded sheet of the present invention for the purpose of imparting rigidity. Examples of the inorganic filler include talc, calcium carbonate, potassium titanate whisker, mica and glass fiber. Of course, two or more kinds of inorganic fillers can be used in combination as well as these single use. The average particle size of the inorganic filler is preferably 15 to 0.5 μm, and if the average particle size is too large, the impact resistance is lowered. Conversely, if the average particle size is too small, the inorganic filler particles tend to aggregate together, It tends to cause deterioration of appearance and impact resistance.

  The production method of the extruded sheet of the present invention is not particularly limited, but as the production method of the sheet, the above-described polyolefin resin composition is used, and a known molding method (extrusion molding method, calender molding method). The method of manufacturing can be illustrated. Among the publicly known molding methods, the extrusion molding method is preferable from the viewpoint of productivity. Specifically, there is a T-die method using an apparatus (T-die sheet forming machine) having processes such as an extruder, a T-die, a cooling roll, a guide roll, a take-up roll, a trimming cutter, masking, a regular cutting cutter, and a stacker. Further preferred. The extrusion temperature is preferably from 100 to 300 ° C., more preferably from 150 to 250 ° C., from the viewpoint of the appearance and formability of the resulting sheet. If the extrusion temperature is 180 ° C. or higher, the resin is sufficiently melted, and the surface of the resulting sheet does not have a crust-like appearance, and if it is 280 ° C. or lower, thermal degradation of the olefin-based resin composition occurs. It is difficult to obtain a good molded product by maintaining the melt tension of the sheet. The cooling roll temperature is preferably 5 to 100 ° C. since a sheet having excellent appearance can be obtained. If the cooling roll temperature is 5 ° C. or higher, the cooling roll does not form a dew pattern on the surface of the sheet, and a good appearance is obtained. If the cooling roll temperature is 100 ° C. or lower, the sheet can be sufficiently cooled. And a good appearance can be obtained by solidifying the surface. The speed | rate which shape | molds a sheet | seat is 0.1-100 m / min from being excellent in productivity. If the speed is 0.1 m / min or more, a sheet having a uniform thickness is obtained and the defect rate is small. If the speed is 100 m / min or less, the sheet can be sufficiently cooled. Although the thickness of the sheet | seat formed is about 0.5-3 mm normally, a thick sheet | seat may be used for the product which is a large sized molded product and deep-draws.

  Extruded sheet of the present invention is not only a single layer, but for the purpose of improving the gloss of the surface of a molded article obtained by thermoforming, adhesiveness, printing ink, adhesiveness with other resins such as urethane resin, etc. It may be a multilayer sheet with a resin other than the resin composition of the present invention.

  The container of the present invention is a molded body obtained by thermoforming the aforementioned sheet. Thermoforming methods include vacuum forming, pressure forming, and applications such as free drawing, plug and ridge, ridge, match mold, straight, drape, reverse draw A molding method, an air slip molding method, a plug assist molding method, a plug assist reverse draw molding method, a snapback molding method, or a combination of these can be applied.

  The extruded sheet of the present invention is made into a container by thermoforming such as vacuum forming. The obtained container is particularly suitable for food.

  Since the extruded sheet of the present invention is excellent in rigidity, draw-down property during thermoforming, and deep drawability, it can be used for a wide range of applications such as large area, deep-drawn food containers and various members. is there.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
-Manufacturing and evaluation of ethylene polymers-
Examples of production will be specifically described below, but the present invention is not limited thereto. Unless otherwise noted, the reagents used were commercially available products or those synthesized according to known methods.

  A jet mill (trade name: CO-JET SYSTEM α MARK III, manufactured by Seishin Enterprise Co., Ltd.) was used for pulverization of the organically modified clay. MT3000) was used to measure ethanol as a dispersant.

  Preparation of the ethylene polymer production catalyst, production of the ethylene polymer and solvent purification were all carried out under an inert gas atmosphere. A hexane solution (20 wt%) of triisobutylaluminum manufactured by Tosoh Finechem Co., Ltd. was used.

