JP2012136599A - Foamed blow molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foamed blow molded product which is uniformly foamed, lightweight, has high foaming magnification and high heat-insulating property, and is excellent in stiffness and heat resistance.SOLUTION: The foamed hollow molded body lightweight, having high foaming magnification, and excellent in heat-insulating property, stiffness, heat resistance and low-temperature impact resistance, is obtained by using a polyethylene-based resin having specific molecular weight distribution and a long-chain branched structure.

Description

  The present invention relates to a foamed hollow molded body made of a polyethylene resin having a specific molecular weight distribution and a long chain branched structure. More specifically, it is made of a polyethylene resin having a specific molecular weight distribution and a long-chain branched structure, has excellent rigidity and heat resistance, and has a foaming ratio that is higher than that of a conventionally known polyethylene resin foamed hollow molded body. The present invention relates to a foamed hollow molded body that is high in weight, lightweight, and excellent in heat insulation.

  In recent years, plastic pipes, films, and hollow molded articles have been actively used in various industrial fields. In particular, hollow molded bodies made of polyethylene resins are used in various applications because they are inexpensive and lightweight, and have excellent molding processability, chemical resistance, and recyclability. Attempts to improve the processing characteristics in these various hollow molding methods are carried out in a molten state of polyethylene, so various melting characteristics such as melt flowability (easy extrudability), melt stretchability, melt tension, etc. An intensive study has been made with an emphasis on improvement.

  Also, from the viewpoints of weight reduction, heat insulation, sound insulation, etc., by melting and kneading a polyethylene resin and a foaming agent with an extruder, the foamed molten resin film (parison) is extruded from a die and sandwiched between molds A foamed hollow molded body to be molded has been studied. Even in such a foamed hollow molded body, in order to obtain a foam having a high expansion ratio, the above-described melting characteristics, particularly the melt tension, is important.

  As an ethylene polymer having a high melt tension, low density polyethylene (LDPE) having a long chain branch, which is produced by a high pressure radical method, is known. Although LDPE is excellent in foamability, since the density range that can be produced is limited, the foamed hollow molded product lacks rigidity and heat resistance, so its use is limited.

  On the other hand, an ethylene polymer obtained with a Ziegler catalyst or a metallocene catalyst is known to have a high density ethylene polymer, but the melt tension is low and sufficient foaming ratio cannot be obtained due to bubble breakage. It was.

  Further, an ethylene polymer produced using a Cr-based catalyst (Phillips catalyst) is known as an ethylene-based polymer having a high density and a high melt tension. However, the ethylene-based polymer produced using a Cr-based catalyst has insufficient melt stretchability, and a good foamed molded product could not be obtained.

  Thus, it has been difficult to obtain a foamed hollow molded article having a high foaming ratio by using a high-density ethylene polymer having high rigidity and heat resistance.

  Therefore, a method of blending LDPE (for example, see Patent Document 1) has been proposed. However, in the method of Patent Document 1, it is necessary to increase the ratio of low-density polyethylene in order to increase foamability, and as a result, a decrease in rigidity and heat resistance cannot be avoided. In addition, blow moldability was not sufficient, and it was easily affected by molding conditions, and thinning and hole opening at the corner portion were likely to occur.

  A method of adding a thickener (for example, see Patent Document 2) has been proposed, but there is a problem in terms of cost because an expensive thickener is used.

  Moreover, the inventor has proposed an uncrosslinked polyethylene foamed molded article having a good foamed state made of a polyethylene resin having specific properties (see, for example, Patent Document 3). Although this polyethylene-based resin is excellent in foaming properties, it has been desired to further improve the physical properties of the foamed hollow molded article such as rigidity and low-temperature impact properties for use in foam blow molding.

JP 2006-305793 A Japanese Patent Laid-Open No. 2007-160582 Japanese Patent Laid-Open No. 2006-96910

  The present invention relates to a foamed hollow molded article that solves the above-described problems and is made of a polyethylene-based resin having a specific molecular weight distribution and a long-chain branched structure. More specifically, it is a foamed hollow molded article using a resin having excellent foaming properties compared to the conventionally known polyethylene resin foamed hollow molded article, because the foaming ratio is high and the bubbles are uniform. The present invention provides a foamed hollow molded article that is lightweight, has high heat insulation properties, has a good molded body skin, and is excellent in rigidity, heat resistance, and low-temperature impact properties.

