JP2012158654A - Non-crosslinked polyethylene-extruded foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-crosslinked polyethylene-extruded foam in which an expansion ratio is high, and that is excellent in mechanical strength and fabrication quality.SOLUTION: The non-crosslinked polyethylene-extruded foam is used, which comprises an ethylene polymer in which a density is 920-950 kg/m, an MFR is 0.1-50 g/10 minutes, two peaks are shown in a molecular weight measurement by a gel permeation chromatography, and a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number-average molecular weight (Mn) is in a range of 2.0-7.0, wherein the ethylene polymer has at least 0.15 long chain branching per 1,000 of a carbon number of a main chain in a fraction in which Mn is at least 100,000 when a molecular weight is classified. In the polyethylene-extruded foam, an expansion ratio is at least threefold.

Description

  The present invention relates to a non-crosslinked polyethylene extruded foam. More specifically, the present invention relates to a non-crosslinked polyethylene extruded foam made of a specific ethylene polymer, having an expansion ratio of 3 times or more, and excellent in mechanical strength and secondary processability.

  Polyethylene resin foams are widely used mainly for cushioning materials, cushioning materials, impact absorbing materials, and the like, and are roughly classified into non-crosslinked foams and crosslinked foams. In recent years, from the viewpoint of reducing environmental impact, interest in improving the recyclability of plastic materials has increased, and there has been an increasing demand for non-crosslinked crosslinked products even in polyethylene resin foams. When producing a non-crosslinked, high-expanding polyethylene resin foam, a polyethylene having a high melt tension is required. Therefore, a low-density polyethylene having a long chain branch produced by a high-pressure method (hereinafter referred to as a high-pressure method). It is known that low density polyethylene) is used. However, non-crosslinked foams made of high-pressure low-density polyethylene are inferior in rigidity and heat resistance compared to crosslinked foams, and the temperature range of molding is extremely high because the viscosity changes rapidly when thermoformed. There was a drawback of being narrow. In order to solve such a problem, a high-pressure low-density polyethylene and a linear low-density polyethylene or high-density polyethylene excellent in rigidity and heat resistance may be used in combination (for example, see Patent Documents 1 and 2). Proposed. In addition, the present inventors have found that a highly rigid polyethylene extruded foam can be provided by extrusion foaming an ethylene polymer that satisfies specific requirements (see, for example, Patent Documents 3 and 4). ).

JP 60-222222 A JP 2006-274038 A JP 2006-096910 A JP 2006-199872 A

  However, in the methods proposed in Patent Documents 1 and 2, linear polyethylene is blended in a specific ratio with high-pressure low-density polyethylene, and molding must be performed under strict foaming conditions. This raises technical difficulties. In the methods of Patent Documents 3 and 4, it is described that an extruded foam having high rigidity and high heat resistance can be obtained by extrusion foaming an ethylene polymer that satisfies specific requirements. It has become clear that the resulting foam is cracked in the molded body during secondary processing. An object of the present invention is to provide a non-crosslinked polyethylene extruded foam that overcomes the above-mentioned drawbacks of the prior art, has a high expansion ratio, and is excellent in mechanical strength and secondary processability.

As a result of intensive studies to solve the above problems, the inventors of the present invention have a density of 920 to 950 kg / m ³ or less, an MFR of 0.1 to 50 g / 10 minutes, and two peaks are observed in the GPC measurement. A component having a number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) in the range, Mn of 100,000 or more obtained by molecular weight fractionation is a specific ratio, and a long chain branching more than a specific in the component In addition to the excellent properties of conventional non-crosslinked polyethylene extruded foams, non-crosslinked polyethylene extruded foams with particularly high secondary processability can be obtained by making the ethylene-based polymer into non-crosslinked polyethylene extruded foams As a result, the present invention has been completed. That is, the present invention has a density of 920 to 950 kg / m ³ , an MFR of 0.1 to 50 g / 10 min, shows two peaks in the molecular weight measurement by gel permeation chromatography, and has a weight average molecular weight (Mw) The ratio (Mw / Mn) of the number average molecular weight (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 The present invention relates to a non-crosslinked polyethylene extruded foam comprising an ethylene polymer having 0.15 or more.

The ethylene polymer constituting the non-crosslinked polyethylene extruded foam of the present invention has a density measured according to JIS K7676 in the range of 920 to 950 kg / m ³ , particularly preferably in the range of 930 to 945 kg / m ³ . is there. Here, when the density is less than 920 kg / m ³ , the obtained non-crosslinked polyethylene extruded foam is inferior in rigidity, and when it is made into a thin-walled foam, the deflection of the foam is large, which causes a problem in secondary processing. . On the other hand, when the density exceeds 950 kg / m ³ , the obtained non-crosslinked polyethylene extruded foam is excellent in rigidity but poor in flexibility and inferior in secondary workability such as various bending workability.