  Furthermore, various physical properties of the ethylene-based polymer in the examples were measured by the following methods. Weight average molecular weight (Mw), number average molecular weight (Mn), ratio of weight average molecular weight to number average molecular weight (Mw / Mn) and peak top molecular weight (Mp) were measured by GPC. The column temperature was set to 140 ° C. using a GPC device (trade name: HLC-8121 GPC / HT, manufactured by Tosoh Corporation) and a column (trade name: TSKgel GMHhr-H (20) HT, manufactured by Tosoh Corporation). The measurement was performed using 1,2,4-trichlorobenzene as an eluent. A measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The calibration curve of molecular weight was calibrated using a polystyrene sample having a known molecular weight. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.

  The density was measured by a density gradient tube method in accordance with JIS K6760 (1995).

  MFR (melt flow rate) was measured by a method according to ASTM D1238 Condition E. Melting point is a crystal melting peak when a sample held at 200 ° C. for 5 minutes is cooled to −20 ° C. using DSC (DSI Nanotechnology Co., Ltd. DSC6200) and then heated at 10 ° C./min. It was calculated by measuring.

  For molecular weight fractionation, a glass bead packed column (diameter: 21 mm, length: 60 cm) is used as the column, the column temperature is set to 130 ° C., and 1 g of sample dissolved in 30 mL of xylene is injected. Next, distillate is removed by using a xylene / 2-ethoxyethanol ratio of 5/5 as a developing solvent. Thereafter, using xylene as a developing solvent, the components remaining in the column are distilled off to obtain a polymer solution. A component having Mn of 100,000 or more was recovered by adding 5-fold amount of methanol to the obtained polymer solution to precipitate the polymer, filtering and drying.

The number of long chain branches was determined by ¹³ C-NMR using a JNM-GSX400 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. and the number of branches equal to or greater than the hexyl group. The solvent is benzene-d6 / orthodichlorobenzene (volume ratio 30/70). The number per 1,000 main chain methylene carbons (chemical shift: 30 ppm) was determined from the average value of the peaks of α-carbon (34.6 ppm) and β-carbon (27.3 ppm).

  The sample for melt tension measurement was prepared by adding a heat-resistant stabilizer (Ciba Specialty Chemicals, Irganox 1010TM; 1,500 ppm, Irgafos 168TM; 1,500 ppm) to an internal mixer (Toyo Seiki Seisakusho, The product kneaded for 30 minutes at 190 ° C. and 30 rpm in a nitrogen stream was used.

  To measure the melt tension, a capillary viscometer (Toyo Seiki Seisakusho, trade name Capillograph) with a barrel diameter of 9.55 mm is attached with a die with a length of 8 mm and a diameter of 2.095 mm so that the inflow angle is 90 °. It was measured. In the measurement of the melt tension of the polypropylene resin (1) and the polypropylene resin composition, the measurement temperature is 190 ° C., in the measurement of the polyethylene resin (2), the measurement temperature is 160 ° C., and the piston lowering speed is 10 mm / min. The draw ratio was set to 47, and the load (mN) required for take-up was the melt tension. When the maximum draw ratio was less than 47, the load (mN) required for taking-up at the highest draw ratio that did not break was taken as the melt tension.

~ Evaluation of sheet formability ~
Using a sheet molding machine (manufactured by Tanabe Plastics) with a screw diameter of 50 mmφ and a die width of 300 mm, a sheet having a thickness of 1 mm is obtained at a resin temperature of 160 ° C., a screw rotation speed of 30 rpm, a take-up roll surface temperature of 50 ° C., and a take-up speed of 1 m / min. Molded.

  The surface state of the molded sheet was visually observed to evaluate the appearance.

○: glossy, smooth ×: no gloss, unevenness on the sheet surface.

  The tensile elastic modulus of the molded sheet was measured using a universal testing machine (manufactured by Shimadzu Corporation, trade name: Autograph AGS-H 50N) in accordance with JIS K7127.

