JP2012136665A - Ethylenic polymer composition for extrusion lamination, and laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylenic polymer composition for extrusion lamination whose laminated molded product has reduced curl while having satisfactory heat resistance.SOLUTION: The ethylenic polymer composition for extrusion lamination comprising 50 to 80 wt.% ethylene-α-olefin copolymer (A) obtained by copolymerizing ethylene having ≥920 kg/mand <955 kg/mdensity and 10 to 50 g/10 min MFR and a 3-6C α-olefin, 10 to 40 wt.% high density polyethylene (B) having 955 to 975 kg/mdensity and 10 to 40 g/10 min MFR, and 10 to 40 wt.% high pressure process low density polyethylene (C) having 915 to 930 kg/mdensity and 1 to 10 g/10 min MFR and satisfying the following requirements (a) to (b) is used. (a) the polymer composition has 10 to 100 mN melt tension measured at 160C°; (b) the composition has 4 to 40 g/10 min MFR.

Description

  The present invention relates to an ethylene polymer composition for extrusion laminating, which has good heat resistance but has little curling of a laminated molded product, and a laminate having at least one layer made of this.

Among laminates obtained by extrusion lamination, laminates comprising at least one layer of polyethylene resin are used in a wide range of application fields such as craft packaging, flexible packaging, photographic paper supports, tapes, and various containers. Conventionally, the polyethylene resin used in these laminates has been mainly branched low density polyethylene (LDPE) synthesized by radical polymerization because of its excellent moldability. However, the density of LDPE is generally 918 to 925 kg / m ³ , and it is difficult to change physical properties that change with density, such as flexibility, heat resistance, rigidity, gas barrier properties, etc., resulting in limitations in use. It was. On the other hand, linear polyethylene such as linear low density polyethylene (L-LDPE) and linear high density polyethylene (HDPE) can vary widely in density according to the number of short chain branches. Because of poor molding processability, it was difficult to obtain a laminate by extrusion lamination. Therefore, a method of obtaining a laminate by extrusion-laminating a mixture of linear polyethylene and LDPE is often used (for example, see Patent Documents 1 to 4). When heat resistance, rigidity, and gas barrier properties are required, it is desirable to use high-density polyethylene, that is, HDPE as linear polyethylene (see, for example, Patent Documents 5 to 6). The occurrence of curling was a problem. Curling of the laminated body is a phenomenon in which the volume shrinks when the resin solidifies, causing a size difference between the base material and the laminated body warps in one direction. In the next processing, the end of the laminate may get caught in the processing machine or the heat seal part may be turned up, which may cause trouble.

  Since the curl size increases in proportion to the resin density, it is necessary to reduce the resin density in order to suppress the curl, and the compatibility with the heat resistance, rigidity, and gas barrier properties that improve with the resin density is It was difficult.

JP-A-6-65443 JP-A-6-322189 JP-A-7-92610 JP 2000-73018 A JP-A-6-49290 Japanese Patent Laid-Open No. 10-36582

  The present invention has been made to solve the above-described problems of the prior art, and an ethylene-based polymer composition for extrusion laminating, which has good heat resistance but has little curling of a laminate molded product, and the present invention A laminate having at least one layer is provided.

The present invention has been found as a result of intensive studies on the above-described object. That is, the present invention relates to ethylene-α obtained by copolymerizing ethylene having a density of 920 kg / m ^{3 to} 955 kg / m ³ and MFR of 10 g / 10 min to 50 g / 10 min and an α-olefin having 3 to 6 carbon atoms. -Olefin copolymer (A) 50 to 80% by weight, high density polyethylene (B) 10 to 40% by weight with a density greater than 955 kg / m ³ and 975 kg / m ³ or less, MFR 10 g / 10 min to 40 g / 10 min and density 915 kg / ^{m 3} or more 930 kg / ^{m 3} or less, made MFR1g / 10 min or more 10 g / 10 minutes or less high-pressure low-density polyethylene (C) 10 to 40 wt%, the following requirements (a) ~ (b) The present invention relates to an ethylene polymer composition for extrusion laminating.
(A) Melt tension measured at 160 ° C. 10 to 100 mN
(B) MFR 4 g / 10 min or more and 40 g / 10 min or less Hereinafter, the present invention will be described in detail.

  The ethylene-α-olefin copolymer (A) constituting the ethylene-based polymer composition for extrusion lamination of the present invention comprises a repeating unit derived from ethylene and a repeating unit derived from an α-olefin having 3 to 6 carbon atoms. This is an ethylene-α-olefin copolymer. Examples of the α-olefin having 3 to 6 carbon atoms include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-butene. You may use together at least 2 types of these C3-C6 alpha olefins.

The ethylene-α-olefin copolymer (A) constituting the ethylene-based polymer composition for extrusion lamination of the present invention has a density measured by the method described in JIS K6760 (1995) of 920 kg / m ³ or more and 955 kg / m ³ or less, preferably 920 kg / ^{m 3} or more 945 kg / ^{m 3} or less, and most preferably is of 920 kg / ^{m 3} or more 935 kg / ^{m 3} or less. Here, when the density is less than 920 kg / m ³ , the heat resistance of the ethylene polymer composition is inferior, which is not preferable. On the other hand, when it exceeds 955 kg / m ³ , the melting temperature of the ethylene-α-olefin copolymer is high, and the ethylene polymer composition is excellent in heat resistance and rigidity, but the composition is used. The curl of the manufactured result layer is undesirably large. The density can be measured by a density gradient tube method in accordance with JIS K6760 (1995).

  The ethylene-α-olefin copolymer (A) constituting the ethylene-based polymer composition for extrusion lamination of the present invention is a melt flow rate (hereinafter referred to as MFR) measured by the method described in JIS K6760 (1995). Is from 10 g / 10 min to 50 g / 10 min, preferably from 20 g / 10 min to 40 g / 10 min. Here, when the MFR is less than 10 g / 10 min, the load on the extruder for producing an ethylene polymer composition is increased, the productivity is lowered, and the extrusion laminate moldability is inferior. On the other hand, if it exceeds 50 g / 10 min, the melt tension is small and the extrusion laminate formability may be inferior. MFR can be measured with a melt indexer under the conditions of 190 ° C. and a load of 2.16 kg.

The ethylene-α-olefin copolymer (A) constituting the ethylene polymer composition for extrusion lamination of the present invention preferably has a long chain branch in the structure. By having a long chain branch in the structure, the melt tension of the ethylene-α-olefin copolymer (A) is increased, and the laminate processability of the ethylene-based polymer composition for extrusion lamination is improved. In addition, when there are 0.01 to 0.2 long-chain branches having 6 or more carbon atoms per 1000 carbon atoms, neck-in (melting film width drop) and draw-down (upper limit of take-up speed) during lamination processing This is preferable because it has the best balance. In addition, the number of long-chain branches is the number of branches of a hexyl group or more (carbon number of 6 or more) detected by ¹³ C-NMR measurement.