  The ethylene polymer constituting the non-crosslinked polyethylene extruded foam of the present invention has an MFR at 190 ° C. and a load of 2160 g of 0.1 to 50 g / 10 minutes, and preferably 1 to 20 g / 10 minutes. Here, when MFR is less than 0.1 g / 10 minutes, the load of the extruder at the time of shaping | molding becomes large, and productivity falls. On the other hand, when it exceeds 50 g / 10 minutes, since foam does not grow uniformly at the time of foam molding, a good foam cannot be obtained.

  The ethylene polymer constituting the non-crosslinked polyethylene extruded foam of the present invention exhibits two peaks in the molecular weight measurement by GPC. The peak top molecular weight (Mp) is obtained by dividing the molecular weight distribution curve obtained by GPC measurement into two peaks by the method described later, and evaluating the top molecular weight of the high molecular weight side peak and the low molecular weight side peak. The case of 100,000 or more was assumed to have two Mp. When it was less than 100,000, the top molecular weight of the actually measured molecular weight distribution curve was defined as one Mp.

  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 measurement by GPC has one peak, the fluidity of the resin at the time of extrusion foaming is poor, resulting in a problem in workability.

  The ratio of the weight average molecular weight (Mw) to Mn (Mw / Mn) is 2.0 to 7.0, preferably 2.5 to 7.0, more preferably 3.0 to 6.0. When Mw / Mn is within this range, good foamability and extrusion foamability are obtained, which is preferable. When Mw / Mn is less than 2.0, a foamed molded product having uniform bubbles cannot be obtained. Further, when Mw / Mn exceeds 7.0, the temperature dependence of the melt viscosity is large, and it is necessary to strictly adjust the molding processing temperature. As a result, there arises a problem that the moldable range is narrowed. 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 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 mechanical strength of the obtained foamed molded product 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 of the fraction having Mn of 100,000 or more obtained by molecular weight fractionation is 0.15 or more per 1000 carbons of the main chain. When the number of long-chain branches in the fraction with Mn of 100,000 or more is less than 0.15 per 1000 carbons of the main chain, a good foam cannot be obtained because bubbles do not grow uniformly during 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, the ratio of the fraction whose Mn obtained by molecular weight fractionation is 100,000 or more is less than 40% of the whole polymer. When the fraction of Mn obtained by molecular weight fractionation is 100,000 or more is 40% or more of the entire polymer, the temperature dependence of the melt viscosity is large, and it is necessary to strictly control the molding processing temperature, and thus molding is possible. The problem arises that the range becomes narrower.
The ethylene polymer constituting the non-crosslinked polyethylene extruded foam of the present invention has a melt tension measured at 160 ° C. of preferably 20 mN or more, particularly preferably 30 mN or more. Here, when the melt tension is 20 mN or more, when foam molding is performed, the bubbles grow uniformly and a good foam is obtained. The melt tension in the present invention is as follows: a die having a length of 8 mm and a diameter of 2.095 mm, an inflow angle of 90 °, a shear rate of 10.8 s ⁻¹ , a stretch ratio of 47, and a measurement temperature of 160 ° C. When the maximum stretch ratio was less than 47, the value measured at the highest stretch ratio that did not break was taken as the melt tension.

  As described above, the ethylene polymer used in the present invention has a specific structure, and becomes an uncrosslinked polyethylene extruded foam excellent in mechanical strength and secondary processability by extrusion foaming.

  Moreover, the non-crosslinked polyethylene extruded foam of the present invention has a foaming ratio of 3 times or more. Here, when the expansion ratio is less than 3 times, the cushioning property of the foam is inferior, which causes a problem in secondary processability such as bending.

The ethylene polymer constituting the non-crosslinked polyethylene extruded foam of the present invention is
The following general formula (1)
M1Q1aQ2bQ3cQ4d (1)
(Wherein, M1 is a titanium atom, a zirconium atom or a hafnium atom, and Q1, Q2, Q3 and Q4 are a cycloalkadienyl group, a substituted cycloalkadienyl group, a chelating ligand, a 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, and the above 1 to 20 carbon atoms In which oxygen is introduced between the carbon-carbon bonds of the hydrocarbon group, a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms, and the carbon number of 1 -20 hydrocarbon groups in which part of carbon is substituted with silicon, these may be the same or different from each other, and Q1, Q2, Q3 and Q4 may be different from each other. Nohara Or shows may be bonded via an atomic group, a, b, c and d integers of 0 to 4.)
The transition metal compound (A) represented by the formula (2) is a clay compound belonging to the smectite group hectorite.

