JP2009293014A - Polyethylene resin composition and laminate comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyethylene resin composition, which is obtained by extrusion lamination, is excellent in appearance, and has good processability; and to provide a laminate produced from the resin composition. <P>SOLUTION: The polyethylene resin composition for extrusion lamination comprises 1-50% by weight of (A) a low-density polyethylene that has a density of 915-935 kg/m<SP>3</SP>as determined by a high-pressure radical polymerization process and a melt mass flow rate (hereinafter referred to as MFR) of 0.5-5.0 g/10 minutes as measured at a load of 2.16 kg measured at 190°C and 99-50% by weight of a (B) polyethylene resin that satisfies the following requirements (a) to (c): (a) the density ranges from 910 to 965 kg/m<SP>3</SP>, (b) the number of long chain branches with 6 or more carbon atoms ranges from 0.01 to 3.0 per 1,000 carbon atoms, (c) the melt tension (MS<SB>190</SB>)(mN) measured at 190°C and the MFR (g/10 min, 190°C) at a load of 2.16 kg satisfy formula (1): MS<SB>190</SB>>22×MFR<SP>-0.88</SP>and the melt tension (MS<SB>160</SB>)(mN) measured at 160°C and the MFR (g/10 min, 190°C) at a load of 2.16 kg satisfy formula (2): MS<SB>160</SB>>110-110×log(MFR). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyethylene resin composition and a laminate comprising the same. More specifically, the present invention relates to a polyethylene resin composition excellent in the appearance of a product obtained by extrusion lamination and having good workability, and a laminate comprising the same.

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, branched low density polyethylene (LDPE) has been mainly used as a polyethylene resin used in these laminates because of its excellent moldability. However, the density of LDPE is generally 0.918 to 0.925 g / cm ³ , and it is difficult to change physical properties that change with the density, such as heat resistance, rigidity, gas barrier property, etc. there were. In addition, LDPE has a high molding speed, and when the laminate thickness is thin, the melted film can be easily cut. Under such conditions, poor adhesion of the base material is likely to occur, so that a product with stable quality can be obtained. It was difficult. 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. Then, the method of carrying out the extrusion lamination process of the mixture of linear polyethylene and LDPE, and obtaining a laminated body is reported (for example, refer patent documents 1-4). However, in this method, heat deterioration occurs in the mixing process of the polyethylene resin, and odor is likely to be generated in the laminate. Melt unevenness occurs at the time of extrusion molding due to poor mixing of the polyethylene resin, resulting in a laminate having a smooth surface. Sometimes it was not possible.

  In addition, a technique has been reported in which long chain branching is introduced into L-LDPE or HDPE by changing the polymerization catalyst of ethylene, and molding processability is improved without mixing LDPE (for example, see Patent Document 5). ). However, the melt tension of the polyethylene resin obtained by using these techniques is still insufficient, and it has been difficult to stably perform extrusion lamination molding. Therefore, the resulting laminate cannot solve the above-mentioned problems.

JP-A-6-65443 JP-A-6-322189 JP-A-7-92610 JP 2000-73018 A JP 2006-43911 A

  The object of the present invention is to solve the above-mentioned problems of the prior art and provide a polyethylene resin composition having a good appearance and good processability of a product obtained by extrusion lamination, and a laminate comprising the same. There is to do.

The present invention has been found as a result of intensive studies to achieve the above-described object. That is, according to the present invention, the density obtained by the high-pressure radical polymerization method is 915 to 935 kg / m ³ , and the melt mass flow rate (hereinafter referred to as MFR) measured at 2.16 kg load (190 ° C.) is 0.5. It is characterized by comprising low density polyethylene (A) 1 to 50% by weight of up to 5.0 g / 10 minutes and 99 to 50% by weight of polyethylene resin (B) satisfying the following requirements (a) to (c). A polyethylene resin composition is provided.
(A) A density of 910-965 kg / m ³ ,
(B) 0.01 to 3.0 long chain branches having 1,000 or more carbon atoms per 1,000 carbon atoms,
(C) Melt tension (MS ₁₉₀ ) (mN) measured at 190 ° C. and MFR (g / 10 min) measured at 2.16 kg load (190 ° C.) are expressed by the following formula (1)
MS ₁₉₀ > 22 × MFR ^−0.88 (1)
In addition, the melt tension (MS ₁₆₀ ) (mN) measured at 160 ° C. and the MFR (g / 10 min) measured at 2.16 kg load (190 ° C.) satisfy the following formula (2).

MS ₁₆₀ > 110-110 × log (MFR) (2)
Hereinafter, the present invention will be described in detail.

The density of the low density polyethylene (A) obtained by the high-pressure radical polymerization method constituting the polyethylene resin composition for extrusion lamination of the present invention is in the range of 915 to 935 kg / m ³ . If the density is less than 915 kg / m ³ , the self-adhesiveness of the film increases and blocking may occur. On the other hand, when the density exceeds 935 kg / m ³ , the low-density polyethylene (A) has a high melting point, which may deteriorate the low-temperature heat sealability.

  The low density polyethylene (A) used in the present invention has an MFR measured at a load of 2.16 kg (190 ° C.) in the range of 0.5 to 5.0 g / 10 minutes, and 0.7 to 3.0 g / 10. More preferably in the range of minutes. If the MFR is less than 0.5 g / 10 minutes, the load on the extruder during melt extrusion increases, and the appearance of a laminate obtained by subjecting the polyethylene resin composition for extrusion lamination to extrusion lamination may be deteriorated. On the other hand, if the MFR exceeds 5.0 g / 10 min, the neck-in may increase.

The low-density polyethylene (A) used in the present invention has a melt tension (MS ₁₆₀ ) measured at 160 ° C. of preferably 100 mN or more, more preferably 150 mN or more. When the melt tension is 100 mN or more, the molten film at the time of lamination is stable, the workability is good, roll contamination is reduced, and excellent cleanliness is obtained.

  The low density polyethylene (A) used in 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.

Density of the polyethylene resin constituting the extruded laminating a polyethylene resin composition (B) of the present invention, 910 kg / ^{m 3} or more and 965 kg / ^{m 3} or less. When the density is less than 910 kg / m ³ , the heat resistance of the obtained laminate may be remarkably deteriorated. On the other hand, if the density exceeds 965 kg / m ³ , curling of the laminate may become remarkable.

The weight average molecular weight (M _w ) in terms of linear polyethylene of the polyethylene resin (B) used in the present invention is preferably 10,000 or more and 1,000,000 or less. If _Mw is less than 10,000 or exceeds 1,000,000, it becomes difficult to perform extrusion lamination molding, and thus a laminate may not be obtained.

  The MFR measured with a 2.16 kg load (190 ° C.) of the polyethylene resin (B) used in the present invention is preferably 0.1 to 100 g / 10 min. If it is less than 0.1 g / 10 minutes or more than 100 g / 10 minutes, it is extremely difficult to perform extrusion lamination molding, and thus a laminate may not be obtained.

The number of long chain branches of the polyethylene resin (B) used in the present invention is 0.01 or more and 3.0 or less per 1,000 carbon atoms. If the number is less than 0.01, it is extremely difficult to perform extrusion lamination molding, and thus a laminate may not be obtained. Moreover, when it exceeds 3.0, there exists a possibility that an ethylene-type resin layer may become a laminated body inferior to a mechanical property. 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.