  Furthermore, the ethylene-α-olefin copolymer (A) constituting the ethylene-based polymer composition for extrusion laminating of the present invention is an ethylene polymer or ethylene and carbon having a vinyl group at the terminal obtained by polymerizing ethylene. In the presence of a macromonomer comprising an ethylene copolymer having a vinyl group at the end obtained by copolymerizing an olefin having a number of 3 to 6, and having a number average molecular weight (Mn) of 2000 or more, or A polyethylene polymer obtained by polymerizing ethylene or ethylene and an olefin having 3 to 6 carbon atoms simultaneously with the synthesis of the macromonomer is desirable.

  A macromonomer is an olefin polymer having a vinyl group at the end, preferably an ethylene polymer having a vinyl group at the end obtained by polymerizing ethylene, or a copolymer of ethylene and an olefin having 3 to 6 carbon atoms. It is an ethylene copolymer having a vinyl group at the terminal obtained by the process.

  Examples of the olefin having 3 to 6 carbon atoms include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-butene, α-olefin such as vinylcycloalkane, butadiene or 1,4 -A diene such as hexadiene can be exemplified. Two or more of these olefins can be mixed and used.

  The number average molecular weight (Mn) in terms of linear polyethylene of the macromonomer is 2,000 or more, preferably 5,000 or more, and more preferably 10,000 or more. The weight average molecular weight (Mw) in terms of linear polyethylene is 4,000 or more, preferably 10,000 or more, more preferably more than 15,000. By increasing the molecular weight of the macromonomer, the length of the long chain branch introduced into the ethylene-α-olefin copolymer (A) is increased, and the melt tension is improved.

  The ethylene-α-olefin copolymer (A) constituting the ethylene-based polymer composition for extrusion lamination of the present invention has a weight average molecular weight (Mw) to number average molecular weight ratio Mw / Mn in the range of 2 to 5. It is desirable to be. Mw / Mn can be calculated by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn), which are standard polyethylene equivalent values, by gel permeation chromatography (GPC). When Mw / Mn is in this range, the content ratio of the low molecular weight component in the resin is small, so roll contamination during lamination molding due to leaching of the low molecular weight component, stickiness of the surface of the laminate molded product, heat seal failure, etc. The adverse effect is suppressed, and at the same time, the extrusion load becomes higher than necessary, and the amount of extrusion during lamination is not limited.

  The ethylene-α-olefin copolymer (A) constituting the ethylene-based polymer composition for extrusion lamination of the present invention may be obtained by any method, for example, the production conditions of the examples of the present invention described later. It can be arbitrarily created by itself or by fine adjustment of the condition factor.

  The catalyst used for the copolymerization of ethylene and α-olefin is not particularly limited, and a Ziegler catalyst, a Phillips catalyst, a metallocene catalyst, or the like can be used. Preferably, the catalyst is polymerized by a metallocene catalyst.

  Examples of the metallocene compound that is the main component of the metallocene catalyst include one kind selected from a cyclopentadienyl group, a substituted cyclopentadienyl group (substituted cyclopentadienyl group), an indenyl group, and a substituted indenyl group. Group, a transition metal compound of Group 4 of the periodic table, in which one group selected from a fluorenyl group and a substituted fluorenyl group has a ligand bridged by a bridging group, a typical example of which is diphenylmethylene. (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2 , 7-dimethyl-9-fluorenyl) zirconium dichlorine Diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl) Of dichloro-forms such as -1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and the above metallocene compounds. Examples include dimethyl, diethyl, dihydro, diphenyl, dibenzyl, and bridged bisindenyl zirconium complexes.

  Furthermore, the following can be illustrated as a metallocene catalyst.

Component (a) and the following general formula (1)
AlR ¹ ₃ (1)
(In the formula, each R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
A catalyst comprising an organoaluminum compound represented by the following (hereinafter referred to as “component (b)”), a catalyst further comprising water,
Component (a) and the following general formula (2)

および／または下記一般式（３）

And / or the following general formula (3)

（式中、Ｒ^２は各々独立して水素原子または炭素数１〜２０の炭化水素基であり、ｐは２〜５０の整数である。）
で表されるアルミノキサン（以下、「成分（ｃ）」と称する）からなる触媒、さらに成分（ｂ）を含んでなる触媒、
成分（ａ）と下記一般式（４）
［Ｒ^３Ｒ^４ _ｙ−１Ｍ^１Ｈ］［Ｍ^２Ａｒ_４］ （４）
（式中、［Ｒ^３Ｒ^４ _ｙ−１Ｍ^１Ｈ］はカチオンであり、Ｍ^１は周期表の第１５族または第１６族から選ばれる元素であり、Ｒ^３は炭素数１〜３０の炭化水素基であり、Ｒ^４は各々独立して水素原子または炭素数１〜３０の炭化水素基であり、ｙはＭ^１が第１５族元素の時ｙ＝３であり、Ｍ^１が第１６族元素の時ｙ＝２であり、［Ｍ^２Ａｒ_４］はアニオンであり、Ｍ^２はホウ素、アルミニウムまたはガリウムであり、Ａｒは各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表されるプロトン酸塩（以下、「成分（ｄ）」と称する）、下記一般式（５）
［Ｃ］［Ｍ^２Ａｒ_４］ （５）
（式中、Ｃはカルボニウムカチオンまたはトロピリウムカチオンであり、Ｍ^２はホウ素、アルミニウムまたはガリウムであり、Ａｒは各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表されるルイス酸塩（以下、「成分（ｅ）」と称する）または下記一般式（６）
［Ｍ^３Ｌ^１ _ｚ］［Ｍ^２Ａｒ_４］ （６）
（式中、Ｍ^３は周期表の第１族、第８族、第９族、第１０族または第１１族の金属の陽イオンであり、Ｌ^１はルイス塩基またはシクロペンタジエニル基であり、ｚは０≦ｚ≦２であり、Ｍ２はホウ素、アルミニウムまたはガリウムであり、Ａｒは各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表される金属塩（以下、「成分（ｆ）」と称する）から選ばれる少なくとも１種類の塩からなる触媒、さらに成分（ｂ）および／または成分（ｃ）を含んでなる触媒、
成分（ａ）と下記一般式（７）
Ｍ^２Ａｒ_３ （７）
（式中、Ｍ^２はホウ素、アルミニウムまたはガリウムであり、Ａｒは各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表されるルイス酸（以下、「成分（ｇ）」と称する）からなる触媒、さらに成分（ｂ）および／または成分（ｃ）を含んでなる触媒、
成分（ａ）と成分（ｇ）と成分（ｄ）、成分（ｅ）、成分（ｆ）から選ばれる少なくとも１種類の塩からなる触媒、さらに成分（ｂ）および／または成分（ｃ）を含んでなる触媒、
成分（ａ）と粘土鉱物（以下、「成分（ｈ）」と称する）からなる触媒、さらに成分（ｂ）を含んでなる触媒、
特開平７−２２４１０６号公報、特開平０９−５９３１０号公報、特開平１０−２３１３１２号公報、特開平１０−２３１３１３号公報等に例示される成分（ａ）と有機化合物で処理された粘土鉱物（以下、「成分（ｉ）」と称する）からなる触媒、さらに成分（ｂ）を含んでなる触媒が挙げられる。また、成分（ａ）とジエチル亜鉛、フッ化フェノール、水、シリカ、およびトリメチルジシラザン（（（ＣＨ_３）_３Ｓｉ）_２ＮＨ）を接触させて得られる担体を含んでなる触媒、さらに成分（ｂ）を含んでなる触媒が挙げられる。