（式中、Ｒ１〜Ｒ３は各々独立して炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数１〜３０のアルキルアミノ基、炭素数１〜３０のアルキルシリル基、上記炭素数１〜３０の炭化水素基の炭素と炭素の結合間に酸素を導入したもの、上記炭素数１〜３０の炭化水素基の一部を炭素数１〜３０のアルキルアミノ基に置換したもの、上記炭素数１〜３０の炭化水素基の一部の炭素をケイ素に置換したもの、であり、かつＲ１〜Ｒ３のうち少なくともひとつが炭素数２１以上であり、Ｍ２は周期表第１５族の原子であり、［Ａ−］はアニオンである。）
で表される有機化合物にて変性した有機変性粘土（Ｂ）及び有機アルミニウム化合物（Ｃ）からなるエチレン系重合体製造用触媒を用いて、エチレン重合を行うことにより製造することができる。

(In the formula, R1 to R3 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 alkylsilyl group having 1 to 30 carbon atoms. , One in which oxygen is introduced between carbon-carbon bonds of the hydrocarbon group having 1 to 30 carbon atoms, and a part of the hydrocarbon group having 1 to 30 carbon atoms is substituted with an alkylamino group having 1 to 30 carbon atoms A part of carbon of the hydrocarbon group having 1 to 30 carbon atoms substituted with silicon, and at least one of R1 to R3 has 21 or more carbon atoms, and M2 is the number 15 in the periodic table. Group atoms and [A-] is an anion.)
It can manufacture by carrying out ethylene polymerization using the catalyst for ethylene polymer manufacture which consists of the organic modified clay (B) modified | denatured with the organic compound represented by (A), and the organoaluminum compound (C).

The transition metal compound (A) has the following general formula (1)
M1Q1aQ2bQ3cQ4d (1)
(Wherein, M1 is a titanium atom, a zirconium atom or a hafnium atom, and Q1, Q2, Q3 and Q4 are a cycloalkadienyl group, a substituted cycloalkadienyl group, a chelating ligand, a 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, and the above 1 to 20 carbon atoms In which oxygen is introduced between the carbon-carbon bonds of the hydrocarbon group, a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms, and the carbon number of 1 -20 hydrocarbon groups in which part of carbon is substituted with silicon, these may be the same or different from each other, and Q1, Q2, Q3 and Q4 may be different from each other. Nohara Or shows may be bonded via an atomic group, a, b, c and d integers of 0 to 4.)
Preferably, the following general formula (3), general formula (4)

［式中、Ｍ３はチタン原子、ジルコニウム原子またはハフニウム原子であり、Ｘは各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基、上記炭素数１〜２０の炭化水素基の炭素と炭素の結合間に酸素を導入したもの、上記炭素数１〜２０の炭化水素基の一部を炭素数１〜２０のアルキルアミノ基に置換したもの、上記炭素数１〜２０の炭化水素基の一部の炭素をケイ素に置換したものであり、Ｒ４，Ｒ５は各々独立して一般式（５）、（６）、（７）または（８）

[Wherein, M3 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, or a carbon number. 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 bonds, and the carbonization having 1 to 20 carbon atoms. A part of the hydrogen 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 R4 and R5 are independent of each other. General formula (5), (6), (7) or (8)

（式中、Ｒ７は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基、上記炭素数１〜２０の炭化水素基の炭素と炭素の結合間に酸素を導入したもの、上記炭素数１〜２０の炭化水素基の一部を炭素数１〜２０のアルキルアミノ基に置換したもの、上記炭素数１〜２０の炭化水素基の一部の炭素をケイ素に置換したものである。）
で表されるＭ３に配位する配位子であり、Ｒ４とＲ５はＭ３と一緒にサンドイッチ構造を形成し、Ｒ６は一般式（９）または（１０）

(In the formula, each R7 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 1). ˜20 hydrocarbon group introduced with oxygen between carbon-carbon bonds, a part of the hydrocarbon group having 1-20 carbon atoms substituted with an alkylamino group having 1-20 carbon atoms, the above carbon (Some carbons of the hydrocarbon group of 1 to 20 are substituted with silicon.)
Wherein R4 and R5 form a sandwich structure together with M3, and R6 is represented by the general formula (9) or (10)

（式中、Ｒ８は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基、上記炭素数１〜２０の炭化水素基の炭素と炭素の結合間に酸素を導入したもの、上記炭素数１〜２０の炭化水素基の一部を炭素数１〜２０のアルキルアミノ基に置換したもの、上記炭素数１〜２０の炭化水素基の一部の炭素をケイ素に置換したものであり、Ｍ４はケイ素原子、ゲルマニウム原子または錫原子である。）
で表され、Ｒ４とＲ５を架橋するように作用しており、ｎは１〜５の整数である。］
で表される化合物が用いられる。

(In the formula, each R8 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, an alkylamino group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. An alkylsilyl group of the above, an oxygen introduced between carbon-carbon bonds of the hydrocarbon group having 1 to 20 carbon atoms, a part of the hydrocarbon group having 1 to 20 carbon atoms is an alkyl having 1 to 20 carbon atoms (Substituted by an amino group, or a part of the hydrocarbon group having 1 to 20 carbon atoms substituted by silicon, and M4 is a silicon atom, a germanium atom or a tin atom.)
And R4 and R5 are cross-linked and n is an integer of 1-5. ]
The compound represented by these is used.