○: Tensile modulus is 600 MPa or more ×: Tensile modulus is less than 600 MPa ~ Evaluation of vacuum formability (container) ~
Extruded sheets were molded at a molding cycle of 10 seconds and a molding heater temperature of 230 ° C. in a vacuum molding machine equipped with a mold having a major axis of 100 mm and a depth of 50 mm, respectively, and the presence or absence of uneven thickness of the container was examined with 10 shots. .

  ◯: All 10 shots are not uneven.

  X: It is uneven in one or more out of 10 shots.

Production Example 1
(1) Denaturation of clay 300 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (manufactured by Lion Corporation) (Product name) Armin DM22D) 42.4 g (120 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 122 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then bis (cyclopenta 0.223 g of dienyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 9.74 wt%).
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 146 mg (corresponding to a solid content of 14.2 mg) of the catalyst suspension obtained in (2) were added to 65 ° C. After the temperature increase, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.75 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 540 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 13.5 g of polymer (activity: 950 g / g catalyst). The MFR of this polymer was 0.60 g / 10 min, the density was 935.8 kg / m ³ , and the melting point was 121.9 ° C. The number average molecular weight was 15,700, the weight average molecular weight was 104,000, and peaks were observed at the molecular weights of 30,300 and 205,000. The number of long chain branches contained in the polymer is 0.03 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number of fractions was 0.16 per number, and the fraction of Mn of 100,000 or more when molecular weight fractionation was 16.7 wt% of the total polymer. The melt tension was 90 mN.

Production Example 2
(1) Denaturation of clay 300 mL of industrial alcohol (trade name: Echinen F-3, manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 18.8 g of concentrated hydrochloric acid and dimethylbehenylamine (manufactured by Lion Corporation) (Product name) Armin DM22D) 53.0 g (150 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature. This slurry was separated by filtration, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 135 g of an organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene bis ( 0.3485 g of cyclopentadienyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 10.7 wt%).
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 75 mg (corresponding to a solid content of 8.0 mg) of the catalyst suspension obtained in (2) were added to 85 ° C. After the temperature increase, ethylene gas was continuously supplied so that the partial pressure was 1.20 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 63.2 g of polymer (activity: 7,900 g / g catalyst). The polymer had an MFR of 0.25 g / 10 min, a density of 954.2 kg / m ³ , and a melting point of 131.5 ° C. The number average molecular weight was 11,400, the weight average molecular weight was 43,000, and peaks were observed at the positions of molecular weights 18,100 and 189,000. Further, the number of long chain branches contained in the polymer is 0.05 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.17 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 9.2 wt% of the total polymer. The melt tension was 95 mN.

Production Example 3
(1) Denaturation of clay 300 mL of industrial alcohol (trade name: Echinen F-3, manufactured by Japan Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 12.5 g of concentrated hydrochloric acid and dimethylbehenylamine (manufactured by Lion Corporation) (Trade name) Armin DM22D) 35.3 g (100 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 118 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclohexane) 0.4266 g of pentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 12.5 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, and 105 mg (corresponding to a solid content of 13.1 mg) of the catalyst suspension obtained in (2) were added, and the mixture was heated to 85 ° C. After the temperature increase, ethylene gas was continuously supplied so that the partial pressure became 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 50.2 g of polymer (activity: 3,800 g / g catalyst). The polymer had an MFR of 9.9 g / 10 min, a density of 955.5 kg / m ³ and a melting point of 134.5 ° C. The number average molecular weight was 17,900, the weight average molecular weight was 65,800, and peaks were observed at the molecular weights of 36,500 and 297,000. The number of long chain branches contained in the polymer is 0.10 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.20 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 7.7 wt% of the total polymer. The melt tension was 30 mN.