(In the formula, each R ² is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and p is an integer of 2 to 50.)
A catalyst comprising an aluminoxane represented by the following (hereinafter referred to as “component (c)”), a catalyst further comprising component (b),
Component (a) and the following general formula (4)
_{^{[R 3 R 4 y-1}} M 1 H] [M 2 Ar 4] (4)
(Wherein [R ³ R ⁴ _y-1 M ¹ H] is a cation, M ¹ is an element selected from Group 15 or Group 16 of the periodic table, and R ³ has 1 to 30 carbon atoms. a hydrocarbon group, ^{R 4} are each independently hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, y is when y = 3 for ^{M 1} is a group 15 element, ^{M 1} is 16 In the case of a group element, y = 2, [M ² Ar ₄ ] is an anion, M ² is boron, aluminum or gallium, and Ar is each independently a halogen-substituted aryl group having 6 to 20 carbon atoms. .)
A protonate represented by the following formula (hereinafter referred to as “component (d)”), the following general formula (5)
[C] [M ² Ar ₄ ] (5)
(Wherein, C is a carbonium cation or a tropylium cation, M ² is boron, aluminum or gallium, and Ar is each independently a halogen-substituted aryl group having 6 to 20 carbon atoms.)
Lewis acid salt represented by the following (hereinafter referred to as “component (e)”) or the following general formula (6)
[M ³ L ¹ _z ] [M ² Ar ₄ ] (6)
(Wherein M ³ is a metal cation of Group 1, Group 8, Group 9, Group 10 or Group 11 of the Periodic Table, and L ¹ is a Lewis base or a cyclopentadienyl group. Z is 0 ≦ z ≦ 2, M2 is boron, aluminum or gallium, and Ar is each independently a halogen-substituted aryl group having 6 to 20 carbon atoms.)
A catalyst comprising at least one salt selected from metal salts represented by the following (hereinafter referred to as “component (f)”), and a catalyst further comprising component (b) and / or component (c),
Component (a) and the following general formula (7)
M ² Ar ₃ (7)
(Wherein M ² is boron, aluminum or gallium, and Ar is each independently a halogen-substituted aryl group having 6 to 20 carbon atoms.)
A catalyst comprising a Lewis acid represented by (hereinafter referred to as “component (g)”), and a catalyst further comprising component (b) and / or component (c),
A catalyst comprising at least one salt selected from component (a), component (g), component (d), component (e) and component (f), and further comprising component (b) and / or component (c) A catalyst consisting of,
A catalyst comprising a component (a) and a clay mineral (hereinafter referred to as “component (h)”), a catalyst further comprising a component (b),
Clay minerals treated with component (a) and an organic compound exemplified in JP-A-7-224106, JP-A-09-59310, JP-A-10-223112, JP-A-10-231313, etc. Hereinafter, a catalyst comprising “component (i)”) and a catalyst further comprising component (b) may be mentioned. Further, a catalyst comprising a support obtained by contacting component (a) with diethyl zinc, fluorinated phenol, water, silica, and trimethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH), a catalyst comprising b).

  Simultaneously with the synthesis of the macromonomer, as a metallocene compound used for polymerizing ethylene or ethylene and an olefin having 3 to 6 carbon atoms, a non-crosslinked bis (indenyl) zirconium complex that synthesizes a macromonomer, a non-crosslinked bis (cyclopenta) Dienyl) zirconium complex, crosslinked bis (cyclopentadienyl) zirconium complex, or crosslinked (cyclopentadienyl) (indenyl) zirconium complex (hereinafter referred to as component (j)), macromonomer and ethylene. A cross-linked (cyclopentadienyl) (fluorenyl) zirconium complex or a cross-linked (indenyl) (fluorenyl) zirconium complex (hereinafter referred to as “component”) that copolymerizes or copolymerizes macromonomer, ethylene, and olefin having 3 to 6 carbon atoms. k).) In the presence of Rothen catalyst, polymerizing ethylene, or ethylene and 3 to 6 carbon atoms α- olefins can be used a method of copolymerization.

  Specific examples of component (j) include, for example, bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, 1,1,3,3-tetramethyldisiloxane-1,3-diyl-bis (cyclo Pentadienyl) zirconium dichloride, 1,1-dimethyl-1-silaethane-1,2-diyl-bis (cyclopentadienyl) zirconium dichloride, propane-1,3-diyl-bis (cyclopentadienyl) zirconium dichloride , Dimethylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4,7-dimethyl) Indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride and the like and dimethyl, diethyl, dihydro, diphenyl and dibenzyl of the above transition metal compounds Can be illustrated.

  Specific examples of component (k) include, for example, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride. Diphenylmethylene (1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) Zirconium dichloride, isopropylidene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dipheni Silanediyl (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilanediyl (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride Diphenylmethylene (2-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, etc. Examples thereof include dimethyl, diethyl, dihydro, diphenyl, and dibenzyl isomers of dichloride and the above transition metal compounds. Moreover, the compound which substituted the zirconium atom of the said transition metal compound by the titanium atom or the hafnium atom can also be illustrated.

  Further, the amount of the component (k) with respect to the component (j) is not particularly limited, and is preferably 0.0001 to 100 times mol, particularly preferably 0.001 to 10 times mol.

  And as a metallocene catalyst using the component (j) and the component (k), for example, a catalyst comprising the component (j), the component (k) and an organoaluminum compound (hereinafter referred to as the component (l)); a catalyst comprising j), component (k) and aluminoxane (hereinafter referred to as component (m)); a catalyst further comprising component (l); component (j), component (k) and protonic acid salt (Hereinafter referred to as component (n)), Lewis acid salt (hereinafter referred to as component (o)) or metal salt (hereinafter referred to as component (p)). Catalyst; catalyst further comprising component (l); catalyst comprising component (j), component (k), component (m) and inorganic oxide (hereinafter referred to as component (q)); component (j ), Component (k), component (q), component (n), component (o), component (p) A catalyst comprising at least one salt; a catalyst further comprising component (l); comprising component (j), component (k), clay mineral (hereinafter referred to as component (r)), and component (l). Catalysts: Catalysts composed of component (j), component (k), and clay mineral treated with an organic compound (hereinafter referred to as component (s)) can be exemplified, preferably component (j) and component ( A catalyst comprising k) and component (s) can be used.

  Here, examples of the clay mineral that can be used as the component (r) and the component (s) include fine particles mainly composed of microcrystalline silicate. As a structural feature, a layered structure is formed, and various layers of negative charges are included in the layer. In this respect, it is greatly different from a metal oxide having a three-dimensional structure such as silica or alumina. These clay minerals are generally of a large layer charge, with pyrophyllite, kaolinite, dickite and talc groups (negative charge per chemical formula is approximately 0), smectite groups (negative charge per chemical formula is from about 0.25). 0.6), vermiculite group (negative charge per chemical formula is approximately 0.6 to 0.9), mica group (negative charge per chemical formula is approximately 1), brittle mica group (negative charge per chemical formula is approximately 2) It is classified. Each group shown here includes various clay minerals, and examples of the clay mineral belonging to the smectite group include montmorillonite, beidellite, saponite, hectorite and the like. Further, a plurality of the above clay minerals can be mixed and used.