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

［式中、Ｍ５は、周期表第４〜５族の遷移金属原子を示し、ｍは、１〜２の整数を示し、Ｒ１１〜Ｒ１６は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基、上記炭素数１〜２０の炭化水素基の炭素と炭素の結合間に酸素を導入したもの、上記炭素数１〜２０の炭化水素基の一部を炭素数１〜２０のアルキルアミノ基に置換したもの、上記炭素数１〜２０の炭化水素基の一部の炭素をケイ素に置換したものであり、Ｒ１１〜Ｒ１６のうちの２個以上の基、好ましくは隣接する基が互いに連結して脂肪環、芳香環または、窒素原子などの異原子を含む炭化水素環を形成していてもよく、これらの環はさらに置換基を有していてもよい。ｐは、Ｍ５の価数を満たす数であり、Ｙは、水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基、上記炭素数１〜２０の炭化水素基の炭素と炭素の結合間に酸素を導入したもの、上記炭素数１〜２０の炭化水素基の一部を炭素数１〜２０のアルキルアミノ基に置換したもの、上記炭素数１〜２０の炭化水素基の一部の炭素をケイ素に置換したものを示し、ｐが２以上の場合は、Ｙで示される複数の基は互いに同一でも異なっていてもよく、またＹで示される複数の基は互いに結合して環を形成してもよい。］

[Wherein, M5 represents a transition metal atom of Groups 4 to 5 of the periodic table, m represents an integer of 1 to 2, and R11 to R16 may be the same or different from each other; An 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, and a carbon-carbon bond between the hydrocarbon groups having 1 to 20 carbon atoms. Oxygen introduced, a part of the hydrocarbon group having 1 to 20 carbon atoms substituted with an alkylamino group having 1 to 20 carbon atoms, a part of carbon atoms of the hydrocarbon group having 1 to 20 carbon atoms Two or more groups out of R11 to R16, preferably adjacent groups, are connected to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. These rings may further have a substituent. It may be. p is a number satisfying the valence of M5, 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. , 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 and carbon, and a part of the hydrocarbon group having 1 to 20 carbon atoms is carbon The one substituted with an alkylamino group having 1 to 20 carbon atoms, one obtained by substituting some carbons of the hydrocarbon group with 1 to 20 carbon atoms with silicon, and when p is 2 or more, These 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. ]

［式中、Ｒ１７は各々の場合に水素、ヒドロカルビル、シリル、ゲルミル、ハロ、シアノおよびこれらの組み合わせから独立して選択され、かつ任意に２個のＲ１７（ここでＲ１７は水素、ハロまたはシアノではない）は一緒になってシクロペンタジエニル環の隣接位置に連結して結合環構造を形成するその２価誘導体を形成してもよく、Ｊは、Ｍ６とΠ−錯体を形成する３０個以下の非水素原子を有する中性のη４−結合ジエン基であり、Ｑは−Ｏ−、−Ｓ−、−ＮＲ１８−、−ＰＲ１８−であり、Ｍ６は＋２形式酸化状態のチタンまたはジルコニウムであり、ＺはＳｉＲ１８_２、ＣＲ１８_２、ＳｉＲ１８_２ＳｉＲ１８_２、ＣＲ１８_２ＣＲ１８_２、ＣＲ１８＝ＣＲ１８、ＣＲ１８_２ＳｉＲ１８_２またはＧｅＲ１８_２であり、ここでＲ^１８は各々の場合独立して水素あるいはヒドロカルビル、シリル、ハロゲン化アルキル、ハロゲン化アリールおよびこれらの組み合わせから選択される一員であり、かつ任意にＺからの２個のＲ１８あるいはＺからのＲ^１８およびＱからのＲ１８（ここでＲ１８は水素ではない）が環系を形成してもよい］
で表される化合物を用いることもできる。

[Wherein R17 is independently selected in each case from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano and combinations thereof, and optionally two R17 (where R17 is hydrogen, halo or cyano; May be linked together to form a divalent derivative that is linked to the adjacent position of the cyclopentadienyl ring to form a bonded ring structure, and J is less than 30 to form a Π-complex with M6. A neutral η4-bonded diene group having a non-hydrogen atom, Q is —O—, —S—, —NR18—, —PR18—, M6 is titanium or zirconium in the +2 formal oxidation state, Z is _{SiR18 2, CR18 2, SiR18 2} SiR18 2, CR18 2 CR18 2, CR18 = CR18, CR18 2 SiR18 2 or GeR18 _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 R ¹⁸ from the two R18 or Z from optionally Z And R18 from Q (where R18 is not hydrogen) may form a ring system]
The compound represented by these can also be used.