The melt tension MS ₁₉₀ (mN) measured at 190 ° C. and the MFR (g / 10 min, 190 ° C.) measured at 2.16 kg load (190 ° C.) of the polyethylene resin (B) used in the present invention are represented by the following formulas: (1)
MS ₁₉₀ > 22 × MFR ^−0.88 (1)
Preferably, the following formula (1) ′
MS ₁₉₀ > 30 × MFR− ^0.88 (1) ′
More preferably, the following formula (1) "
MS ₁₉₀ > 5 + 30 × MFR ^−0.88 (1) ”
It is in the relationship shown by. When the formula (1) is not satisfied, for example, L-LDPE and HDPE that do not satisfy MS ₁₉₀ > 22 × MFR ^−0.88 are extremely difficult to perform extrusion lamination molding, and thus a laminate cannot be obtained. There is a fear.

In addition, the melt tension MS ₁₆₀ (mN) measured at 160 ° C. and the MFR (g / 10 minutes, 190 ° C.) measured at 2.16 kg load (190 ° C.) of the polyethylene resin (B) used in the present invention are: Following formula (2)
MS ₁₆₀ > 110-110 × log (MFR) (2)
Preferably, the following formula (2) ′
MS ₁₆₀ > 130-110 × log (MFR) (2) ′
More preferably, the following formula (2) "
MS ₁₆₀ > 150-110 × log (MFR) (2) ”
It is in the relationship shown by. When the formula (2) is not satisfied, for example, L-LDPE or HDPE that does not satisfy MS ₁₆₀ > 110−110 × log (MFR) becomes extremely difficult to perform extrusion lamination molding, and thus a laminate is obtained. There is no fear.

The polyethylene resin (B) satisfying the requirements (a), (b) and (c) used in the present invention is preferably in the presence of a macromonomer comprising a polymer or copolymer capable of polymerizing olefins. Or a (co) polymer obtained by polymerizing ethylene simultaneously with the synthesis of the macromonomer. That is, a macromonomer composed of an olefin polymer or copolymer having a vinyl group at the terminal obtained by polymerizing olefin, more preferably an ethylene polymer having a vinyl group at the terminal obtained by polymerizing ethylene alone. A macromonomer composed of a copolymer or an ethylene copolymer having a vinyl group at a terminal obtained by copolymerizing ethylene and an olefin having 3 or more carbon atoms,
(D) the number average molecular weight (M _n ) is 2,000 or more,
(E) a weight average molecular weight _{(M n)} and the number average molecular weight in the presence of _{(M n)} and the ratio _(M w / _{M n)} is 2.0 to 5.0 macromonomer, or of the macromonomer Simultaneously with the synthesis, it is an ethylene (co) polymer obtained by polymerizing ethylene alone or by polymerizing ethylene and an olefin having 3 or more carbon atoms.

  A polymer of ethylene having a vinyl group at a terminal or a copolymer of ethylene and an olefin having 3 or more carbon atoms having a vinyl group at a terminal used as a macromonomer is disclosed in JP-A Nos. 2004-346304 and 2005-2005. Nos. 248013, 2006-321991, and 2007-169341.

  For example, the polyethylene resin (B) is prepared by the following general formula (4) in the presence of the macromonomer or simultaneously with the synthesis of the macromonomer.

で表される遷移金属化合物［成分（ｉ）］を主成分とする触媒を用いて、エチレンを単独で重合するか、または、エチレンと炭素数３以上のオレフィンとを共重合する方法により製造することができる。

Produced by a method of polymerizing ethylene alone or copolymerizing ethylene and an olefin having 3 or more carbon atoms, using a transition metal compound [component (i)] represented by be able to.

M ¹ in component (i) is a titanium atom, a zirconium atom or a hafnium atom, and X ¹ is each independently, for example, a hydrogen atom, a halogen, or a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms in X ¹ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, norbornyl group, Phenyl, styryl, biphenylyl, naphthyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, dimethylphenyl, diethylphenyl, dipropylphenyl, dibutylphenyl, diphenylphenyl, trimethylphenyl Group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group, vinyl group, propenyl Base , Butenyl group, butadienyl group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like.

R ¹ in component (i) is represented by the following general formula (5), (6) or (7)

で表され、これらの式中の置換基Ｒ^４は例えば各々独立して水素原子、ハロゲン、炭素数１〜２０の炭化水素基である。

The substituents R ⁴ in these formulas are each independently, for example, a hydrogen atom, a halogen, or a hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of R ¹ in component (i) include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, ethyl Cyclopentadienyl group, diethylcyclopentadienyl group, triethylcyclopentadienyl group, tetraethylcyclopentadienyl group, propylcyclopentadienyl group, dipropylcyclopentadienyl group, tripropylcyclopentadienyl group, Tetrapropylcyclopentadienyl group, butylcyclopentadienyl group, dibutylcyclopentadienyl group, tributylcyclopentadienyl group, tetrabutylcyclopentadienyl group, phenylcyclopentadienyl group, diphenylcyclopentadienyl group , Naphth Tylcyclopentadienyl group, methoxycyclopentadienyl group, trimethylsilylcyclopentadienyl group, indenyl group, methylindenyl group, dimethylindenyl group, trimethylindenyl group, tetramethylindenyl group, pentamethylindenyl group , Hexamethyl indenyl group, ethyl indenyl group, diethyl indenyl group, triethyl indenyl group, tetraethyl indenyl group, pentaethyl indenyl group, hexaethyl indenyl group, propyl indenyl group, dipropyl indenyl group, Tripropyl indenyl group, tetrapropyl indenyl group, pentapropyl indenyl group, hexapropyl indenyl group, butyl indenyl group, dibutyl indenyl group, tributyl indenyl group, tetrabutyl indenyl group, pentabutyl ind Group, hexamethylene butyl indenyl group, phenylindenyl group, diphenyl indenyl group, benzoindenyl group, naphthyl indenyl group, a methoxy indenyl group, and a trimethylsilyl indenyl group.

R ² in component (i) is represented by the following general formula (8)

で表され、置換基Ｒ^５は例えば各々独立して水素原子、ハロゲン、炭素数１〜２０の炭化水素基である。

The substituents R ⁵ are each independently, for example, a hydrogen atom, a halogen, or a hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of R ² represented by the general formula (8) include, for example, a fluorenyl group, a methyl fluorenyl group, a dimethyl fluorenyl group, a trimethyl fluorenyl group, a tetramethyl fluorenyl group, a pentamethyl fluorene group. Nyl group, hexamethylfluorenyl group, heptamethylfluorenyl group, octamethylfluorenyl group, ethylfluorenyl group, diethylfluorenyl group, triethylfluorenyl group, tetraethylfluorenyl group, pentaethyl Fluorenyl group, hexaethylfluorenyl group, heptaethylfluorenyl group, octaethylfluorenyl group, propylfluorenyl group, dipropylfluorenyl group, tripropylfluorenyl group, tetrapropylfluorene group Nyl group, pentapropylfluorenyl group, hexapropylfluorenyl group, heptap Propylfluorenyl group, octapropylfluorenyl group, butylfluorenyl group, dibutylfluorenyl group, tributylfluorenyl group, tetrabutylfluorenyl group, pentabutylfluorenyl group, hexabutylfluorenyl group Nyl group, heptabutylfluorenyl group, octabutylfluorenyl group, phenylfluorenyl group, diphenylfluorenyl group, benzylfluorenyl group, dibenzylfluorenyl group, benzofluorenyl group, dimethylamino Examples include fluorenyl group, bis (dimethylamino) fluorenyl group, methoxyfluorenyl group, dimethoxyfluorenyl group and the like.