  The organic compound treatment in component (s) refers to introducing an organic ion between clay mineral layers to form an ionic complex. Examples of the organic compound used in the organic compound treatment include N, N-dimethyl-n-octadecylamine hydrochloride, N, N-dimethyl-n-eicosylamine hydrochloride, N, N-dimethyl-n-docosylamine hydrochloride, N, N-dimethyloleylamine hydrochloride, N, N-dimethylbehenylamine hydrochloride, N-methyl-bis (n-octadecyl) amine hydrochloride, N-methyl-bis (n-eicosyl) amine hydrochloride, N-methyl -Dioleylamine hydrochloride, N-methyl-dibehenylamine hydrochloride, N, N-dimethylaniline hydrochloride can be exemplified.

  The catalyst composed of component (j), component (k) and component (s) can be obtained by bringing component (j), component (k) and component (s) into contact in an organic solvent. A method of adding component (k) to the contact product of (j) and component (s); a method of adding component (j) to the contact product of component (k) and component (s); A method of adding the component (s) to the contact product of the component (k); a method of adding the contact product of the component (j) and the component (k) to the component (s) can be exemplified.

  As the contact solvent, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane or cyclohexane, aromatic hydrocarbons such as benzene, toluene or xylene, ethyl ether or n-butyl ether And ethers such as halogenated hydrocarbons such as methylene chloride or chloroform, 1,4-dioxane, acetonitrile, or tetrahydrofuran.

  About a contact temperature, it is preferable to select between 0-200 degreeC and to process.

  As for the usage-amount of each component, the component (j) is 0.0001-100 mmol per 1 g of component (s), Preferably it is 0.001-10 mmol.

  The contact product of component (j), component (k), and component (s) thus prepared may be used without washing, or may be used after washing. In addition, when the component (j) or the component (k) is a dihalogen, it is preferable to further add the component (l). Further, the component (l) can be added for the purpose of removing impurities in the component (s), the polymerization solvent and the olefin.

  When producing the ethylene-α-olefin copolymer (A) constituting the laminate of the present invention, it is preferably carried out at a polymerization temperature of −100 to 120 ° C. Preferably, it is preferable to carry out in the range of 60 to 120 ° C. The polymerization time is preferably in the range of 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 300 MPa. The polymerizable monomer is ethylene alone or ethylene and an α-olefin having 3 to 6 carbon atoms. When ethylene is an α-olefin having 3 to 6 carbon atoms, ethylene and α-olefin having 3 to 8 carbon atoms are used. As the olefin supply ratio, ethylene / C3-C6 α-olefin (molar ratio) of 1 to 200, preferably 3 to 100, and more preferably 5 to 50 can be used. 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. In addition, the ethylene copolymer can be obtained by separating and recovering from the polymerization solvent by a conventionally known method after the completion of the polymerization and drying.

  Polymerization can be carried out in a slurry state, a solution state, or a gas phase state. In particular, when the polymerization is performed in a slurry state, an ethylene-based copolymer having a powder particle shape is efficiently and stably produced. Can do. Further, the solvent used for the polymerization may be any organic solvent that is generally used, and specific examples include benzene, toluene, xylene, propane, isobutane, pentane, hexane, heptane, cyclohexane, gasoline, and the like, propylene, Olefin itself such as 1-butene, 1-hexene and 1-octene can also be used as a solvent.

  The number of long chain branches of the ethylene-α-olefin copolymer (A) of the present invention can be increased by increasing the number of terminal vinyls of the macromonomer. The number of terminal vinyls of the macromonomer can be controlled by selecting a metallocene compound for synthesizing the macromonomer. For example, it can be increased by changing the non-bridged metallocene compound to a bridged metallocene compound.

  The Mw / Mn of the ethylene-α-olefin copolymer (A) of the present invention can be increased by decreasing the Mn of the macromonomer. The Mn of the macromonomer can be controlled by selecting a metallocene compound for synthesizing the macromonomer. For example, it can be reduced by changing a non-bridged metallocene compound to a bridged metallocene compound.

  The high-density polyethylene (B) constituting the ethylene polymer composition of the present invention is an ethylene homopolymer and / or an ethylene-α-olefin copolymer polymerized by a Ziegler catalyst, a Phillips catalyst, a metallocene catalyst, or the like. . Examples of the α-olefin include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene and vinylcycloalkane.

High-density polyethylene constituting the ethylene polymer composition (B) of the present invention, JIS K6760 (1995) Density measured by the method of 955 kg / ^{m 3} greater than 975 kg / ^{m 3} or less, preferably a density of 955 kg / m ³ is intended greater than the 970 kg / ^{m 3} or less. A density of 955 kg / m ³ or less is not preferable because the heat resistance of the ethylene polymer composition of the present invention decreases. On the other hand, when the density is greater than 975 kg / m ³ , the curl of the laminate formed by molding the ethylene polymer composition of the present invention becomes very large, which is not preferable.

  The high density polyethylene (B) constituting the ethylene polymer composition of the present invention has an MFR measured by the method of JIS K6760 (1995) of 10 g / 10 min or more and 40 g / 10 min or less, preferably 20 g / 10 min or more. 40 g / 10 min or less. Here, when the MFR is less than 10 g / 10 minutes, the extrusion load at the time of laminating the ethylene polymer composition is increased, the productivity is lowered, and the high-speed spreadability is inferior. On the other hand, if it exceeds 40 g / 10 minutes, the melt tension becomes small and the neck-in at the time of laminating increases, which is not preferable.

  The high-pressure method low-density polyethylene (C) constituting the ethylene-based polymer composition for extrusion lamination of the present invention can be obtained by a conventionally known high-pressure radical polymerization method, and is appropriately selected within the scope of the present invention.

High-pressure low-density polyethylene constituting the ethylene polymer composition of the present invention (C) is, JIS K6760 (1995) Density measured by the method of 915 kg / ^{m 3} or more 930 kg / ^{m 3} or less, preferably 915 kg / m ³ or more and 925 kg / m ³ or less. When the density is less than 915 kg / m ³ , the heat resistance of the ethylene polymer composition of the present invention may be lowered. On the other hand, when the density is higher than 930 kg / m ³ , the high-temperature low-density polyethylene has a high melting temperature, and the ethylene polymer composition has excellent heat resistance and rigidity, but has poor laminate processability.

  The high pressure low density polyethylene (C) constituting the ethylene polymer composition of the present invention has an MFR measured by the method of JIS K6760 (1995) of 1 g / 10 min to 10 g / 10 min, preferably 1 g / 10. Min. To 5 g / 10 min. Here, when the MFR is less than 1 g / 10 minutes, the extrusion load at the time of laminating the ethylene polymer composition is increased, the productivity is lowered, and the high-speed spreadability is inferior. On the other hand, if it exceeds 10 g / 10 minutes, the melt tension becomes small and the neck-in at the time of lamination increases, which is not preferable.