  Examples of the cycloalkadienyl group of Q1, Q2, Q3, and Q4 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)

（式中、Ｒ１〜Ｒ３は各々独立して炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数１〜３０のアルキルアミノ基、炭素数１〜３０のアルキルシリル基、上記炭素数１〜３０の炭化水素基の炭素と炭素の結合間に酸素を導入したもの、上記炭素数１〜３０の炭化水素基の一部を炭素数１〜３０のアルキルアミノ基に置換したもの、上記炭素数１〜３０の炭化水素基の一部の炭素をケイ素に置換したものであり、かつＲ１〜Ｒ３のうち少なくともひとつが炭素数２１以上であり、Ｍ２は周期表第１５族の原子であり、［Ａ］はアニオンである。）
で表される有機化合物にて変性したものであり、有機化合物の具体的な例としては、次に例示することができる。

(In the formula, R1 to R3 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 alkylsilyl group having 1 to 30 carbon atoms. , One in which oxygen is introduced between carbon-carbon bonds of the hydrocarbon group having 1 to 30 carbon atoms, and a part of the hydrocarbon group having 1 to 30 carbon atoms is substituted with an alkylamino group having 1 to 30 carbon atoms A part of carbon of the hydrocarbon group having 1 to 30 carbon atoms is substituted with silicon, and at least one of R1 to R3 has 21 or more carbon atoms, and M2 is Group 15 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), the hydrocarbon group having 1 to 30 carbon atoms of R1, R2 and R3 is methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-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 R1, R2 and R3 is a hydrocarbon group having 21 or more carbon atoms represented by a behenyl group.

  M2 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 M2 is a nitrogen atom include N, N-dimethyl-behenylamine hydrochloride, N-methyl-N-ethyl-behenylamine hydrochloride, N -Compounds such as methyl-Nn-propyl-behenylamine hydrochloride and the like, and compounds in which the hydrochloride of the above compound is replaced with hydrofluoride, hydrobromide, hydroiodide or sulfate However, it is not limited to these.

  Examples of the compound in which M2 is a phosphorus atom include compounds such as P, P-dimethyl-behenylphosphine hydrochloride, P, P-diethyl-behenylphosphine hydrochloride, P, P-dipropyl-behenylphosphine hydrochloride, and hydrochloric acid of the above compound Although the compound which replaced the salt with hydrofluoric acid salt, hydrobromide, hydroiodide, or sulfate can be illustrated, it is not limited to these.

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

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

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

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

  Further, the particle size of the organically modified clay (B) used for the polymerization of the ethylene polymer used in the present invention is not particularly limited, but if it is too small, it is difficult to settle and the catalyst cannot be prepared efficiently and is too large. When the catalyst is transferred as a slurry, the pipe is clogged in the middle. The method for adjusting the particle size is not particularly limited, and large particles may be pulverized to an appropriate particle size, small particles may be granulated to an appropriate particle size, or pulverization and granulation may be combined. Also good. The particle size may be adjusted for unmodified clay or for modified organically modified clay.

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

  The organoaluminum compound (C) is a constituent of the catalyst for producing an ethylene polymer 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)

（式中、Ｒ９は炭素数１〜２０の炭化水素基であり、Ｒ１０は各々独立して炭素数１〜２０の炭化水素基、水素原子または塩素原子である。）
で表され、遷移金属化合物をアルキル化することが可能な化合物が好ましく、具体的にはトリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウムなどのアルキルアルミニウムなどを挙げることができる。

(In the formula, R9 is a hydrocarbon group having 1 to 20 carbon atoms, and R10 is each independently a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a chlorine atom.)
And a compound capable of alkylating a transition metal compound is preferable, and specific examples include alkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum.

  Transition metal compound (A) ((A) component) and organically modified clay (B) ((B) component) used in the polymerization of the ethylene polymer used in the present invention, and organoaluminum compound (C) ((C) Although there is no restriction | limiting in the ratio of (component), it is desirable that it is the ratio shown next.

  The molar ratio of the component (A) to the component (C) per metal atom is in the range of (component A) :( component C) = 100: 1 to 1: 100000, particularly in the range of 1: 1 to 1: 10000. It is preferable that the weight ratio of the component (A) to the component (B) is (component A) :( component B) = 10: 1 to 1: 10000, particularly 3: 1 to 1: 1000. It is preferable. In particular, by combining one kind of component (A), component (B) and component (C), it is possible to produce an ethylene polymer in which two peaks are observed in molecular weight measurement by GPC. By using a polymer, an extruded foam excellent in mechanical strength and secondary processability 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 having a 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 of a specific or more in the component having a Mn of 100,000 or more. An ethylene-based copolymer capable of producing an extruded foam having excellent properties can be obtained.

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

  The catalyst used in the polymerization of the ethylene polymer 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 ethylene polymers obtained by these polymerizations are used to include not only homopolymers but also copolymers. .
The ethylene polymerization in the ethylene polymer 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 ethylene polymer having a uniform particle shape is efficiently used. It can be produced stably. Further, when the polymerization is performed in a liquid phase, the solvent used may be any organic solvent that is generally used, and specific examples include benzene, toluene, xylene, pentane, hexane, heptane, and the like. Olefins such as 1-butene, 1-octene and 1-hexene can also be used as a solvent.

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

There are no particular restrictions on the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration in producing the ethylene polymer used in the present invention, 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. The ethylene polymer obtained after the completion of the polymerization can be obtained by separating and recovering from the polymerization solvent by a conventionally known method and drying.