The crosslinking group R ³ for crosslinking R ¹ and R ² in the formula (4) representing the component (i) is represented by the following general formula (9).

で表され、置換基Ｒ^６は、例えば、各々独立して水素原子、ハロゲン、炭素数１〜２０の炭化水素基である。Ｙ^１は周期表１４族の原子であり、具体的には例えば炭素原子、ケイ素原子、ゲルマニウム原子、錫原子等が挙げられ、その中でも好ましくは炭素原子、ケイ素原子等であり、ｍは１から５の整数である。

The substituent R ⁶ is each independently, for example, a hydrogen atom, a halogen, or a hydrocarbon group having 1 to 20 carbon atoms. Y ¹ is an atom of Group 14 of the periodic table, and specifically includes, for example, a carbon atom, a silicon atom, a germanium atom, a tin atom, etc. Among them, a carbon atom, a silicon atom, etc. are preferable, and m is from 1 It is an integer of 5.

  Specific examples of the general formula (9) include, for example, a methylene group, an ethylidene group, an ethylene group, a propylidene group, a propylene group, a butylidene group, a butylene group, a pentylidene group, a pentylene group, a hexylidene group, an isopropylidene group, and a methylethylmethylene group. , Methylpropylmethylene group, methylbutylmethylene group, bis (cyclohexyl) methylene group, methylphenylmethylene group, diphenylmethylene group, phenyl (methylphenyl) methylene group, di (methylphenyl) methylene group, bis (dimethylphenyl) methylene group Bis (trimethylphenyl) methylene group, phenyl (ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (diethylphenyl) methylene group, phenyl (propylphenyl) methylene group, di (propylphenyl) methylene Len group, bis (dipropylphenyl) methylene group, phenyl (butylphenyl) methylene group, di (butylphenyl) methylene group, phenyl (naphthyl) methylene group, di (naphthyl) methylene group, phenyl (biphenyl) methylene group, di (Biphenyl) methylene group, phenyl (trimethylsilylphenyl) methylene group, bis (trimethylsilylphenyl) methylene group, bis (pentafluorophenyl) methylene group, silanediyl group, disilanediyl group, trisilanediyl group, tetrasilanediyl group, dimethylsilanediyl group, Bis (dimethylsilane) diyl group, diethylsilanediyl group, dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediyl group, etc. Door can be.

As a specific compound represented by the general formula (4), when M ¹ is a zirconium atom, X ¹ is a chlorine atom, and the bridging group R ³ is a diphenylmethylene group, for example, diphenylmethylene (1-cyclopentadienyl) is used. ) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (9-fluorenyl) Zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride , Diphenylmethyle (3,4-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Diphenylmethylene (2,3,4,5-tetramethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride , Diphenyl Tylene (3-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-phenyl- 1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) ) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-silane) Clopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (3-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-propyl-1-cyclopentadienyl) (2,7-dimethyl-9- Fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2, 7-Dimethyl-9-fluor Nyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-diethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) ( 2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (3- Enyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1) -Indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenyl Methylene (1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diph Enylmethylene (2-methyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-indenyl) (2,7-di-t-butyl- 9-fluorenyl) zirconium dichloride, and the like. The compounds obtained by substituting X ¹ of the above transition metal compounds fluorine atom, a bromine atom or an iodine atom can be exemplified. Also exemplified are compounds in which R ³ of the above transition metal compound is substituted with a methylene group, an ethylene group, an isopropylidene group, a methylphenylmethylene group, a dimethylsilanediyl group, a diphenylsilanediyl group, a silacyclobutanediyl group, or a silacyclohexanediyl group. can do. Furthermore, the M ² of the transition metal compounds can also be exemplified compounds obtained by replacing the titanium atom or a hafnium atom. These compounds can also be used in combination.

  Examples of the catalyst having component (i) as a main component include a catalyst obtained by bringing component (i) into contact with an activation co-catalyst [component (iii)].

  As the component (iii), all known compounds can be used, and among them, clay minerals, clay minerals treated with organic compounds, aluminoxanes, ionic compounds, Lewis acids, magnesium chloride, surface-treated Inorganic oxides or inorganic halides are preferred.

  In the production of the preferred polyethylene resin (B), the olefin having 3 or more carbon atoms copolymerized with ethylene includes propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3- Examples include α-olefins such as methyl-1-butene and vinylcycloalkane, cyclic olefins such as norbornene and norbornadiene, dienes such as butadiene and 1,4-hexadiene, and styrene. Two or more of these olefins can be mixed and used.

The macromonomer is an olefin polymer having a vinyl group at the terminal, preferably an ethylene polymer having a vinyl group at the terminal obtained by polymerizing ethylene alone or ethylene and an olefin having 3 or more carbon atoms. It is an ethylene copolymer having a vinyl group at the terminal obtained by copolymerization, and more preferably, among branches other than branches derived from olefins having 3 or more carbon atoms, methyl branch, ethyl branch, propyl branch, butyl Short chain branches such as branching and pentyl branching are less than 0.01 per 1,000 main chain methylene carbons, and long chain branching (that is, branching of hexyl group or more detected by ¹³ C-NMR measurement) Is a linear ethylene polymer having a vinyl group at the end, less than 0.01 per 1,000 main chain methylene carbons Or a linear ethylene copolymer.

  In the synthesis of the macromonomer, the olefin having 3 or more carbon atoms copolymerized with ethylene includes propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, and 3-methyl-1-butene. Alternatively, an α-olefin such as vinylcycloalkane, a cyclic olefin such as norbornene or norbornadiene, a diene such as butadiene or 1,4-hexadiene, or styrene can be exemplified. Two or more of these olefins can be mixed and used.

When an ethylene polymer having a vinyl group at the end or an ethylene copolymer having a vinyl group at the end is used as the macromonomer, the linear polyethylene equivalent (D) number average molecular weight (M _n ) is 2,000 or more. Preferably, it is 3,000 or more, More preferably, it is 5,000 or more. When M _n <2,000, the formula (1) and / or the formula (2) is not satisfied, and it is extremely difficult to perform extrusion lamination molding, so there is a possibility that a laminate cannot be obtained. Moreover, (E) Ratio ( _Mw / _Mn ) of a weight average molecular weight ( _Mw ) and a number average molecular weight ( _Mn ) is 2.0-5.0, Preferably it is 2.0-4.0. More preferably, it is 2.0-3.5. When _Mw / _Mn > 5.0, the ethylene resin layer may be a laminate having poor mechanical strength. In addition, when M _w / M _n <2.0, it is difficult to perform extrusion lamination molding, and thus a laminate may not be obtained.

  There are no particular limitations on the method for producing the macromonomer in the present invention. For example, JP-A-2005-281676, JP-A-2006-28326, JP-A-2006-315999, JP-A-2007-169340, It can be produced by using the methods described in JP 2007-246433 A and JP 2008-50278 A.