  An ethylene-based polymer composition for extrusion laminating a specific amount of an ethylene-α-olefin copolymer (A), high-density polyethylene (B) and high-pressure low-density polyethylene (C) satisfying the above requirements is obtained by extrusion laminating. It has excellent heat resistance and curl balance when made into a laminate. The ethylene-based polymer composition of the present invention has an ethylene-α-olefin copolymer (A) of 50 to 80% by weight, preferably 50 to 70% by weight, and high density polyethylene (B) of 10 to 40% by weight, preferably It is composed of 10 to 30% by weight, and 10 to 40% by weight, preferably 20 to 35% by weight of high-pressure low-density polyethylene (C). If the blending amount of the high density polyethylene (B) is less than 10% by weight, the density of the ethylene polymer composition is lowered and the heat resistance is lowered, which is not preferable. On the other hand, if the blending amount exceeds 40% by weight, While the density of the combined composition is increased and the heat resistance and rigidity are improved, curling of the laminate is increased, which is not preferable. On the other hand, when the blending amount of the high-pressure method low density polyethylene (C) is less than 10% by weight, the melt tension of the ethylene polymer composition becomes small, and the neck-in at the time of laminating increases, which is not preferable. When the amount is more than% by weight, the density of the ethylene-based polymer composition becomes low and the heat resistance becomes poor, which is not preferable.

  The ethylene polymer composition for extrusion lamination of the present invention has a melt tension measured at 160 ° C. of 10 to 100 mN, preferably 20 to 100 mN. When the melt tension is less than 10 mN, the neck-in at the time of laminating becomes large, which is not preferable. On the other hand, if the melt tension exceeds 100 mN, the high-speed spreadability during lamination may be inferior, which is not preferable.

  Further, the ethylene polymer composition for extrusion lamination of the present invention has an MFR measured by the method of JIS 6760 (1995) of 4 g / 10 min to 40 g / 10 min, preferably 7 g / 10 min to 30 g / 10 min. It is below, More preferably, they are 10 g / 10min or more and 25 g / 10min or less. When the MFR is less than 4 g / 10 minutes, the high-speed spreadability at the time of lamination may be inferior, which is not preferable. On the other hand, when MFR exceeds 40 g / 10 minutes, the neck-in at the time of laminating becomes large, which is not preferable.

  In the ethylene polymer composition of the present invention, a stabilizer, a lubricant, a flame retardant, a dispersant, a filler, a foaming agent, a foaming nucleating agent, and a crosslinking agent are included in the range not departing from the gist of the present invention. , UV inhibitors, antioxidants, colorants, and the like can be included.

  For the ethylene polymer composition of the present invention, a method for forming a resin composition usually can be used. For example, as a melting / mixing method, extrusion kneading using a single screw extruder or a twin screw extruder, roll kneading. And the like, and can be obtained by melt-kneading by this method.

  The ethylene polymer composition of the present invention may be formed into a laminate by directly bonding a molten film made of an ethylene polymer composition extruded from a T die to a substrate by a known extrusion laminating machine. it can.

The extrusion laminate molding method may be any of single laminate, tandem laminate, coextrusion laminate, and sandwich laminate, and is not particularly limited. Moreover, when performing an extrusion lamination process, in order to obtain a laminated body with favorable adhesiveness of a base material and an ethylene-type polymer composition layer, it is preferable to extrude from a die | dye at the temperature of 250-350 degreeC. Further, at least the surface where the molten film of the ethylene polymer composition is in contact with the substrate may be oxidized with air or ozone gas. When the oxidation reaction with air proceeds, it is preferable to extrude from a die at a temperature of 270 ° C. or higher, and when the oxidation reaction with ozone gas proceeds, it is preferable to extrude at 250 ° C. or higher. In addition, it is preferable that the processing amount of ozone gas is 0.5 mg or more per 1 m ^{2 of} the film extruded from the die. Moreover, in order to improve adhesiveness with a base material, you may perform well-known surface treatments, such as an anchor-coat agent process, a corona discharge process, a flame process, and a plasma process, to the adhesion surface of a base material.

  Examples of the substrate include synthetic polymer film and sheet, woven fabric, non-woven fabric, metal foil, paper, cellophane and the like. Examples thereof include films and sheets made of a synthetic polymer such as polyethylene terephthalate, polyamide, polyvinyl alcohol, polycarbonate, polyethylene, and polypropylene. Further, these polymer films and sheets may be further subjected to aluminum vapor deposition, alumina vapor deposition, or silicon dioxide vapor deposition. Further, these polymer films and sheets may be further printed using urethane-based ink or the like. Examples of the metal foil include aluminum foil and copper foil, and examples of the paper include kraft paper, stretched paper, high-quality paper, glassine paper, board paper such as cup base paper and photographic paper base paper.

  Laminates of the present invention are dried foods such as snacks and instant noodles, soups, miso, pickles, sauces, aquatic food and beverage packaging such as beverages, medicine packaging such as medicines and infusion bags, shampoos, cosmetics, diaper back sheets To be used as a wide range of films, containers, tapes, supports, such as toiletries, photographic paper supports, paper containers and lids, paper plates, release papers and release tapes, easy-release films, paper semi-retort packs, etc. Can do.

  The ethylene-based polymer composition for extrusion laminating of the present invention has good heat resistance, but has little curling of the laminate molded product, and can be used as a film, container, tape, and support for a wide range of applications. It is extremely useful as a material.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these.

-Measurement of molecular weight and molecular weight distribution-
The weight average molecular weight (Mw), number average molecular weight (Mn), and ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) of the macromonomer and the ethylene-α-olefin copolymer (A) are gel permeation Measured by chromatography (GPC). Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC apparatus, Tosoh Co., Ltd. TSKgel GMHhr-H (20) HT is used as the column, the column temperature is set to 140 ° C., and 1 is used as the eluent. Measurement was performed using 2,4-trichlorobenzene. 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 is 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.

~ Measurement of density ~
The density of the ethylene-α-olefin copolymer (A) and the ethylene polymer composition was measured by a density gradient tube method in accordance with JIS K6760 (1995).

~ Measurement of MFR ~
The MFR of the ethylene-α-olefin copolymer (A) and the ethylene polymer composition was measured with a melt indexer in accordance with JIS K6760 (1995).

~ Measurement of melt tension ~
The melt tension of the ethylene-based polymer composition is a die having a length of 8 mm, a diameter of 2.095 mm, and an inflow angle of 90 ° on a capillary viscometer (Toyo Seiki Seisakusho, trade name: Capillograph) with a barrel diameter of 9.55 mm. Was measured. For the melt tension, 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 measured. 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.

-Measurement of the number of long chain branches-
The number of long chain branches of the ethylene-α-olefin copolymer (A) was measured by 13C-NMR using a Varian VNMRS-400 nuclear magnetic resonance apparatus by 13C-NMR. The solvent is tetrachloroethane-d2. The number per 1,000 main chain methylene carbons was determined from the following formula (4) described in “Macromolecules” Vol. 31, No. 25, pages 8679-8683 (1998).