  As a result of intensive studies on the above object, the present inventor has a high expansion ratio, a uniform cell diameter, a light weight by using a polyethylene-based resin having a specific molecular weight distribution and a long-chain branched structure. It has been found that it becomes a foamed hollow molded article having excellent heat insulating properties, rigidity, and low-temperature impact properties, and has completed the present invention.

That is, the present invention has a density of 925 to 970 kg / m ³ , a melt flow rate (MFR) of 0.1 to 100 g / 10 min, and shows two peaks in molecular weight measurement by gel permeation chromatography (GPC). The ratio of the weight 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 fraction with a Mn of 100,000 or more when molecular weight fractionation is long. The present invention relates to a foamed hollow molded body made of a polyethylene resin having 0.15 or more chain branches per 1000 carbon atoms in the main chain.

  First, the polyethylene resin used for the foamed hollow body of the present invention will be described. The polyethylene resin belongs to a category generally referred to as a polyethylene-based resin, and in particular, an ethylene homopolymer composed of a repeating unit derived from ethylene, or a repeating unit derived from ethylene and an α-carbon having 3 to 8 carbon atoms. An ethylene-α-olefin copolymer composed of repeating units derived from olefins is preferred.

The density of the polyethylene resin of the present invention measured in accordance with JIS K7676 is 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 foamed hollow body is excellent in heat resistance but inferior in impact strength. When the density is less than 925 kg / m ³ , the obtained foamed hollow body is inferior in heat resistance, and the foam is deformed in an environment of about 100 ° C., which causes a problem in use.

  The polyethylene resin of the present invention shows two peaks in 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.

  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.

  When the molecular weight is measured by GPC, one having a peak is not preferable because the extrusion load at the time of processing is increased, the molding processability is lowered, and the foamability is not sufficient, so that a good foamed sheet cannot be obtained.

  The polyethylene resin has a weight average molecular weight (Mw) to Mn ratio (Mw / Mn) of 2.0 to 7.0, preferably 2.5 to 7.0, more preferably 3.0 to 6.0. . When Mw / Mn is less than 2.0, the extrusion load at the time of processing becomes high, and the moldability decreases. 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), decreasing the temperature during polymerization, and increasing the amount of olefin other than ethylene.

  The number average molecular weight (Mn) measured by GPC of the polyethylene resin is preferably 15,000 or more, more preferably 15,000 to 100,000, and particularly preferably 15,000 to 50,000. When Mn is 15,000 or more, the strength of the foamed hollow molded article obtained 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). 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 number of long chain branches in the fraction having a Mn of 100,000 or more obtained by molecular weight fractionation of the polyethylene resin is 0.15 or more per 1000 carbons of the main chain. When the number of long-chain branches in the fraction having Mn of 100,000 or more is less than 0.15 per 1000 carbons of the main chain, a problem occurs in foam molding. The number of long-chain branches in the fraction with Mn of 100,000 or more obtained by molecular weight fractionation increases due to a decrease in the amount of organic compound added during synthesis of the organically modified clay (B) and an increase in the amount of olefin other than ethylene during polymerization. be able to. 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.

  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 proportion of the fraction having Mn of 100,000 or more obtained by molecular weight fractionation is less than 40% of the whole polymer, foam moldability 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.

  As described above, by using a polyethylene-based resin having a specific molecular weight distribution and a long-chain branched structure in the present invention, a foamed hollow molded body having a high expansion ratio and excellent in strength and heat resistance is obtained.

  Moreover, since it is excellent in the manufacturing efficiency at the time of manufacture of a foaming hollow molded object, 190 degreeC and the melt flow rate in a 2.16kg load are 0.1-100 g / 10min, and it is 1-20 g / 10min. preferable.