  The ethylene polymer used in the present invention includes a heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a slip agent, a lubricant, a nucleating agent, a pigment, carbon black, talc, glass powder, Known additives such as inorganic fillers or reinforcing agents such as glass fibers, organic fillers or reinforcing agents, flame retardants, and neutron shielding agents can be blended. Moreover, it can also be used by mixing with other thermoplastic resins. Examples of these include HDPE, linear low density polyethylene (L-LDPE), LDPE, polypropylene resin, poly-1-butene, poly-4-methyl-1-pentene, ethylene / vinyl acetate copolymer, ethylene -A vinyl alcohol copolymer, polystyrene, these maleic anhydride graft products, etc. can be illustrated.

  As a method for producing the non-crosslinked polyethylene extruded foam of the present invention, any method may be used as long as a non-crosslinked polyethylene extruded foam can be obtained. For example, the ethylene polymer and talc added if necessary The air conditioner, anti-shrinkage agent and the like are supplied to an extruder, heated and melted and kneaded, and further, a foaming agent is supplied to make a foamable molten resin mixture, and then the extrusion resin temperature, extrusion die internal pressure, discharge amount, etc. And a method of extruding into a low pressure region from a die attached to the tip of the extruder and foaming.

  Also, extrusion foams of various shapes such as round bar foams, sheet foams, plate foams, etc. are manufactured by selecting a die attached to the extruder tip according to the desired foam shape can do. For example, if a strand die is attached, a round bar-like foam can be obtained; if an annular die is attached, a sheet-like foam can be obtained; and if a slit die is attached, a plate-like foam can be produced. .

  In the non-crosslinked polyethylene extruded foam of the present invention, the ethylene polymer, additive, foaming agent and the like are supplied to an extruder, heated and melt-kneaded to obtain a foamable molten resin mixture, and then the extruded resin temperature is in an appropriate range. It can be formed by adjusting the inside and extruding from the extruder to the low pressure region. The specific extrusion resin temperature is based on the melting point of the ethylene polymer, and the extrusion resin temperature of the foamable molten resin is (melting point of the ethylene polymer−10 ° C.) to (melting point of the ethylene polymer + 10. It is preferable to adjust within the range of (degreeC), and it is more preferable to adjust within the range of (melting point of the said ethylene polymer -5 degreeC)-(melting point of the said ethylene polymer +5 degreeC). When the extrusion resin temperature is in the above range, the molten resin immediately after extrusion foams uniformly, and a foam having a good shape is obtained. The melting point of the ethylene-based polymer is a peak apex temperature obtained from a test piece subjected to a constant heat treatment by a heat flux DSC curve based on JIS K7121 (1987). When two or more peaks appear, the vertex temperature of the main peak having the largest peak area is defined as the melting point. Examples of the foaming agent in extrusion foam molding include inorganic gas foaming agents such as carbon dioxide, nitrogen, argon, and air; propane, butane, pentane, hexane, cyclobutane, cyclohexane, trichlorofluoromethane, dichlorodifluoromethane, and the like. Volatile foaming agents of: azodicarbonamide, barium azodicarboxylate, N, N-dinitrosopentamethylenetetramine, 4,4′-oxybis (benzenesulfonylhydrazide) which is liquid or solid at room temperature and generates gas upon heating ), Chemical blowing agents such as diphenylsulfone-3,3′-disulfonylhydrazide, p-toluenesulfonyl semicarbazide, trihydrazinotriazine, biurea, zinc carbonate, and the like. Non-crosslinked polyethylene extruded foam of the present invention Preferably 1-20 parts by weight with respect to the ethylene-based polymer 100 parts by weight of formed, particularly preferably in the range of 5 to 15 parts by weight.

  The use of the non-crosslinked polyethylene extruded foam of the present invention is not particularly limited, and can be suitably used as a heat insulating molded body for food containers, building materials, heating equipment and the like.

  According to the present invention, a non-crosslinked polyethylene extruded foam having a high expansion ratio and excellent mechanical strength and secondary workability can be easily obtained.

  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, and the particle size after pulverization was measured using a microtrack particle size distribution analyzer (trade name, manufactured by Nikkiso Co., Ltd.). 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, Irgafos 168TM; 1,500 ppm) to an internal mixer (Toyo Seiki Seisakusho, The product kneaded for 30 minutes at 190 ° C. and 30 rpm in a nitrogen stream was used.