Number of long chain branches = IAα / (3 × IAtot) (4)
[Wherein, IAα is the integrated intensity of a long-chain branched α-carbon peak (chemical shift: 34.6 ppm) above the hexyl group, and IAtot is the integrated intensity of the main chain methylene carbon peak (30.0 ppm). . ]
~ Neck-in ~
The ethylene polymer composition was supplied to an extruder of an extrusion laminator (manufactured by Musashinokikai Co., Ltd.) having a 90 mmφ screw, extruded from a T-die having an opening width of 600 mm at a temperature of 315 ° C., and a substrate take-up speed of 200 m / As a part, the T die opening width and the coating width of the ethylene polymer composition when the extrusion laminating resin composition was extruded to a thickness of 20 μm on a kraft paper substrate having a basis weight of 50 g / m ² The difference was taken as the neck-in, and the value was measured.

~curl~
The laminate produced in the measurement of ~ neck-in ~ was placed on a flat surface with the ethylene polymer composition layer facing upward, and a 10 cm square was drawn on this. A cut was made in the diagonal line of the square, and after standing for 24 hours under conditions of an air temperature of 23 ° C. and a relative humidity of 50%, the height at which the cut portion was warped from the flat surface was measured.

-Heat resistance (gross change)-
~ Neck-in ~ The laminate produced in the measurement of the neck is heated for 30 seconds at a temperature of 110 to 135 ° C (at intervals of 5 ° C) using a small oven (manufactured by Werner Mathis), and an ethylene polymer composition before and after heating. The gloss on the layer side was measured with a gloss meter (manufactured by Nippon Denshoku). The temperature at which the gloss value after heating exceeded 120% of the gloss value before heating was defined as the heat resistant temperature.

Synthesis example 1
[Preparation of modified hectorite]
After adding 3 liters of ethanol and 100 ml of 37% concentrated hydrochloric acid to 3 liters of water, 585 g (1.1 mol) of N-methyl-dioleylamine was added to the resulting solution and heated to 60 ° C. to form the hydrochloride salt. A solution was prepared. 1 kg of hectorite was added to this solution. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 50 L of 60 ° C. water. Then, it dried at 60 degreeC and 10 < ^-3 > torr for 24 hours, and obtained the modified | denatured hectorite with an average particle diameter of 5.2 micrometers by grind | pulverizing with a jet mill.
[Preparation of polyethylene resin production catalyst]
500 g of the modified hectorite was suspended in 1.7 liters of hexane, and 8.25 g (20.0 mmol) of dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride and a hexane solution of triisobutylaluminum ( 0.714M) Add 2.8 liters (2 mol) of mixture, stir at 60 ° C. for 3 hours, let stand and remove supernatant, add triisobutylaluminum in hexane (0.15M) Thus, a macromonomer synthesis catalyst (100 g / L) was obtained.

In the macromonomer synthesis catalyst prepared above, 10 mol% of isopropylidene (1-cyclopentadienyl) (2,7-di-) with respect to dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride is used. 1.21 g (2.22 mmol) of t-butyl-9-fluorenyl) zirconium dichloride was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a 100 g / L polyethylene resin production catalyst.
[Production of ethylene-α-olefin copolymer (A-1)]
In a polymerization vessel having an internal volume of 540 L, the above-mentioned [145 kg / hour of hexane, 33.0 kg / hour of ethylene, 4.9 kg / hour of butene-1, 20 NL / hour of hydrogen and 30 kg / hour of polymer production] The polyethylene resin production catalyst prepared in [Preparation of polyethylene resin production catalyst] was continuously supplied, and the polymerization reaction was continuously carried out while maintaining the total pressure at 3,000 kPa and the polymerization vessel internal temperature at 60 ° C. The slurry was continuously extracted from the polymerization vessel to remove unreacted hydrogen, ethylene, and butene-1, and then separated and dried to obtain an ethylene-α-olefin copolymer (A-1) powder. This was melt-kneaded using a 50 mm diameter single screw extruder set at 200 ° C. and pelletized to obtain ethylene-α-olefin copolymer (A-1) pellets. The density of the obtained ethylene-α-olefin copolymer (A-1) pellets is 925 kg / m ³ , MFR is 24.1 g / 10 min, the number of long-chain branches is 0.13 per 1000 carbon atoms, weight average The ratio Mw / Mn between the molecular weight (Mw) and the number average molecular weight (Mn) was 3.8.

  In this synthesis example, ethylene and 1-butene are polymerized simultaneously with the production of the macromonomer shown in Reference Example 1 below.

Reference example 1
[Synthesis of macromonomer]
In Synthesis Example 1 [Production of ethylene-α-olefin copolymer (A-1)], the macromonomer synthesis catalyst prepared in Synthesis Example 1 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. Except having used, it carried out similarly to the synthesis example 1, and obtained the macromonomer pellet. Mn of the obtained macromonomer pellet was 15,000, and Mw / Mn was 2.5. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1,000 carbons was 0.07.

Synthesis example 2
[Preparation of polyethylene resin production catalyst]
500 g of modified hectorite prepared in Synthesis Example 1 [Preparation of modified hectorite] was suspended in 1.7 liters of hexane, and dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride was suspended. Add a mixed solution of 8.81 g (20.0 mmol) and hexane solution (0.714 M) of triisobutylaluminum (2.814 M), stir at 60 ° C. for 3 hours, and leave to stand to remove the supernatant. After removal, a hexane solution (0.15 M) of triisobutylaluminum was added to obtain a macromonomer synthesis catalyst (100 g / L).

The macromonomer synthesis catalyst prepared above was mixed with 5 mol% of diphenylmethylene (1-cyclopentadienyl) (9- 9%) based on dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride. Fluorenyl) zirconium dichloride (0.58 g, 1.05 mmol) was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a 100 g / L polyethylene resin production catalyst.
[Production of ethylene-α-olefin copolymer (A-2)]
In Synthesis Example 1 [Production of ethylene-α-olefin copolymer (A-1)], butene-1 was changed from 4.9 kg / hour to 5.3 kg / hour, and the hydrogen supply amount was changed from 20 NL / hour to 5 NL / hour. The ethylene-α-olefin copolymer (A-2) was prepared in the same manner as in Synthesis Example 1 except that the catalyst was changed to the polyethylene resin production catalyst prepared in [Preparation of polyethylene resin production catalyst]. Obtained. The density of the obtained ethylene-α-olefin copolymer (A-2) is 920 kg / m ³ , MFR is 12.7 g / 10 min, the number of long-chain branches is 0.10 per 1000 carbon atoms, and the weight average molecular weight The ratio Mw / Mn between (Mw) and the number average molecular weight (Mn) was 4.2.

Reference example 2
[Synthesis of macromonomer]
In Synthesis Example 2 [Production of ethylene-α-olefin copolymer (A-2)], the macromonomer synthesis catalyst prepared in Synthesis Example 2 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. A macromonomer pellet was obtained in the same manner as in Synthesis Example 2 except that it was used. Mn of the obtained macromonomer pellet was 20,000, and Mw / Mn was 2.8. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1,000 carbons was 0.05.