Production Example 4
(1) Modification of clay The same procedure as in Example 1 was performed.
(2) Preparation of catalyst suspension Instead of bis (cyclopentadienyl) zirconium dichloride / 0.2923 g, dimethylsilylene (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride / The same operation as in Example 1 was performed except that 0.4406 g was used (solid weight: 11.5 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 90 mg of the catalyst suspension obtained in (2) (corresponding to a solid content of 10.4 mg) was added to 65 ° C. After the temperature increase, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.75 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 550 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 61.4 g of polymer (activity: 5,900 g / g catalyst). This polymer had an MFR of 0.078 g / 10 min, a density of 926.1 kg / m ³ and a melting point of 112.8 ° C. The number average molecular weight was 21,900, the weight average molecular weight was 127,000, and peaks were observed at molecular weights of 31,300 and 248,000. Further, the number of long chain branches contained in the polymer is 0.17 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.32 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 36.9 wt% of the total polymer. The melt tension was 140 mN.

Production Example 5
(1) Modification of clay The same procedure as in Example 1 was performed.
(2) Preparation of catalyst suspension Instead of bis (cyclopentadienyl) zirconium dichloride / 0.2923 g, dimethylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium The same procedure as in Example 1 was carried out except that dichloride / 0.5447 g was used (solid weight content: 10.9 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, and 86 mg of the catalyst suspension obtained in (2) (equivalent to 9.4 mg of solid content) were added to 65 ° C. After the temperature increase, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.75 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 610 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 17.9 g of polymer (activity: 1,900 g / g catalyst). The polymer had an MFR of 5.0 g / 10 min, a density of 910.3 kg / m ³ , and melting points of 79.7 ° C. and 99.3 ° C. Further, the number average molecular weight was 28,000, the weight average molecular weight was 82,300, and peaks were observed at the positions of molecular weights 42,500 and 261,000. The number of long chain branches contained in the polymer is 0.25 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.40 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 39.8 wt% of the total polymer. The melt tension was 45 mN.

Production Example 6
(1) Modification of clay (2) Preparation of catalyst suspension The same procedure as in Example 4 was performed.
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 64 mg (corresponding to a solid content of 7.3 mg) of the catalyst suspension obtained in (2) were added. After the temperature increase, 17.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.80 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 570 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 61.7 g of polymer (activity: 8,500 g / g catalyst). The polymer had an MFR of 1.4 g / 10 min, a density of 929.0 kg / m ³ , and a melting point of 116.8 ° C. Moreover, the number average molecular weight was 19,500, the weight average molecular weight was 92,700, and peaks were observed at the positions of molecular weight 31,200 and 183,000. Further, the number of long chain branches contained in the polymer is 0.16 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.31 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 21.8 wt% of the total polymer. The melt tension was 78 mN.

Production Example 7
(1) Modification of clay Performed in the same manner as in Example 2.
(2) Preparation of catalyst suspension Dimethylsilylene (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium instead of dimethylsilylene bis (cyclopentadienyl) zirconium dichloride / 0.3485 g The same operation as in Example 2 was carried out except that dichloride / 0.4406 g was used (solid weight: 11.9 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, and 54 mg of catalyst suspension obtained in (2) (corresponding to a solid content of 6.4 mg) were added, and the mixture was heated to 70 ° C. After the temperature increase, 17.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.80 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 580 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 37.6 g of polymer (activity: 5,900 g / g catalyst). The polymer had an MFR of 0.068 g / 10 min, a density of 925.3 kg / m ³ , and a melting point of 114.4 ° C. Moreover, the number average molecular weight was 26,300, the weight average molecular weight was 146,000, and peaks were observed at the positions of molecular weights 42,800 and 261,000. The number of long chain branches contained in the polymer is 0.20 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.37 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 32.7 wt% of the total polymer. The melt tension was 150 mN.