The polyethylene resin 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. In which a part of carbon of the hydrocarbon group having 1 to 30 carbon atoms is substituted with silicon, and at least one of R ^{1 to} R ³ has 21 or more carbon atoms, and M ² 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 η ⁴ -bonded diene group having 30 or less non-hydrogen atoms, Q is —O—, —S—, —NR ¹⁸ —, —PR ¹⁸ —, and M ⁶ is a +2 formal oxidation Z or SiR ¹⁸ ₂ , CR ¹⁸ ₂ , SiR ¹⁸ ₂ SiR ¹⁸ ₂ , CR ¹⁸ ₂ CR ¹⁸ ₂ , CR ¹⁸ = CR ¹⁸ , CR ¹⁸ 2SiR ¹⁸ ₂ or GeR ¹⁸ _2, wherein R ¹⁸ is a member selected in each case independently hydrogen or a hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, and two R from optionally Z ¹⁸ 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. In which a part of carbon of the hydrocarbon group having 1 to 30 carbon atoms is substituted with silicon, and at least one of R ^{1 to} R ³ has 21 or more carbon atoms, and M ² is (It is a group 15 atom of the periodic table, 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. .

  In addition, the particle size of the organically modified clay (B) used in the polymerization of the polyethylene resin used in the present invention is not particularly limited, but if it is too small, it is difficult to settle and catalyst preparation cannot be performed efficiently. Since the catalyst is clogged in the middle when the catalyst is transferred as a slurry, 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, disc 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 component of the catalyst for producing the polyethylene resin 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) (component (A)) and organically modified clay (B) (component (B)), and organoaluminum compound (C) (component (C)) used in the polymerization of the polyethylene resin used in the present invention ) Ratio is not limited, but is preferably the following ratio.

  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 type of component (A), component (B) and component (C), it is possible to produce a polyethylene resin in which two peaks are observed in molecular weight measurement by GPC. By using the resin, the foamed hollow molded article having excellent 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 foamed hollow molded product is obtained.

  There is no limitation on the method for preparing the polyethylene resin production catalyst comprising the component (A), the component (B) and the component (C) used in the polymerization of the polyethylene resin used in the present invention. For example, a method of mixing by using an inert solvent or a monomer for polymerization as a solvent can be used. 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 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-based resin obtained by these polymerizations is used in the meaning including not only a homopolymer but also a copolymer.
The polymerization of ethylene in the polyethylene resin 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 having a uniform particle shape is efficiently and stably used. Can be produced. 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 polyethylene resins used in the polymerization of polyethylene resins used in the present invention with ethylene include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Α-olefin, styrene and styrene derivatives, butadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, etc. Conjugated and non-conjugated dienes, 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.

In producing the polyethylene resin used in the present invention, there are no particular restrictions on the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration, but the polymerization temperature is -100 to 300 ° C., and the polymerization time is 10 The polymerization pressure is preferably in the range of normal pressure to 3000 kg / cm ² G for seconds to 20 hours. 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. Further, the polyethylene resin obtained after completion of the polymerization can be obtained by separating and recovering from the polymerization solvent by a conventionally known method and drying.

  Next, the manufacturing method of the foaming hollow molding of this invention is demonstrated.

  The foamed hollow molded article of the present invention is manufactured by melt-kneading the polyethylene resin of the present invention and a foaming agent with an extruder, extruding a foamed molten resin film (parison) from a die, and sandwiching it with a mold. Can do. As a molding machine at that time, a known blow molding machine such as an accumulator type and a direct mold, a foam blow molding machine having a device capable of injecting a foaming agent in the middle of an extruder, or the like can be used.

  Examples of the foaming agent include inorganic gas foaming agents such as carbon dioxide, nitrogen, argon, and air; and volatile foaming agents such as propane, butane, pentane, hexane, cyclobutane, cyclohexane, trichlorofluoromethane, and dichlorodifluoromethane. be able to. Also, azodicarbonamide, barium azodicarboxylate, N, N-dinitrosopentamethylenetetramine, 4,4′-oxybis (benzenesulfonylhydrazide), diphenylsulfone that is liquid or solid at room temperature and generates gas upon heating. Examples thereof include chemical blowing agents such as -3,3'-disulfonylhydrazide, p-toluenesulfonyl semicarbazide, trihydrazinotriazine, biurea, zinc carbonate, and sodium bicarbonate (sodium bicarbonate). A plurality of foaming agents can be used in combination. The addition amount of the foaming agent is preferably 0.1 to 20 parts by weight, particularly preferably 2 to 8 parts by weight, based on 100 parts by weight of the polyethylene resin composition of the present invention.