Synthesis example 3
[Production of ethylene-α-olefin copolymer (A-3)]
In Synthesis Example 1 [Production of ethylene-α-olefin copolymer (A-1)], butene-1 was changed from 4.9 kg / hour to 5.3 kg / hour, and the hydrogen supply amount was changed from 20 NL / hour to 30 NL / hour. The ethylene-α-olefin copolymer (A-3) was prepared in the same manner as in Synthesis Example 1 except that the catalyst was changed to the polyethylene resin production catalyst prepared in Synthesis Example 2 [Preparation of Polyethylene Resin Production Catalyst]. ) The density of the obtained ethylene-α-olefin copolymer (A-3) is 920 kg / m ³ , MFR is 39.2 g / 10 min, the number of long chain branches is 0.12 per 1000 carbon atoms, and the weight average molecular weight The ratio Mw / Mn between (Mw) and the number average molecular weight (Mn) was 4.1.

Reference example 3
[Synthesis of macromonomer]
In Synthesis Example 3 [Production of ethylene-α-olefin copolymer (A-3)], the macromonomer synthesis catalyst prepared in Synthesis Example 2 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. A macromonomer pellet was obtained in the same manner as in Synthesis Example 3 except that it was used. Mn of the obtained macromonomer pellet was 10,000, and Mw / Mn was 3.0. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1,000 carbons was 0.05.

Synthesis example 4
[Preparation of polyethylene resin production catalyst]
500 g of modified hectorite prepared in Synthesis Example 1 [Preparation of modified hectorite] was suspended in 1.7 liters of hexane, and 7.85 g (20.0 mmol) of bis (indenyl) zirconium dichloride and a hexane solution of triisobutylaluminum ( 0.714M) Add 2.8 liters (2 mol) of mixture, stir at 60 ° C. for 3 hours, let stand and remove supernatant, add triisobutylaluminum in hexane (0.15M) Thus, a macromonomer synthesis catalyst (100 g / L) was obtained.

In the macromonomer synthesis catalyst prepared above, 5 mol% of isopropylidene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was added to bis (indenyl) zirconium dichloride. 57 g (1.05 mmol) was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a 100 g / L polyethylene resin production catalyst.
[Production of ethylene-α-olefin copolymer (A-4)]
In Synthesis Example 1 [Production of ethylene-α-olefin copolymer (A-1)], butene-1 is 4.9 kg / hour to 0.5 kg / hour, hydrogen supply amount is 20 NL / hour to 5 NL / hour, Except that the polymerization temperature was changed from 60 ° C. to 85 ° C. and the catalyst was changed to the polyethylene resin production catalyst prepared in [Preparation of polyethylene resin production catalyst], ethylene-α- An olefin copolymer (A-4) was obtained. The resulting ethylene-α-olefin copolymer (A-4) has a density of 955 kg / m ³ , an MFR of 11.3 g / 10 min, a long-chain branch number of 0.03 per 1000 carbon atoms, and a weight average molecular weight. The ratio Mw / Mn of (Mw) to the number average molecular weight (Mn) was 2.4.

Reference example 4
[Synthesis of macromonomer]
In Synthesis Example 4 [Production of ethylene-α-olefin copolymer (A-4)], the macromonomer synthesis catalyst prepared in Synthesis Example 4 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. Except having used, it carried out similarly to the synthesis example 4, and obtained the macromonomer pellet. Mn of the obtained macromonomer pellet was 20,000 and Mw / Mn was 2.2. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1,000 carbons was 0.02.

Synthesis example 5
[Production of ethylene-α-olefin copolymer (A-5)]
In Synthesis Example 1 [Production of ethylene-α-olefin copolymer (A-1)], butene-1 is 4.9 kg / hour to 0.5 kg / hour, hydrogen supply amount is 20 NL / hour to 30 NL / hour, The polymerization temperature was changed from 60 ° C. to 85 ° C., and the catalyst was changed to the polyethylene resin production catalyst prepared in Synthesis Example 4 [Preparation of polyethylene resin production catalyst]. An α-olefin copolymer (A-5) was obtained. The resulting ethylene-α-olefin copolymer (A-5) has a density of 955 kg / m ³ , an MFR of 38.4 g / 10 min, a long-chain branch number of 0.03 per 1000 carbon atoms, and a weight average molecular weight. The ratio Mw / Mn between (Mw) and the number average molecular weight (Mn) was 2.3.

Reference Example 5
[Synthesis of macromonomer]
In Synthesis Example 5 [Production of ethylene-α-olefin copolymer (A-5)], the macromonomer synthesis catalyst prepared in Synthesis Example 4 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. A macromonomer pellet was obtained in the same manner as in Synthesis Example 5 except that it was used. Mn of the obtained macromonomer pellet was 17,000, and Mw / Mn was 2.3. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1,000 carbons was 0.02.

下記実施例および比較例で用いた高密度ポリエチレンおよび高圧法低密度ポリエチレンの特性を表２に示す。

Table 2 shows the characteristics of the high-density polyethylene and high-pressure method low-density polyethylene used in the following Examples and Comparative Examples.

実施例１
合成例１に示したエチレン−α−オレフィン共重合体（Ａ−１）６５重量％、高密度ポリエチレン（東ソー（株）製 商品名ニポロンハード １０００；密度９６６ｋｇ／ｍ^３、ＭＦＲ２０．１ｇ／１０分）（以下、（Ｂ−１）という。）１５重量％、高圧ラジカル重合法で得られた低密度ポリエチレン（東ソー（株）製 商品名ペトロセン ３６０；密度９１９ｋｇ／ｍ^３、ＭＦＲ１．６ｇ／１０分）（以下、（Ｃ−１）という。）２０重量％、をタンブラーミキサーにて予備混合した後、シリンダー温度１８０℃に調整した単軸押出機（（株）プラコー製、型式 ＰＤＡ−５０）で溶融混練、造粒し、エチレン系重合体組成物のペレットを得た。得られたペレットは、エチレン系重合体組成物の評価方法に示した方法によりラミネート成形した。 得られたエチレン系重合体組成物により密度、ＭＦＲ、溶融張力、および融点を測定し、押出ラミネート成形時にネックインとカールの評価を行った。これらの評価結果を表３に示す。

Example 1
65% by weight of ethylene-α-olefin copolymer (A-1) shown in Synthesis Example 1, high-density polyethylene (trade name Nipolon Hard 1000 manufactured by Tosoh Corporation; density 966 kg / m ³ , MFR 20.1 g / 10 min) (Hereinafter referred to as (B-1)) 15% by weight, low density polyethylene obtained by high-pressure radical polymerization method (trade name Petrocene 360 manufactured by Tosoh Corporation; density 919 kg / m ³ , MFR 1.6 g / 10 min) (Hereinafter referred to as (C-1)) 20% by weight was premixed with a tumbler mixer and then melted with a single screw extruder (model PDA-50, manufactured by Plako Co., Ltd.) adjusted to a cylinder temperature of 180 ° C. It knead | mixed and granulated and the pellet of the ethylene-type polymer composition was obtained. The obtained pellets were laminated by the method shown in Evaluation method for ethylene polymer composition. Density, MFR, melt tension, and melting point were measured from the obtained ethylene polymer composition, and neck-in and curl were evaluated during extrusion lamination molding. These evaluation results are shown in Table 3.