Production Example 8
(1) Denaturation of clay 300 mL of industrial alcohol (trade name: Echinen F-3, manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 17.5 g of concentrated hydrochloric acid and dimethylbehenylamine (manufactured by Lion Corporation) (Trade name) Armin DM22D) 49.4 g (140 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 132 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclohexane) 0.4406 g of pentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.4 wt%).
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 52 mg (corresponding to a solid content of 6.4 mg) of the catalyst suspension obtained in (2) were added. After the temperature increase, 17.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.80 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 590 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 61.8 g of polymer (activity: 9,700 g / g catalyst). The polymer had an MFR of 1.6 g / 10 min, a density of 929.5 kg / m ³ and a melting point of 118.3 ° C. The number average molecular weight was 17,600, the weight average molecular weight was 86,700, and peaks were observed at the molecular weights of 30,500 and 155,000. The number of long chain branches contained in the polymer is 0.14 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.27 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 20.1 wt% of the total polymer. The melt tension was 75 mN.

Production Example 9
(1) Denaturation of clay 300 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 20.0 g of concentrated hydrochloric acid and dimethylbehenylamine (manufactured by Lion Corporation) (Product Name) Armin DM22D) 56.5 g (160 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature. This slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 145 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclohexane) 0.4406 g of pentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 11.2 wt%).
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 74 mg (corresponding to a solid content of 8.3 mg) of the catalyst suspension obtained in (2) were added to 65 ° C. After the temperature increase, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.75 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 570 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 51.5 g of polymer (activity: 6,200 g / g catalyst). The MFR of this polymer was 0.79 g / 10 min, the density was 928.2 kg / m ³ , and the melting point was 115.0 ° C. The number average molecular weight was 17,900, the weight average molecular weight was 99,300, and peaks were observed at the molecular weights 28,100 and 229,000. The number of long chain branches contained in the polymer is 0.14 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.26 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 25.4 wt% of the total polymer. The melt tension was 90 mN.

Production Example 10
(1) Modification of clay (2) Preparation of catalyst suspension The same procedure as in Production Example 4 was performed.
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 125 mg (corresponding to a solid content of 15.0 mg) of the catalyst suspension obtained in (2) was added at 65 ° C. After raising the temperature to 17.5 g of 1-butene, the ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.75 MPa (the concentration of hydrogen in the ethylene / hydrogen mixed gas: 1,000 ppm). ). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 75.0 g of polymer (activity: 5,000 g / g catalyst). This polymer had an MFR of 1.0 g / 10 min, a density of 920.0 kg / m ³ , and a melting point of 107.9 ° C. The number average molecular weight was 20,700, the weight average molecular weight was 106,000, and peaks were observed at the molecular weights of 32,400 and 250,000. Further, the number of long chain branches contained in the polymer is 0.19 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.34 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 24.6 wt% of the total polymer. The melt tension was 81 mN.

Production Example 11
(1) Modification of clay (2) Preparation of catalyst suspension The same procedure as in Production Example 4 was performed.
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 58 mg (corresponding to a solid content of 7.0 mg) of the catalyst suspension obtained in (2) were added. After the temperature rise, 8.3 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.85 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 850 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 49.0 g of polymer (activity: 7,000 g / g catalyst). The polymer had an MFR of 3.7 g / 10 min, a density of 939.4 kg / m ³ and a melting point of 125.4 ° C. The number average molecular weight was 20,300, the weight average molecular weight was 75,200, and peaks were observed at the molecular weights of 40,700 and 216,000. The number of long chain branches contained in the polymer is 0.06 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.17 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 14.3 wt% of the total polymer. The melt tension was 50 mN.

Production Example 12
(1) Modification of clay (2) Preparation of catalyst suspension The same procedure as in Production Example 4 was performed.
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, and 60 mg of the catalyst suspension obtained in (2) (equivalent to a solid content of 7.2 mg) were added to 80 ° C. After the temperature increase, 8.3 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.85 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 350 ppm). After 90 minutes, the pressure was released, and the slurry was filtered off and dried to obtain 54.0 g of polymer (activity: 7,500 g / g catalyst). The polymer had an MFR of 0.35 g / 10 min, a density of 935.2 kg / m ³ , and a melting point of 124.7 ° C. The number average molecular weight was 35,500, the weight average molecular weight was 124,000, and peaks were observed at molecular weights 71,200 and 338,000. The number of long chain branches contained in the polymer is 0.10 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.20 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 17.0 wt% of the total polymer. The melt tension was 95 mN.