  Any method may be used as a method of mixing these foam and ethylene polymer as long as a foamed hollow molded body is obtained. For example, an ethylene polymer and a foaming agent are mixed in advance with a Henschel mixer, a V-blender, a ribbon. The composition mixed in a blender represented by a blender, tumbler blender, etc. is put into a blow molding machine and foamed. The polyethylene polymer and the blowing agent are separately introduced into the extruder, Examples thereof include a melt mixing method.

  The foaming magnification of the foamed hollow molded article of the present invention thus produced is 1.5 to 30 times, more preferably 2 to 30 times.

  The ethylene-based polymer constituting the foamed hollow molded article of the present invention may be blended with other optional blending components according to various purposes without departing from the object of the present invention. As a compounding component, it may be used as a normal polyolefin additive or compounding material, such as a crystallization nucleating agent, an antioxidant, a neutralizing agent, a weather resistance improving agent, a dispersing agent, an antistatic agent, a lubricant, Molecular weight regulators (peroxides, etc.), heat stabilizers, light stabilizers, UV absorbers, lubricants, antifogging agents, antiblocking agents, slip agents, flame retardants, conductivity-imparting agents, crosslinking agents, crosslinking aids And various auxiliary agents such as metal deactivators, antibacterial agents and fluorescent brighteners, other various resins and elastomers, fillers, colorants and the like.

  The foamed hollow molded article of the present invention provides a molded article having a high foaming ratio, light weight and high heat insulation. Moreover, it is excellent in rigidity, heat resistance, and low-temperature impact properties, and can be used for a wide range of applications such as containers and various members.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

  Below, the measuring method used by the Example and the comparative example is shown.

-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 13C-NMR using a JNM-GSX400 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, Irgaphos 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. The temperature was set to 160 ° C., the piston lowering speed was set to 10 mm / min, the stretch 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.
~ Molding of foamed hollow molding ~
Using a single-layer blow molding machine (made by Plako Co., Ltd.) having a 65 mmφ extrusion screw, a 0.2 μm filter was attached to the blowing air port, a cylinder temperature of 220 ° C., a thickness of 1.5 mm, and a container volume of 1000 ml. A container was formed.

~ Measurement of foaming ratio ~
The apparent specific gravity of the foamed hollow molded article was measured with a hydrometer (manufactured by Shinko Denshi Co., Ltd., trade name: DME-220H), and the expansion ratio was determined from the ratio to the density of the polyethylene resin.
~ Bending elastic modulus ~
The bending elastic modulus of the foamed hollow molded body is a universal testing machine (trade name: Autograph AGS, manufactured by Shimadzu Corporation) in accordance with JIS K7171, taking a sample from the flat part at the center of the side surface of the container. -H 50N).

~ Properties of foamed hollow moldings ~
The appearance of the foamed hollow molded body and the state of bubbles in the cross section were visually evaluated.
Smooth surface foam shape, uniform bubble state ... ○,
Slightly non-uniform bubble state with slight surface roughness ... △,
Uneven foam shape, tearing of corners, non-uniform bubble state… ×
~ Heated dimensional stability of foamed hollow moldings ~
The foamed hollow molded body was left in an oven at 90 ° C. for 24 hours. Thereafter, the container was taken out of the oven, and the shrinkage rate and the presence / absence of deformation of the container were visually observed. The case where no deformation was observed in any part of the container and the dimensional stability was good was marked with ○, and the case where deformation was found was marked with ×.

-Low temperature impact-
300 mL of tap water was added to the foamed hollow molded body and left in a freezer at −20 ° C. for 24 hours. Thereafter, the container was taken out from the freezer and dropped onto the concrete surface from a height of 50 cm, and the occurrence of tearing and cracking of the container was examined.