  As a specific method for producing a macromonomer, for example, the following general formula (10)

で表される遷移金属化合物［成分（ｉｉ）］を主成分とする触媒を用いて、エチレンを単独で重合するか、または、エチレンと炭素数３以上のオレフィンとを共重合する方法を用いて製造することができる。

And a method of polymerizing ethylene alone or copolymerizing ethylene and an olefin having 3 or more carbon atoms, using a catalyst having a transition metal compound [component (ii)] as a main component. Can be manufactured.

M ² in the component (ii) is a titanium atom, a zirconium atom or a hafnium atom, and X ² is each independently, for example, a hydrogen atom, a halogen or a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms in X ² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a norbornyl group, and a phenyl group. Group, styryl group, biphenylyl group, naphthyl group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group , Triethylphenyl group, tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group, vinyl group, propenyl group , Examples include butenyl group, butadienyl group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like.

R ⁷ and R ⁸ in component (ii) are represented by the following general formula (11), (12) or (13)

で表され、それぞれ同じでも異なっていてもよく、Ｍ^２とともにサンドイッチ構造を形成する。一般式（１１）、（１２）または（１３）におけるＲ^１０は例えば各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基である。

In expressed, which may be the same or different, to form a sandwich structure together with M ^2. R ¹⁰ in the general formula (11), (12) or (13) is, for example, each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms of R ^{10 in} the general formula (11), (12) or (13) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Octyl group, nonyl group, decyl group, norbornyl group, phenyl group, styryl group, biphenylyl group, naphthyl group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group, dipropyl Phenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, diphenylethyl group , Diphenylpropyl group, di Examples include phenylbutyl group, vinyl group, propenyl group, butenyl group, butadienyl group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like.

Specific examples of R ⁷ and R ^{8 in} the general formula (10) include, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopenta Dienyl, ethylcyclopentadienyl, diethylcyclopentadienyl, triethylcyclopentadienyl, tetraethylcyclopentadienyl, propylcyclopentadienyl, dipropylcyclopentadienyl, tripropylcyclo Pentadienyl group, tetrapropylcyclopentadienyl group, butylcyclopentadienyl group, dibutylcyclopentadienyl group, tributylcyclopentadienyl group, tetrabutylcyclopentadienyl group, phenylcyclopentadienyl group, diphenyl Cyclo Antadienyl group, naphthylcyclopentadienyl group, methoxycyclopentadienyl group, trimethylsilylcyclopentadienyl group, indenyl group, methylindenyl group, dimethylindenyl group, trimethylindenyl group, tetramethylindenyl group, pentamethyl Indenyl, hexamethylindenyl, ethylindenyl, diethylindenyl, triethylindenyl, tetraethylindenyl, pentaethylindenyl, hexaethylindenyl, propylindenyl, dipropylindenyl Nyl group, tripropyl indenyl group, tetrapropyl indenyl group, pentapropyl indenyl group, hexapropyl indenyl group, butyl indenyl group, dibutyl indenyl group, tributyl indenyl group, tetrabutyl indenyl Group, pentabutylindenyl group, hexabutylindenyl group, phenylindenyl group, diphenylindenyl group, benzoindenyl group, naphthylindenyl group, methoxyindenyl group, trimethylsilylindenyl group and the like.

In addition, the crosslinking group R ⁹ that bridges R ⁷ and R ⁸ in the general formula (10) is represented by the following general formula (14), (15), or (16)

で表され、これらの式（１４）、（１５）、（１６）において、置換基Ｒ^１１は例えば各々独立して水素原子、ハロゲン、炭素数１〜２０の炭化水素基である。また、Ｙ^２は周期表１４族の原子であり、具体的には例えば炭素原子、ケイ素原子、ゲルマニウム原子、錫原子等が挙げられ、その中でも好ましくは炭素原子、ケイ素原子であり、ｎは１から５の整数である。

In these formulas (14), (15), and (16), the substituents R ¹¹ are each independently, for example, a hydrogen atom, a halogen, or a hydrocarbon group having 1 to 20 carbon atoms. Y ² is an atom belonging to Group 14 of the periodic table, and specifically includes, for example, a carbon atom, a silicon atom, a germanium atom, a tin atom, etc. Among them, a carbon atom and a silicon atom are preferable, and n is 1 To an integer of 5.

Formula (14) may be the same as the hydrocarbon group having 1 to 20 carbon atoms in the hydrocarbon as the base, for example, ^{R 10} having 1 to 20 carbon atoms for ^{R 11} in (15) or (16) .

Specific examples of the general formula (14) include, for example, a methylene group, an ethylidene group, an ethylene group, a propylidene group, a propylene group, a butylidene group, a butylene group, a pentylidene group, a pentylene group, a hexylidene group, an isopropylidene group, and a methylethylmethylene group. , Methylpropylmethylene group, methylbutylmethylene group, bis (cyclohexyl) methylene group, methylphenylmethylene group, diphenylmethylene group, phenyl (methylphenyl) methylene group, di (methylphenyl) methylene group, bis (dimethylphenyl) methylene group Bis (trimethylphenyl) methylene group, phenyl (ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (diethylphenyl) methylene group, phenyl (propylphenyl) methylene group, di (propylphenyl) Tylene group, bis (dipropylphenyl) methylene group, phenyl (butylphenyl) methylene group, di (butylphenyl) methylene group, phenyl (naphthyl) methylene group, di (naphthyl) methylene group, phenyl (biphenyl) methylene group, di (Biphenyl) methylene group, phenyl (trimethylsilylphenyl) methylene group, bis (trimethylsilylphenyl) methylene group, bis (pentafluorophenyl) methylene group, silanediyl group, disilanediyl group, trisilanediyl group, tetrasilanediyl group, dimethylsilanediyl group, Bis (dimethylsilane) diyl group, diethylsilanediyl group, dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediyl group, divinyli Silanediyl group, diallyl silane diyl group, (methyl) (vinyl) silanediyl group, and (allyl) (methyl) silanediyl group. Specific examples of the general formula (15) include, for example, 1,1,3,3-tetramethyldisiloxane-1,3-diyl group, 1,1,3,3-tetraethyldisiloxane-1,3-diyl group. 1,1,3,3-tetraisopropyldisiloxane-1,3-diyl group, 1,1,3,3-tetraphenyldisiloxane-1,3-diyl group, and the like.
Specific examples of the general formula (16) include, for example, 1,1-dimethyl-1-silaethane-1,2-diyl group, 1,1-diethyl-1-silaethane-1,2-diyl group, 1,1- A diisopropyl-1-silaethane-1,2-diyl group, a 1,1-diphenyl-1-silaethane-1,2-diyl group and the like can be exemplified.