Production Example 13
(1) Modification of clay (2) Preparation of catalyst suspension The same procedure as in Production Example 4 was performed.
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 70 mg of the catalyst suspension obtained in (2) (corresponding to a solid content of 8.4 mg) was added to 80 ° C. After the temperature increase, 2.4 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.90 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 750 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 63.0 g of polymer (activity: 7,500 g / g catalyst). The MFR of this polymer was 16 g / 10 min, the density was 953.5 kg / m ³ , and the melting point was 135.2 ° C. Moreover, the number average molecular weight was 15,500, the weight average molecular weight was 52,700, and peaks were observed at positions of molecular weights 27,900 and 179,000. Further, the number of long chain branches contained in the polymer is 0.05 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.16 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 6.5 wt% of the total polymer. The melt tension was 35 mN.

Production Example 14
(1) Modification of clay (2) Preparation of catalyst suspension The same procedure as in Production Example 4 was performed.
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 70 mg of the catalyst suspension obtained in (2) (corresponding to a solid content of 8.4 mg) was added to 80 ° C. After the temperature increase, an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.90 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 550 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 58.8 g of polymer (activity: 7,000 g / g catalyst). The MFR of this polymer was 5.9 g / 10 min, the density was 958.7 kg / m ³ , and the melting point was 136.7 ° C. The number average molecular weight was 16,700, the weight average molecular weight was 58,500, and peaks were observed at the molecular weights of 30,100 and 177,000. The number of long chain branches contained in the polymer is 0.04 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.15 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 5.7 wt% of the total polymer. The melt tension was 40 mN.

Production Example 15
(1) Denaturation of clay 300 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 18.8 g of concentrated hydrochloric acid and dimethylhexacosylamine (Me2N (C26H53) are added. ), Synthesized by a conventional method) 49.1 g (120 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 140 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 14 μm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclohexane) 0.4406 g of pentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, and 75 mg (corresponding to a solid content of 9.0 mg) of the catalyst suspension obtained in (2) were added to 80 ° C. After the temperature rise, 8.3 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.85 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 850 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 58.5 g of polymer (activity: 6,500 g / g catalyst). The MFR of this polymer was 4.0 g / 10 min, the density was 940.5 kg / m ³ , and the melting point was 124.9 ° C. Further, the number average molecular weight was 21,200, the weight average molecular weight was 74,000, and peaks were observed at the positions of molecular weights 41,500 and 217,000. Further, the number of long chain branches contained in the polymer is 0.07 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.18 per number. Moreover, the ratio of the fraction of Mn of 100,000 or more when molecular weight fractionation was 14.8 wt% of the total polymer. The melt tension was 49 mN.

Production Example 16
(1) Denaturation of clay 300 mL of industrial alcohol (trade name: Echinen F-3, manufactured by Japan Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 18.8 g of concentrated hydrochloric acid and methyl dioleylamine (manufactured by Lion Corporation) (Product Name) Armin M2O) 53.1 g (100 mmol) was added and heated to 45 ° C. to disperse 100 g of (Rockwood Additives (Product Name) Laponite RD), and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature.
The slurry was separated by filtration, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 138 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 12 μm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclohexane) 0.4266 g of pentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 66 mg (corresponding to a solid content of 7.9 mg) of the catalyst suspension obtained in (2) were added. After the temperature increase, 23.8 g of 1-butene was added, and ethylene gas was continuously supplied so that the partial pressure became 1.20 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 43.6 g of polymer (activity: 5,500 g / g catalyst). The MFR of this polymer was 72 g / 10 min, the density was 953.5 kg / m ³ , and the melting point was 113.7 ° C. Further, the number average molecular weight was 15,600, the weight average molecular weight was 37,300, and a peak was observed only at the position of the molecular weight 30,300. Further, the number of long chain branches contained in the polymer is less than 0.01 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 The number was less than 0.01 per carbon number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 5.0 wt% of the total polymer. The melt tension was less than 10 mN.