  ○: No tearing or cracking occurred.

X: The tear and the crack have generate | occur | produced.

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 weight 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. The number average molecular weight was 19,500, the weight average molecular weight was 92,700, and peaks were observed at molecular weights of 31,200 and 183,200. 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 124,250, and peaks were observed at the 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 (product 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 (Me ₂ N) are added. (C ₂₆ H ₅₃ ), synthesized by a conventional method) 49.1 g (120 mmol) was added and heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), The mixture was heated to 60 ° C. and 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
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 were placed in a 1 L flask, and 18.8 g of concentrated hydrochloric acid and methyl dioleylamine (product of Lion Corporation (trade name) ) Armin M2O) 53.1 g (100 mmol) was added and heated to 45 ° C. to disperse 100 g of (Rockwood Additives (trade name) Laponite RD), and then the temperature was raised to 60 ° C. and the temperature was maintained. The mixture was stirred for 1 hour.
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, 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 1 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 dimethylsilanediyl Bis (cyclopentadienyl) zirconium dichloride (0.3485 g) and triethylaluminum in hexane (1.18 M) (85 mL) were added, and the mixture was 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, a 20% triisobutylaluminum hexane solution (0%) was added to a suspension of diphenylmethylene (1-cyclopentadienyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride 0.1165 g in hexane 10 mL. .71M) The solution prepared by adding 5 ml 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 and 1.0 mL of 20% triisobutylaluminum were 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) were added to 85 ° C. After the temperature increase, 2.4 g of 1-butene was added, and 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 45.0 g of polymer (activity: 3,000 g / g catalyst). The polymer had an MFR of 4.4 g / 10 min, a density of 950.7 kg / m ³ and a melting point of 128.4 ° C. The number average molecular weight was 9,094, the weight average molecular weight was 77,100, and peaks were observed at molecular weights of 10,400 and 168,000. Further, the number of long chain branches contained in the polymer is 0.11 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 0.24 per number. Moreover, the ratio of the fraction of Mn of 100,000 or more when molecular weight fractionation was 15.7 wt% of the total polymer. The melt tension was 210 mN.

Production Example 21
(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
[Molding of foamed hollow moldings]
3 parts by weight of polyethylene resin and baking soda-based foaming agent masterbatch (manufactured by Eiwa Chemical Co., Ltd., trade name EE-275F) produced in Production Example 1 are dry blended, and using a single-layer blow molding machine (manufactured by Placo). A foamed container having a cylinder temperature of 220 ° C., a thickness of 1.5 mm, and a container volume of 1000 ml was molded.
The apparent specific gravity, bending elastic modulus, heating dimensional stability, and low temperature impact property of this foamed container were measured. Moreover, the external appearance of the foam container was observed. These results are shown in Table 1.

Examples 2-11
The same procedure as in Example 1 was performed except that the polyethylene resin was changed to the resin shown in Table 1. The evaluation results of the foam container are shown in Table 1.

Comparative Examples 1-12
The same procedure as in Example 1 was performed except that the polyethylene resin was changed to the resin shown in Table 2. The evaluation results of the foam container are shown in Table 2.

  The foamed hollow molded body of the present invention can be used, for example, as a container, a bath tub, a duct, an automobile member, an electrical product member, a building member, or the like.

Claims (2)

The density is 925 to 970 kg / m ³ , the melt flow rate (MFR) is 0.1 to 100 g / 10 min, and two peaks are shown in the molecular weight measurement by gel permeation chromatography, and the weight average molecular weight (Mw) and number The ratio of the average molecular weight (Mn) (Mw / Mn) is in the range of 2.0 to 7.0, and long chain branching per 1000 carbons of the main chain in the fraction with Mn of 100,000 or more when molecular weight fractionation is performed A foamed hollow molded article comprising a polyethylene resin having 0.15 or more and an expansion ratio of 1.5 to 30 times. The foamed hollow molded article according to claim 1, wherein Mw / Mn of the polyethylene resin is in the range of 3.0 to 6.0 and Mn is 15,000 or more.