Example 2
Except having changed the compounding ratio of the composition into A-1 50 weight%, B-1 40 weight%, and C-1 10 weight%, it carried out similarly to Example 1, and obtained the pellet of the ethylene-type polymer composition. . The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 3.

Example 3
Except having changed the compounding ratio of the composition into A-1 50 weight%, B-1 10 weight%, and C-1 40 weight%, it obtained the pellet of the ethylene polymer composition like Example 1 was obtained. . The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 3.

Example 4
Except having changed the compounding ratio of the composition into A-1 80% by weight, B-1 10% by weight, and C-1 10% by weight, the pellets of the ethylene-based polymer composition were obtained in the same manner as in Example 1. . The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 3.

Example 5
An ethylene polymer composition in the same manner as in Example 1 except that the ethylene-α-olefin copolymer A-2 shown in Synthesis Example 2 was used instead of A-1 as the ethylene-α-olefin copolymer. Pellets were obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 3.

Example 6
An ethylene polymer composition in the same manner as in Example 1 except that the ethylene-α-olefin copolymer A-3 shown in Synthesis Example 3 was used instead of A-1 as the ethylene-α-olefin copolymer. Pellets were obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 3.

Example 7
An ethylene-based polymer composition as in Example 1 except that the ethylene-α-olefin copolymer A-4 shown in Synthesis Example 4 was used instead of A-1 as the ethylene-α-olefin copolymer. Pellets were obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 3.

Example 8
An ethylene polymer composition in the same manner as in Example 1 except that the ethylene-α-olefin copolymer A-5 shown in Synthesis Example 5 was used instead of A-1 as the ethylene-α-olefin copolymer. Pellets were obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 3.

Example 9
The same as Example 1 except that instead of B-1, high density polyethylene B-2 (trade name Nipolon Hard 2000; density 959 kg / m ³ , MFR 13.5 g / 10 minutes) was used instead of B-1. Thus, pellets of the ethylene polymer composition were obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 3.

Example 10
Implemented except using high pressure method low density polyethylene C-2 (trade name Petrocene 205; density 924 kg / m ³ , MFR 3.1 g / 10 min, manufactured by Tosoh Corporation) instead of C-1 as high pressure method low density polyethylene In the same manner as in Example 1, pellets of an ethylene polymer composition were obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 3.

Example 11
Example except that high-pressure low-density polyethylene C-3 (trade name Petrocene 203 manufactured by Tosoh Corporation); density 919 kg / m3, MFR 7.9 g / 10 min) was used as the high-pressure low-density polyethylene instead of C-1. In the same manner as in No. 1, pellets of an ethylene polymer composition were obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 3.

比較例１
高密度ポリエチレン（Ｂ）を配合せず、配合比率をＡ−１ ８０重量％、Ｃ−１ ２０重量％に変更した以外は実施例１と同様にしてエチレン系重合体組成物のペレットを得た。得られたペレットは、実施例１と同様にラミネート成形し評価を行った。これらの評価結果を表４に示す。

Comparative Example 1
A pellet of an ethylene polymer composition was obtained in the same manner as in Example 1 except that the high-density polyethylene (B) was not blended and the blending ratio was changed to 80 wt% A-1 and 20 wt% C-1. . The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 4.

  The obtained ethylene-based polymer composition was inferior in heat resistance as compared with Examples 3 to 6 having the same density.

Comparative Example 2
The pellets of the ethylene-based polymer composition were prepared in the same manner as in Example 1 except that the high-pressure method low-density polyethylene (C) was not blended and the blending ratio was changed to 80 wt% A-1 and 20 wt% B-1. Obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 4.

The obtained ethylene-based polymer composition had a large neck-in of 91 mm and was inferior in laminate processability. Comparative Example 3
The ethylene-based polymer composition was the same as in Example 1 except that the ethylene-α-olefin copolymer (A) was not blended and the blending ratio was changed to 80 wt% B-1 and 20 wt% C-1. Pellets were obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 4.

  The obtained ethylene polymer composition had a large neck-in of 90 mm and was inferior in laminate processability.

Comparative Example 4
The pellets of the ethylene-based polymer composition were prepared in the same manner as in Example 1 except that the high-density polyethylene (B) and the high-pressure method low-density polyethylene (C) were not blended and the blending ratio was changed to A-1 100% by weight. Obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 4.

  The obtained ethylene-based polymer had a large neck-in of 85 mm and was inferior in laminate processability. Moreover, it was inferior to heat resistance.

Comparative Example 5
Ethylene polymer in the same manner as in Example 1 except that the tylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (C) were not blended and the blending ratio was changed to 100 wt% B-1. A pellet of the composition was obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 4.

  The obtained ethylene-based polymer had a large neck-in of 122 mm and was inferior in laminate processability.

Comparative Example 6
Ethylene polymer composition in the same manner as in Example 1 except that the ethylene-α-olefin copolymer (A) and the high-density polyethylene (B) were not blended and the blending ratio was changed to 100% by weight of C-2. Pellets were obtained. The obtained pellets were laminated and evaluated in the same manner as in Example 1. These evaluation results are shown in Table 4.

  The obtained ethylene polymer was inferior in heat resistance.

Claims (5)

An ethylene-α-olefin copolymer obtained by copolymerizing ethylene having a density of 920 kg / m ^{3 to} 955 kg / m ³ and MFR of 10 g / 10 min to 50 g / 10 min and an α-olefin having 3 to 6 carbon atoms ( a) 50 to 80 wt%, density 955 kg / ^{m 3} greater than 975 kg / ^{m 3} or less, MFR10g / 10 min or more 40 g / 10 minutes or less high density polyethylene (B) 10 to 40 wt% and a density 915 kg / ^{m 3} More than 930 kg / m ³ or less, MFR 1 g / 10 min or more and 10 g / 10 min or less, high pressure method low density polyethylene (C) 10 to 40 wt%, satisfying the following requirements (a) to (b) Polymer composition.
(A) Melt tension measured at 160 ° C. 10 to 100 mN
(B) MFR 4 g / 10 min or more and 40 g / 10 min or less The ethylene-based polymer composition according to claim 1, wherein the ethylene-α-olefin copolymer (A) satisfies the requirement (c).
(C) having 0.01 to 0.2 long chain branches having 6 or more carbon atoms per 1000 carbon atoms The ethylene-based polymer composition according to claim 1 or 2, wherein the ethylene-α-olefin copolymer (A) satisfies the requirement (d).
(D) The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 5 It is a macromonomer comprising an ethylene polymer having a vinyl group at the end obtained by polymerizing ethylene or an ethylene copolymer having a vinyl group at the end obtained by copolymerizing ethylene and an olefin having 3 to 6 carbon atoms. In the presence of a macromonomer having a number average molecular weight (Mn) of 2000 or more, or simultaneously with the synthesis of the macromonomer, a polyethylene-based polymer obtained by polymerizing ethylene or ethylene and an olefin having 3 to 6 carbon atoms. The ethylene polymer composition according to any one of claims 1 to 3, wherein the coalescence is used as an ethylene-α-olefin copolymer (A). A laminate comprising at least one layer made of the ethylene-based polymer composition according to claim 1.