Production Example 17
(1) Modification of clay The same procedure as in Production Example 16 was performed.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene bis ( 0.3485 g of cyclopentadienyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 93 mg of the catalyst suspension obtained in (2) (corresponding to a solid content of 11.2 mg) was added to 85 ° C. After the temperature increase, 15.8 g of 1-butene was added, and ethylene was continuously supplied so that the partial pressure became 1.20 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 67.0 g of polymer (activity: 6,000 g / g catalyst). The MFR of this polymer was 200 g / 10 min or more, the density was 954.7 kg / m ³ , and the melting point was 135.6 ° C. The number average molecular weight was 8,930, the weight average molecular weight was 18,000, and a peak was observed only at the position of molecular weight 12,900. Further, the number of long-chain branches contained in the polymer was less than 0.01 per 1000 carbons of the main chain, and a fraction of Mn of 100,000 or more when molecular weight fractionation was not obtained. The melt tension was less than 10 mN.

Production Example 18
(1) Modification of clay (2) Preparation of catalyst suspension The same procedure as in Production Example 16 was performed.
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 105 mg (corresponding to a solid content of 12.6 mg) of the catalyst suspension obtained in (2) was added to 85 ° C. After the temperature increase, ethylene was continuously supplied so that the partial pressure became 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 78.1 g of polymer (activity: 6,200 g / g catalyst). The MFR of this polymer was 200 g / 10 min or more, the density was 948.9 kg / m ³ , and the melting point was 135.0 ° C. The number average molecular weight was 8,700, the weight average molecular weight was 20,000, and a peak was observed only at the position of molecular weight 13,100. Further, the number of long-chain branches contained in the polymer was less than 0.01 per 1000 carbons of the main chain, and a fraction of Mn of 100,000 or more when molecular weight fractionation was not obtained. The melt tension was less than 10 mN.

Production Example 19
(1) Modification of clay Performed in the same manner as in Production Example 16 (2) Preparation of catalyst suspension Performed in the same manner as in Production Example 17.
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 110 mg of the catalyst suspension obtained in (2) (corresponding to solid content of 13.2 mg) was added to 85 ° C. After the temperature increase, ethylene was continuously supplied so that the partial pressure was 1.20 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 72.6 g of polymer (activity: 5,500 g / g catalyst). The MFR of this polymer was 200 g / 10 min or more, the density was 943.5 kg / m ³ , and the melting point was 132.0 ° C. The number average molecular weight was 9,050, the weight average molecular weight was 19,900, and a peak was observed only at the position of molecular weight 13,600. Further, the number of long-chain branches contained in the polymer was less than 0.01 per 1000 carbons of the main chain, and a fraction of Mn of 100,000 or more when molecular weight fractionation was not obtained. The melt tension was less than 10 mN.

Production Example 20
(1) Modification of clay The same procedure as in Production Example 16 was performed.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) was suspended in 165 mL of hexane, and dimethylsilylene ( 0.4406 g of cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride and 85 mL of a hexane solution of triethylaluminum (1.18 M) were added and stirred at 60 ° C. for 3 hours. After allowing to stand and cooling to room temperature, the supernatant was taken out and washed twice with 200 mL of a 1% triisobutylaluminum hexane solution. The supernatant liquid after washing was extracted and the whole was made up to 250 mL with a 5% triisobutylaluminum hexane solution. Subsequently, it was prepared by separately adding 5 ml of a 20% triisobutylaluminum hexane solution (0.71 M) to a suspension of 0.062 g of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride in 10 ml of hexane. The solution was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and after washing twice with 200 mL of hexane, 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 92 mg (corresponding to a solid content of 11.0 mg) of the catalyst suspension obtained in (2) was added to 85 ° C. After the temperature increase, 16.6 g of 1-butene was added, and ethylene was continuously supplied so that the partial pressure became 0.80 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 59.7 g of polymer (activity: 5,430 g / g catalyst). The polymer had an MFR of 12 g / 10 min, a density of 932.3 kg / m ³ and a melting point of 119.8 ° C. The number average molecular weight was 19,600, the weight average molecular weight was 74,300, and a peak was observed at a molecular weight of 35,500. The number of long chain branches contained in the polymer is 0.04 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.07 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 12.5 wt% of the total polymer. The melt tension was 15 mN.