To measure the melt tension, a capillary viscometer (Toyo Seiki Seisakusho, trade name Capillograph) with a barrel diameter of 9.55 mm is attached with a die with a length of 8 mm and a diameter of 2.095 mm so that the inflow angle is 90 °. It was measured. 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.
-Evaluation of physical properties and moldability of extruded foam sheet-
~ Foaming ratio ~
From an extruded foam sheet obtained by molding the ethylene polymer used in the present invention, a foam having a width of 5 cm, a length of 5 cm, and a thickness of about 1.5 cm (which differs slightly depending on the sample) was cut out and weight Wg) Was measured, and the apparent density was calculated by the following formula in accordance with JIS K 6767.
Apparent density (g / cm ³ ) = W / (5 × 5 × 1.5)
The expansion ratio was determined from the apparent density by the following formula.
Foaming ratio = 1 / apparent density-foamed sheet property-
The appearance of the extruded foam sheet obtained by molding the ethylene polymer used in the present invention and the state of bubbles in the cross section were visually evaluated.
○: Smooth surface foam shape, uniform cell state Δ: Smooth surface foam shape, non-uniform cell state ×: Uneven foam shape, non-uniform cell state… ×
~ Foam sheet compression strength ~
A test piece having a width of 10 mm, a length of 50 mm, and a thickness of 10 mm was cut out from an extruded foam sheet obtained by molding the ethylene polymer used in the present invention, and a tensile tester (manufactured by A & D Co., Ltd., product) Name: Tensilon RTE-1210) compression mode, and calculated based on compressive stress at the time of 25% compression in the thickness direction at a compression speed of 10 mm / min.
-Secondary workability (thermoformability)-
Extruded foam sheets obtained by molding the ethylene polymer used in the present invention were each molded with a molding machine having a molding cycle of 10 seconds and a molding heater temperature of 140 ° C. in a vacuum molding machine equipped with a mold having a major axis of 100 mm and a depth of 50 mm. Molding was performed, and the occurrence of tearing and cracking of the container was examined with 10 shots.
○: No shape defect, no tearing or cracking occurred in all 10 shots.
(Triangle | delta): The shape defect, the tear, and the crack do not generate | occur | produce in 1 or more in 10 shots.
X: Shape failure, tearing and cracking occur in all 10 shots.
-Secondary workability (folding workability)-
A test piece having a width of 10 mm and a length of 100 mm was cut out from an extruded foam sheet obtained by molding the ethylene-based polymer used in the present invention, bent by hand, and generation of cracks or cracks in the ten test pieces. The presence or absence was confirmed visually.
○: No cracks or cracks occurred in all 10 pieces.
(Triangle | delta): The crack and the crack have not generate | occur | produced in 1 or more of 10 pieces.
X: Cracks and cracks occur in all 10 pieces.

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 15,698, the weight average molecular weight was 103,717, and peaks were observed at 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 11,431, the weight average molecular weight was 43,000, and peaks were observed at molecular weights 18,100 and 189,200. 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). This polymer had an MFR of 9.86 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 17,938, the weight average molecular weight was 65,834, and peaks were observed at the positions of molecular weights 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 21,858, the weight average molecular weight was 126,956, and peaks were observed at the molecular weights 31,300 and 247,800. 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 5.00 g / 10 min, a density of 910.3 kg / m ³ , and melting points of 79.7 ° C. and 99.3 ° C. The number average molecular weight was 27,967, the weight average molecular weight was 82,325, and peaks were observed at the positions of molecular weights 42,500 and 260,900. 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). This polymer had an MFR of 1.42 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 19,505, the weight average molecular weight was 92,677, and peaks were observed at the positions of molecular weights 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. The number average molecular weight was 26,313, the weight average molecular weight was 146,261, and peaks were observed at the positions of molecular weights 42,800 and 260,800. 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). This polymer had an MFR of 1.56 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 17,639, the weight average molecular weight was 86,656, and peaks were observed at the molecular weights of 30,500 and 155,300. 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 17,880, the weight average molecular weight was 99,274, and peaks were observed at molecular weights of 28,100 and 229,100. 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 20,699, the weight average molecular weight was 105,696, and peaks were observed at molecular weights of 32,430 and 250,290. 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 20,304, the weight average molecular weight was 75,200, and peaks were observed at the positions of molecular weights 40,730 and 216,240. 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 positions of molecular weights 71, 210 and 338,100. 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 15.5 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 58,450, and peaks were observed at the molecular weights of 30,060 and 176,620. The number of long chain branches contained in the polymer is 0.04 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.15 per number. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 5.7 wt% of the total polymer. The melt tension was 40 mN.

Production Example 15
(1) Denaturation of clay 300 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 18.8 g of concentrated hydrochloric acid and dimethylhexacosylamine (Me2N (C26H53) are added. ), Synthesized by a conventional method) 49.1 g (120 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 140 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 14 μm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclohexane) 0.4406 g of pentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, and 75 mg (corresponding to a solid content of 9.0 mg) of the catalyst suspension obtained in (2) were added to 80 ° C. After the temperature rise, 8.3 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.85 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 850 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 58.5 g of polymer (activity: 6,500 g / g catalyst). The MFR of this polymer was 4.0 g / 10 min, the density was 940.5 kg / m ³ , and the melting point was 124.9 ° C. The number average molecular weight was 21,150, the weight average molecular weight was 74,025, and peaks were observed at the molecular weights 41,500 and 217,050. Further, the number of long chain branches contained in the polymer is 0.07 per 1000 carbons of the main chain, and the number of long chain branches contained in the fraction of Mn of 100,000 or more when molecular weight fractionation is 1000 carbons of the main chain. The number was 0.18 per number. Moreover, the ratio of the fraction of Mn of 100,000 or more when molecular weight fractionation was 14.8 wt% of the total polymer. The melt tension was 49 mN.