As specific compounds represented by the general formula (10) used in the present invention, when M ² is a zirconium atom and X ² is a chlorine atom, for example, methylenebis (cyclopentadienyl) zirconium dichloride, isopropylidenebis ( Cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (cyclopentadienyl) zirconium dichloride, diphenylmethylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, methylenebis (methyl) Cyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (methylcyclopentadienyl) Luconium dichloride, diphenylmethylenebis (methylcyclopentadienyl) zirconium dichloride, ethylenebis (methylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclo Pentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (methylcyclopentadiyl) Enyl) zirconium dichloride, ethylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, methylenebis (2,4-dimethylsilane) Clopentadienyl) zirconium dichloride, isopropylidenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylmethylenebis ( 2,4-dimethylcyclopentadienyl) zirconium dichloride, ethylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (Indenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (indenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ) (Indenyl) zirconium dichloride, ethylene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, diethylsilanediylbis (cyclopentadienyl) zirconium dichloride, di (n- Propyl) silanediylbis (cyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (cyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (cyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride , Di (p-tolyl) silanediylbis (cyclopentadienyl) zirconium dichloride, divinylsilane di Rubis (cyclopentadienyl) zirconium dichloride, diallylsilanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (vinyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (allyl) (methyl) silanediylbis (cyclopentadi) Enyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (cyclopentadi) Enyl) zirconium dichloride, (cyclohexyl) (methyl) bis (cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silane Diylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (methylcyclopentadiyl) Enyl) zirconium dichloride, diisopropylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, (ethyl) (Methyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl Silanediylbis (methylcyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) ) Silanediylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, Di (n-propyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diisopropyl chloride Diyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) Enyl) zirconium dichloride, (ethyl) (methyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) Zirconium dichloride, (methyl) (isopropyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) Clopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopenta) Dienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis ( 2,4-dimethylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilane Irbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (2,4- Dimethylcyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (2,4-dimethylcyclopentadienyl) zirconium dichloride (Methyl) (phenyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, Ethylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, di (n-propyl) silanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, diisopropylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, dicyclohexyl Silanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (2-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (3-Methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (3-isopropylcyclopente Tadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (2,3-dimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (2,4-dimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilane Diyl (2,3,4-trimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (2,3,5-trimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) ) (2-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclohexane) Ntadienyl) (7-ethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-phenylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethylindenyl) zirconium Dichloride, dimethylsilanediyl (cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methoxy-7-methylindenyl) zirconium dichloride, dimethylsilanediyl ( Cyclopentadienyl) (2-dimethylamino-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-trimethylsilyl-7-methylindenyl) zirco Um dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (7-methylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (Cyclopentadienyl) (4-isopropyl-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-phenyl-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadiyl) Enyl) (4-methoxy-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-dimethylamino-7-methylindenyl) zirconium dichloride, di Methylsilanediyl (cyclopentadienyl) (4-trimethylsilyl-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl ( Cyclopentadienyl) (3,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,3,4,7-tetramethylindenyl) zirconium dichloride, dimethylsilanediyl (3 , 4-Dimethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (3,4-bis (trimethylsilyl) cyclopentadienyl) (2,4,7-trimethylindenyl) ) Jill Nium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4-phenyl-7-methylindenyl) zirconium dichloride , Dimethylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride (1,1,3,3-tetramethyldisiloxane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (1,1,3,3-tetraisopropyldisiloxane-1,3-diyl- Bisshik Pentadienyl) zirconium dichloride, (1,1,3,3-tetraphenyldisiloxane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl) -Biscyclopentadienyl) zirconium dichloride, (1,1-diisopropyltyl-1-silaethane-1,2-diyl-biscyclopentadienyl) zirconium dichloride, (1,1-diphenyl-1-silaethane-1, 2-diyl-biscyclopentadienyl) zirconium dichloride, (propane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (1,1,3,3-tetramethylpropane-1,3-diyl- Biscyclopentadienyl) zirconium dichloride (2,2-dimethylpropane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (butane-1,4-diyl-biscyclopentadienyl) zirconium dichloride, (pentane-1,5-diyl) -Biscyclopentadienyl) zirconium dichloride, (1,1,2,2-tetramethyldisilane-1,2-diyl-biscyclopentadienyl) zirconium dichloride, (1,1,2,2-tetraphenyldisilane) -1,2-diyl-biscyclopentadienyl) zirconium dichloride and the like. The compounds obtained by substituting X ¹ of the above transition metal compounds fluorine atom, a bromine atom or an iodine atom can be exemplified. Furthermore, the M ² of the transition metal compound can also be exemplified compounds obtained by replacing the titanium atom or a hafnium atom. These compounds can also be used in combination.

  Examples of the catalyst mainly composed of the component (ii) represented by the formula (10) include a catalyst obtained by bringing the component (ii) into contact with the activation promoter component (iii). As a specific example of the component (iii), the same catalyst as the component (iii) used in combination with the component (i) can be used for the catalyst having the component (i) as a main component.

  Although the specific manufacturing method of the polyethylene resin (B) of the present invention is not particularly limited, (1) ethylene and optionally an olefin having 3 or more carbon atoms are polymerized using a catalyst mainly composed of component (ii). After synthesizing the macromonomer, in the presence of the obtained macromonomer, ethylene and optionally an olefin having 3 or more carbon atoms are polymerized using a catalyst having component (i) as a main component to obtain a polyethylene resin (B). And (2) ethylene and optionally an olefin having 3 or more carbon atoms are polymerized using a catalyst mainly composed of component (i) and component (ii), and a polyethylene resin ( A method for producing B) can be exemplified.

  The polyethylene-based resin (B) is a resin in which a part of the macromonomer obtained by using the component (ii) is incorporated as a comonomer so that a part thereof has a long chain branch. In general, when the molecular weight of the macromonomer is low, the number of macromonomers increases, so that the amount of long chain branching increases and the processability is excellent, but the number average molecular weight decreases and the mechanical strength decreases. On the other hand, when the molecular weight of the macromonomer is high, the mechanical strength is increased, but long chain branching is not generated and processability is lowered. The polyethylene resin (B) of the present invention is preferably a polyethylene resin (B) having a long-chain branched structure, a high number average molecular weight, and a narrow molecular weight distribution, and having excellent processability. High mechanical strength.

  The polyethylene resin (B) of the present invention can be produced by any of gas phase polymerization, slurry polymerization, and solution polymerization, but when it is carried out by slurry polymerization, an excellent particle-form polyethylene resin is produced. can do.

  There are no particular restrictions on the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration in the synthesis of the macromonomer and the production of the polyethylene resin (B), but the polymerization temperature is -100 to 120 ° C., taking productivity into consideration. Then, it is preferable to carry out in the range of 20-120 degreeC, Furthermore, 60-120 degreeC. The polymerization time is usually carried out in the range of 10 seconds to 20 hours, and the polymerization pressure can be carried out in the range of normal pressure to 300 MPa. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions.

  The polyethylene-based resin (B) satisfying the above requirements (a) to (c) can be arbitrarily made according to the manufacturing conditions themselves of the examples described later or minor variations of the condition factors. Specific examples of condition factor fluctuations include: requirements for catalyst components such as the structure of component (ii) and component (i) used, the amount of component (i) relative to component (ii), the type of promoter component used, and the polymerization temperature It can also be made by controlling polymerization conditions such as ethylene partial pressure, the amount of a molecular weight modifier such as hydrogen to be coexisted, and the amount of comonomer to be added. Furthermore, the range of physical properties can be expanded by combining with multi-stage polymerization.