Example 1
[Production of polyolefin resin composition]
Polypropylene (Nippon Polypropylene, trade name: Novatec PP FB3HAT) (1) 85 wt% and polyethylene resin (2) 15 wt% produced in Production Example 1 were dry blended, and this was put into a 50 mm diameter single screw extruder made by Placo. And melt mixed. The barrel temperature was C1; 180 ° C., C2; 200 ° C., C3; 220 ° C., die head: 220 ° C. This polypropylene resin composition pellet was used for extrusion foaming. Table 1 shows the physical properties of the used polypropylene resin (1) and polyethylene resin (2), and Table 3 shows the obtained polyolefin resin composition.
[Forming extruded sheet]
The resin composition produced in [Production of polyolefin-based resin composition] is heat-melt plasticized at a barrel temperature of 190 ° C. using a sheet molding machine (manufactured by Tanabe Plastics Co., Ltd.) having a screw diameter of 50 mmφ and a die width of 300 mm. A sheet extruded from a die is sandwiched between mirror-finished metal cast rolls whose surface temperature is controlled at 60 ° C., and continuously taken out at a speed of 1 m / min while being cooled and solidified. A sheet was obtained. The tensile elastic modulus of this extruded sheet was measured. Further, the appearance of the sheet was observed. These results are shown in Table 3.
[Molding of container]
Extruded sheets were molded at a molding cycle of 10 seconds and a molding heater temperature of 230 ° C. in a vacuum molding machine equipped with a mold having a major axis of 100 mm and a depth of 50 mm, respectively, and the presence or absence of uneven thickness of the container was examined with 10 shots. . These results are shown in Table 3.

Examples 2-11
The same procedure as in Example 1 was conducted except that the polypropylene resin (1) and the polyethylene resin (2) were changed to the resins shown in Table 1 and the blend ratio was changed to the ratio shown in Table 3. Tables 1 and 2 show the physical properties of the polypropylene resin (1) and the polyethylene resin (2), and Table 3 shows the physical properties of the obtained polyolefin resin composition and the evaluation results of the extruded sheet and the container.

Comparative Example 1
The same procedure as in Example 3 was performed except that the polyolefin resin composition consisting only of the polypropylene resin (1) was used without using the polyethylene resin (2). The physical properties of the polypropylene resin (1) are shown in Tables 1 and 2, and the physical properties of the obtained polyolefin resin composition and the evaluation results of the extruded sheet and the container are shown in Table 3.

Comparative Examples 2-13
The same procedure as in Example 1 was performed except that the polypropylene resin (1) and the polyethylene resin (2) were changed to the resins shown in Table 4 and the blend ratio was changed to the ratio shown in Table 6. Table 4 shows the physical properties of the polypropylene resin (1) and the polyethylene resin (2), and Table 6 shows the physical properties of the obtained polyolefin resin composition and the evaluation results of the extruded sheet and the container.

Claims (3)

Polypropylene resin (1), density is 925 to 970 kg / m ³ , melt flow rate (MFR) is 0.1 to 50 g / 10 min, molecular weight measurement by gel permeation chromatography shows two peaks, weight Long chain branching in fractions where the ratio of the average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) is in the range of 2.0 to 7.0 and the Mn is over 100,000 Is a polyolefin-based resin having a weight ratio of 30/70 to 95/5 of the polypropylene-based resin (1) and the polyethylene-based resin (2). An extruded sheet made of a resin composition. The extruded sheet according to claim 1, wherein Mw / Mn of the polyethylene resin (2) is in the range of 3.0 to 6.0, and Mn is 15,000 or more. A container obtained by thermoforming the extruded sheet according to claim 1.