Production Example 16
(1) Denaturation of clay 300 mL of industrial alcohol (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 methyl dioleylamine (manufactured by Lion Corporation) (Product Name) Armin M2O) 53.1 g (100 mmol) was added and heated to 45 ° C. to disperse 100 g of (Rockwood Additives (Product Name) Laponite RD), and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature.
The slurry was separated by filtration, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 138 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 12 μm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclohexane) 0.4266 g of pentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 66 mg (corresponding to a solid content of 7.9 mg) of the catalyst suspension obtained in (2) were added. After the temperature increase, 23.8 g of 1-butene was added, and ethylene gas was continuously supplied so that the partial pressure became 1.20 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 43.6 g of polymer (activity: 5,500 g / g catalyst). The polymer had an MFR of 72.4 g / 10 min, a density of 953.5 kg / m ³ , and a melting point of 113.7 ° C. Further, the number average molecular weight was 15,600, the weight average molecular weight was 37,284, and a peak was observed only at the position of 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 17,950, and a peak was observed only at the position of molecular weight 12,930. Further, the number of long-chain branches contained in the polymer was less than 0.01 per 1000 carbons of the main chain, and a fraction of Mn of 100,000 or more when molecular weight fractionation was not obtained. The melt tension was less than 10 mN.

Production Example 18
(1) Modification of clay (2) Preparation of catalyst suspension The same procedure as in Production Example 16 was performed.
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 105 mg (corresponding to a solid content of 12.6 mg) of the catalyst suspension obtained in (2) was added to 85 ° C. After the temperature increase, ethylene was continuously supplied so that the partial pressure became 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 78.1 g of polymer (activity: 6,200 g / g catalyst). The MFR of this polymer was 200 g / 10 min or more, the density was 948.9 kg / m ³ , and the melting point was 135.0 ° C. The number average molecular weight was 8,700, the weight average molecular weight was 20,010, and a peak was observed only at the position of molecular weight 13,070. 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 19,910, 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 77,115, and peaks were observed at molecular weights of 10,400 and 168,350. 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 12.2 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 19,567, the weight average molecular weight was 74,304, 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
Foam molding containing talc (trade name: MS, manufactured by Nippon Talc, average particle size of 8 μm) as a foam nucleating agent at a ratio of 0.1 part by weight with respect to 100 parts by weight of the ethylene-based polymer obtained in Production Example 1. A polyethylene-based resin composition was prepared by dry blending. And using a foam molding extrusion equipment of a single screw extruder (screw diameter 50 mmφ, L / D = 36, manufactured by Kyodo Machine) having a barrel hole for injecting a volatile liquid in the middle of the barrel, a polyethylene system for foam molding After the resin composition was supplied at 15 kg / hour and melt-kneaded, the compressed liquid butane was pressed through the barrel hole at 1200 g / hour to disperse and dispersed by a slit die (width 500 mm) set at 130 ° C. A sheet-like foamed molded product was extruded.

  The obtained non-crosslinked polyethylene extruded foam sheet had high surface smoothness and uniform fine cells, and the expansion ratio was 35 times. It was confirmed that both the compressive strength and secondary processability were better than the general high pressure method low density polyethylene foam. The results are shown in Table 1.

Examples 2-10
The same procedure as in Example 1 was conducted except that the ethylene polymer was changed to Table 1. The results are shown in Table 1.

Example 11
The same procedure as in Example 1 was conducted except that the amount of liquid butane during foam molding was changed to 100 g / hour. The results are shown in Table 1.

Comparative Examples 1-12
The same procedure as in Example 1 was conducted except that the ethylene polymer was changed to Table 2. The results are shown in Table 2.

Comparative Example 13
The same procedure as in Example 1 was conducted except that the amount of liquid butane during foam molding was changed to 60 g / hour.

  The results are shown in Table 2.

Claims (2)

The density is 920 to 950 kg / m ³ , the MFR is 0.1 to 50 g / 10 min, and two peaks are shown in the molecular weight measurement by gel permeation chromatography. The weight average molecular weight (Mw) and the number average molecular weight (Mn) The ratio (Mw / Mn) is in the range of 2.0 to 7.0, and the fraction having a Mn of 100,000 or more at the time of molecular weight fractionation has 0.15 or more long chain branches per 1000 carbons of the main chain. A non-crosslinked polyethylene extruded foam comprising an ethylene-based polymer and having an expansion ratio of 3 times or more. The non-crosslinked polyethylene extruded foam according to claim 1, wherein Mw / Mn of the ethylene polymer is in the range of 3.0 to 6.0, and Mn is 15,000 or more.