More specifically, it is possible to reduce the number of terminal vinyls by, for example, reducing the ethylene partial pressure, reducing the amount of comonomer addition, or changing the structure of component (ii). Also, the melt tension can change the structure of component (ii), increase the number of terminal vinyls, change the structure of component (i), decrease ethylene partial pressure, increase the number of long chain branches. It can be increased by increasing the long chain branching length, changing the amount of component (i) relative to component (ii), increasing Mw / Mn, and the like. Further, the flow activation energy (E _a ) is based on the structure of component (ii), the number of terminal vinyls, the structure of component (i), the ethylene partial pressure, the number of long chain branches, the length of long chain branches, and the component (ii). Control is possible by the amount of component (i).

  A polyethylene resin composition obtained by blending a specific amount of a low density polyethylene (A) and a polyethylene resin (B) satisfying the above requirements has an excellent appearance of a product obtained by extrusion lamination and good workability. The polyethylene resin composition of the present invention has a low density polyethylene (A) of 1 to 50% by weight, preferably 1 to 30% by weight, more preferably 1 to 20% by weight, polyethylene resin (B) 99 to 50% by weight, Preferably it is 99 to 70% by weight, more preferably 99 to 80% by weight. If the blending amount of the low density polyethylene (A) is less than 1% by weight, it may be difficult to stably perform extrusion laminate molding. On the other hand, when the blending amount of the low density polyethylene (A) exceeds 50% by weight, it may be difficult to reduce the laminate thickness.

The density of the polyethylene resin composition of the present invention is preferably 915 to 965 kg / m ³ , more preferably 920 to 960 kg / m ³ . When the density is in the range of 915 to 965 kg / m ³ , both heat resistance and sealing performance of the laminated product can be achieved.

  The polyethylene resin composition of the present invention preferably has an MFR measured at a load of 2.16 kg (190 ° C.) of 3.0 to 30.0 g / 10 minutes, more preferably 4.0 to 20 g / 10 minutes. When the MFR is in the range of 3.0 to 30.0 g / 10 min, the laminate thickness can be reduced and the extrusion laminate can be stably formed.

The polyethylene resin composition of the present invention has a melt tension (MS ₁₆₀ ) measured at 160 ° C. of preferably 30 mN or more, and more preferably 40 mN or more. When the melt tension (MS ₁₆₀ ) is 30 mN or more, extrusion lamination can be stably performed.

  Each of the low density polyethylene (A) and the polyethylene resin (B) constituting the polyethylene resin composition for extrusion lamination of the present invention may be one kind or a mixture of two or more kinds.

  The polyethylene resin composition of the present invention may be prepared by dry blending a low density polyethylene (A) and a polyethylene resin (B), but a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, etc. The one obtained by melt kneading by a conventionally known method is preferable because a composition having stable quality can be obtained. Among these, from the viewpoint of productivity, a method of melt kneading and granulating using a single screw extruder or a twin screw extruder is common.

  The polyethylene resin of the present invention includes a heat stabilizer, a weather stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a slip agent, a lubricant, a nucleating agent, a pigment, a tackifier, 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 are tackifying resins, waxes, HDPE, L-LDPE, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers. , Polystyrene, or a maleic anhydride graft product thereof, and the like.

  The laminate of the present invention can be obtained by laminating and / or coating a polyethylene-based resin composition forming at least one layer on various substrates by an extrusion laminate molding method. 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, it is preferable to extrude from a die | dye at the temperature of 250-350 degreeC in order to obtain the laminated body with favorable adhesiveness of a base material and a polyethylene-type resin layer.

In addition, at least the surface where the molten film of the polyethylene resin 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.

  The laminate of the present invention is a dry food such as snacks and instant noodles, soup, miso, pickles, sauces, aquatic food and beverage packaging such as beverages, medicine packaging such as medicines and infusion bags, shampoos, cosmetics, and 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 polyethylene resin composition of the present invention has an excellent appearance of a product obtained by extrusion lamination and good workability, and is useful as a resin for extrusion lamination.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  Various physical properties of polyethylene resins in Synthesis Examples, Examples and Comparative Examples were measured by the following methods.

<Molecular weight, molecular weight distribution>
The weight average molecular weight (M _w ) and number average molecular weight (M _n ) were measured by gel permeation 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.

<Number of long-chain branches>
The number of long-chain branches was determined by ¹³ C-NMR using a Varian VNMRS-400 nuclear magnetic resonance apparatus and measuring the number of long-chain branches above the hexyl group. The solvent is tetrachloroethane -d _2. 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 = IA _α / (3 × IA _tot ) (4)
[Wherein, IA _α is the integrated intensity of a long-chain branched α-carbon peak (chemical shift: 34.6 ppm) above the hexyl group, and IA _tot is the integrated intensity of the main chain methylene carbon peak (30.0 ppm). It is. ]
The terminal structure of the polymer such as vinyl terminal and saturated terminal was measured by ¹³ C-NMR using a Varian VNMRS-400 type nuclear magnetic resonance apparatus. The solvent is tetrachloroethane -d _2. The number of vinyl ends was determined from the average value of peaks at 114 ppm and 139 ppm as the number per 1,000 main chain methylene carbons (chemical shift: 30 ppm). Similarly, the number of saturated terminals was determined from the average value of peaks at 32.3 ppm, 22.9 ppm, and 14.1 ppm. From the vinyl terminal number (X) and the saturated terminal number (Y), the vinyl terminal content Z (= X / (X + Y) × 2) was determined.

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

<MFR>
MFR was measured at 190 ° C. and 2.16 kg load according to JIS K6760 (1995).

<Melting tension>
Polyethylene used for the measurement of melt tension (MS) was previously added with 1,500 ppm Irganox 1010 ^TM (manufactured by Ciba Specialty Chemicals) and 1,500 ppm Irgafos 168 ^TM (manufactured by Ciba Specialty Chemicals) as a heat-resistant stabilizer. Was kneaded for 3 minutes at 190 ° C. and at a rotation speed of 30 rpm under a nitrogen stream using an internal mixer (manufactured by Toyo Seiki Seisakusho, trade name: Labo Plast Mill). The melt tension (MS) is a capillary viscometer (Toyo Seiki Seisakusho, trade name: Capillograph) with a barrel diameter of 9.55 mm, a length (L) of 8 mm, a diameter (D) of 2.095 mm, and an inflow angle of 90 °. A die was mounted and measured. In MS ₁₆₀ , 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. In MS ₁₉₀ , the temperature was set to 190 ° 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.

<Neck-in>
The polyethylene resin 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 / min. As the difference between the opening width of the T die and the coating width of the polyethylene resin composition when the extrusion laminating resin composition is 20 μm thick on a kraft paper substrate having a basis weight of 50 g / m ² Was the neck-in, and the value was measured. At this time, the case where the neck-in was smaller than that of the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corp.) laminated under the same conditions was marked with ◯, when the neck-in was large, and when the neck-in was equal, Δ.

<Minimum film thickness>
The polyethylene resin 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 / min. As above, extrusion lamination was performed on a kraft paper substrate having a basis weight of 50 g / m ^{2 so that} the resin composition for extrusion lamination had a thickness of 20 μm. Thereafter, the discharge amount was reduced, and the laminate thickness at which continuous extrusion lamination could not be continuously performed for 100 m or more was made the minimum film thickness, and the value was measured. At this time, the case where the minimum film thickness was thinner than that of the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) laminated under the same conditions was indicated as ◯, the case where it was thick as x, and the case where it was equivalent as △.

<Appearance of molten film>
The polyethylene resin 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 the appearance of the molten film was visually observed. At this time, a case where the appearance was better than that of a high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corp.) which was laminated under the same conditions was indicated as ◯, a case where the appearance was poor, and a case where the appearance was equivalent were indicated as △.

<Contamination of cooling roll surface>
The polyethylene resin 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 20 m / min. Then, extrusion lamination molding was continuously performed for 500 m on a kraft paper substrate having a basis weight of 50 g / m ^{2 so that} the resin composition for extrusion lamination had a thickness of 20 μm. After laminating, the deposit on the surface of the cooling roll was measured. In this case, the case where the surface of the cooling roll was better than the high pressure method low density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) laminated under the same conditions was rated as ◯, the case where it was defective as x, and the case where it was equivalent as △. . In addition, the cooling roll used the mirror roll and the roll cooling temperature was 45 degreeC.

  Furthermore, the preparation of the modified hectorite, the preparation of the catalyst, the production of the polyethylene resin and the solvent purification were all carried out under an inert gas atmosphere. The solvent used for the preparation of the modified hectorite, the catalyst, and the polyethylene resin were all purified, dried and deoxygenated by a known method in advance. Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, propane-1,3-diylbis (cyclopentadienyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilanediyl (Cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, 1,1,3,3-tetramethyldisiloxane-1,3-diylbis (cyclopentadienyl) zirconium dichloride, diphenylmethylene (1- Indenyl) (9-fluorenyl) zirconium dichloride was synthesized and identified by a known method. A hexane solution (0.714M) of triisobutylaluminum was manufactured by Tosoh Finechem Corporation.

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, 330 g (1.1 mol) of N, N-dimethyl-octadecylamine was added to the resulting solution and heated to 60 ° C. A hydrochloride 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 the modified | denatured hectorite with an average particle diameter of 5.2 micrometers was obtained by grind | pulverizing with a jet mill.

[Preparation of catalyst (p)]
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 catalyst precursor slurry (100 g / L) was obtained.

  10 mol% of isopropylidene (1-cyclopentadienyl) (2,7-di-) with respect to dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride was added to the catalyst precursor slurry prepared above. 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 (0.15M) of triisobutylaluminum was further added to finally obtain a catalyst slurry of 100 g / L.

[Production of polyethylene resin (B-1)]
Into a polymerization vessel having an internal volume of 540 liters, 300 liters of hexane and 5.9 liters of 1-butene were introduced, and the internal temperature of the autoclave was raised to 70 ° C. 120 ml of the catalyst (p) was added to the autoclave, and an ethylene / hydrogen mixed gas (hydrogen: containing 500 ppm) was introduced until the partial pressure reached 0.9 MPa to initiate polymerization. During the polymerization, an ethylene / hydrogen mixed gas (containing hydrogen: 500 ppm) was continuously introduced so that the partial pressure was maintained at 0.9 MPa. The polymerization temperature was controlled at 70 ° C. After 90 minutes from the start of polymerization, the internal pressure of the polymerization vessel was released, and the contents were filtered and dried to obtain 54 kg of a polyethylene resin powder. The density of the obtained polyethylene resin (B-1) is 924 kg / m ³ , MFR is 25 g / 10 min, the number of long chain branches is 0.13 per 1000 carbon atoms, MS ₁₉₀ is 22 mN, and MS ₁₆₀ is 34 mN. there were.

  In this production example, the production of a macromonomer shown in Reference Example 1 below and the production of a polyethylene resin (B-1) by copolymerization of ethylene and 1-butene in the presence of the macromonomer are performed. Yes.

Reference example 1
[Manufacture of macromonomer]
Synthetic Example 1 [Production of Polyethylene Resin (B-1)], except that 120 ml of the catalyst precursor slurry prepared in Synthesis Example 1 [Preparation of Catalyst (p)] was added instead of Catalyst (p). Polymerization was performed in the same manner to obtain an ethylene copolymer powder. Mn of the obtained ethylene copolymer was 15,500, Mw / Mn = 2.25, and Z = 0.28. Further, no long chain branching was detected.

Synthesis example 2
[Production of polyethylene resin (B-2)]
5.6 liters of 1-butene was introduced, 131 ml of catalyst (p) prepared in Synthesis Example 1 [Preparation of catalyst (p)] was added, and only ethylene was used instead of the ethylene / hydrogen mixed gas. Was polymerized in the same manner as in Synthesis Example 1 [Production of polyethylene resin (B-1)] to obtain 57 kg of polyethylene resin powder. The density of the obtained polyethylene resin (B-2) is 924 kg / m ³ , MFR is 15 g / 10 min, the number of long chain branches is 0.13 per 1000 carbon atoms, MS ₁₉₀ is 24 mN, and MS ₁₆₀ is 38 mN. there were.

  In this production example, the production of a macromonomer shown in Reference Example 2 below and the production of a polyethylene resin (B-1) by copolymerization of ethylene and 1-butene in the presence of the macromonomer are performed. Yes.

Reference example 2
[Manufacture of macromonomer]
Synthetic example 2 [Production of polyethylene resin (B-2)] except that 131 ml of the catalyst precursor slurry prepared in Synthesis example 1 [Preparation of catalyst (p)] was added instead of catalyst (p). Polymerization was performed in the same manner to obtain an ethylene copolymer powder. Mn of the obtained ethylene copolymer was 16,000, Mw / Mn = 2.35, and Z = 0.28. Further, no long chain branching was detected.

Synthesis example 3
[Preparation of catalyst (q)]
Instead of dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride, 8.53 g (20.0 mmol) of dimethylsilanediyl (cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride was used. In addition to isopropylidene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-di- t-butyl-9-fluorenyl) zirconium dichloride was added in the same manner as in Synthesis Example 1 [Preparation of catalyst (p)] except that 0.70 g (1.05 mmol) was added, and a catalyst of 100 g / L was prepared. A slurry was obtained.

[Production of polyethylene resin (B-3)]
Synthesis Example 1 [polyethylene system, except that 5.2 liters of 1-butene was introduced, 106 ml of the catalyst (q) was added instead of the catalyst (p), and ethylene was used instead of the ethylene / hydrogen mixed gas. Polymerization was carried out in the same manner as in Production of Resin (B-1)] to obtain 55 kg of polyethylene resin powder. The density of the obtained polyethylene resin (B-3) is 924 kg / m ³ , MFR is 5 g / 10 min, the number of long chain branches is 0.10 per 1000 carbon atoms, MS ₁₉₀ is 44 mN, and MS ₁₆₀ is 66 mN. there were.

  In this production example, the production of a macromonomer shown in Reference Example 3 below and the production of a polyethylene resin (B-3) by copolymerization of ethylene and 1-butene in the presence of the macromonomer were performed. Yes.

Reference example 3
[Manufacture of macromonomer]
Synthetic Example 3 [Production of Polyethylene Resin (B-3)], except that 106 ml of the catalyst precursor slurry prepared in Synthesis Example 3 [Preparation of Catalyst (q)] was added instead of Catalyst (q). Polymerization was performed in the same manner to obtain an ethylene copolymer powder. Mn of the obtained ethylene copolymer was 19,000, Mw / Mn = 2.50, and Z = 0.25. Further, no long chain branching was detected.

Synthesis example 4
[Preparation of catalyst (r)]
Instead of dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride, 7.43 g (18.0 mmol) of dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride and 1, Synthesis Example 1 [Preparation of catalyst (p)] except that 0.85 g (2.0 mmol) of 1,3,3-tetramethyldisiloxane-1,3-diylbis (cyclopentadienyl) zirconium dichloride was added Was prepared in the same manner as above to obtain a catalyst slurry of 100 g / L.

[Production of polyethylene resin (B-4)]
6.4 liters of 1-butene was introduced, 133 ml of the catalyst (r) was added instead of the catalyst (p), and an ethylene / hydrogen mixed gas (hydrogen: 500 ppm) instead of the ethylene / hydrogen mixed gas (hydrogen: 500 ppm included). Polymerization was carried out in the same manner as in Synthesis Example 1 [Production of polyethylene resin] except that 1000 ppm was used) to obtain 53 kg of polyethylene resin powder. The density of the obtained polyethylene resin (B-4) is 924 kg / m ³ , MFR is 15 g / 10 min, the number of long-chain branches is 0.12 per 1000 carbon atoms, MS ₁₉₀ is 27 mN, and MS ₁₆₀ is 40 mN. there were.

  In this production example, the production of a macromonomer shown in the following Reference Example 4 and the production of a polyethylene resin (B-4) by copolymerization of ethylene and 1-butene in the presence of the macromonomer were performed. Yes.

Reference example 4
[Manufacture of macromonomer]
Synthetic example 4 [Production of polyethylene resin (B-4)] except that 133 ml of the catalyst precursor slurry prepared in Synthesis example 4 [Preparation of catalyst (r)] was added instead of catalyst (r). Polymerization was performed in the same manner to obtain an ethylene copolymer powder. Mn of the obtained ethylene copolymer was 16,000, Mw / Mn = 2.75, and Z = 0.27. Further, no long chain branching was detected.

Synthesis example 5
[Preparation of catalyst (s)]
Instead of dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride, 6.83 g (16.0 mmol) of dimethylsilanediyl (cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride was used. In addition to isopropylidene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-di- t-butyl-9-fluorenyl) zirconium dichloride was added in the same manner as in Synthesis Example 1 [Preparation of catalyst (p)] except that 2.68 g (4.0 mmol) was added, and a 100 g / L catalyst was prepared. A slurry was obtained.

[Production of polyethylene resin (B-5)]
7.6 liters of 1-butene was introduced, 135 ml of the catalyst (s) was added instead of the catalyst (p), ethylene was used instead of the ethylene / hydrogen mixed gas, and the polymerization temperature was controlled at 60 ° C. Except for the above, polymerization was carried out in the same manner as in Synthesis Example 1 [Production of polyethylene resin (B-1)] to obtain 54 kg of polyethylene resin powder. The density of the obtained polyethylene resin (B-5) is 918 kg / m ³ , MFR is 5 g / 10 min, the number of long chain branches is 0.10 per 1000 carbon atoms, MS ₁₉₀ is 49 mN, and MS ₁₆₀ is 70 mN. there were.

  In this production example, the production of a macromonomer shown in the following Reference Example 5 and the production of a polyethylene resin (B-5) by copolymerization of ethylene and 1-butene in the presence of the macromonomer were performed. Yes.

Reference Example 5
[Manufacture of macromonomer]
Synthetic Example 5 [Production of Polyethylene Resin (B-5)], except that 135 ml of the catalyst precursor slurry prepared in Synthesis Example 5 [Preparation of Catalyst (s)] was added instead of Catalyst (s). Polymerization was performed in the same manner to obtain an ethylene copolymer powder. Mn of the obtained ethylene copolymer was 21,000, Mw / Mn = 2.48, and Z = 0.25. Further, no long chain branching was detected.

Synthesis Example 6
[Preparation of catalyst (t)]
500 g of the modified hectorite prepared in Synthesis Example 1 [Preparation of modified hectorite] was suspended in 1.8 liters of hexane, 2.9 liters of a hexane solution of triisobutylaluminum (0.714 M) was added, and 1 at room temperature. By stirring for a time, a contact product of modified hectorite and triisobutylaluminum was obtained. On the other hand, a catalyst slurry (100 g / L) was obtained by adding a solution obtained by dissolving 6.97 g (20 mmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride in toluene and stirring at room temperature overnight. .

[Manufacture of macromonomer]
7.6 liters of 1-butene was introduced, 135 ml of the catalyst (t) was added instead of the catalyst (p), ethylene was used instead of the ethylene / hydrogen mixed gas, and the ethylene partial pressure was controlled to 1.2 MPa. The polymerization was carried out in the same manner as in Synthesis Example 1 [Production of polyethylene resin (B-1)] except that the polymerization temperature was controlled at 85 ° C. The macromonomer extracted from the polymerization vessel had Mn = 10,950, Mw / Mn = 2.61, and Z = 0.57. Further, no long chain branching was detected.

[Production of polyethylene resin (B-6)]
In the polymerization vessel containing the macromonomer produced above and having an internal volume of 540 liters, 0.22 liter of 1-butene, 0.75 liter of a hexane solution of triisobutylaluminum (0.714 mol / L) and diphenylmethylene (1- Indenyl) (9-fluorenyl) zirconium dichloride (3.75 mmol) was introduced, and the internal temperature of the autoclave was raised to 85 ° C. Polymerization was started by introducing an ethylene / hydrogen mixed gas (hydrogen 22,000 ppm) until the partial pressure reached 0.2 MPa. During the polymerization, an ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure was maintained at 0.2 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 54 kg of a polyethylene resin was obtained. The density of the obtained polyethylene resin (B-6) is 948 kg / m ³ , MFR is 30 g / 10 min, the number of long chain branches is 0.15 per 1000 carbon atoms, MS ₁₉₀ is 21 mN, and MS ₁₆₀ is 30 mN. there were.

Synthesis example 7
[Production of polyethylene resin (B-7)]
Polymerization was carried out in the same manner as in Synthesis Example 6 [Production of polyethylene resin (B-6)] except that 1-butene was not added, and 50 kg of polyethylene resin was obtained. The density of the obtained polyethylene resin (B-7) is 963 kg / m ³ , MFR is 15 g / 10 min, the number of long chain branches is 0.12 per 1000 carbon atoms, MS ₁₉₀ is 30 mN, and MS ₁₆₀ is 55 mN. there were.

  Table 1 shows the characteristics of the macromonomer and the characteristics of the polyethylene resins (B-1) to (B-7) in Synthesis Examples 1 to 7.

下記実施例および比較例で用いた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 low density polyethylene used in the following Examples and Comparative Examples.

実施例１
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、ＭＳ_１６０２９５ｍＮ）（以下、（Ａ−１）という。）１５重量％、合成例３に示したポリエチレン系樹脂（Ｂ−３）８５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、ポリエチレン樹脂組成物のペレットを得た。得られたペレットは、ポリエチレン系樹脂の評価方法に示した方法によりラミネート成形した。

Example 1
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 360 manufactured by Tosoh Corporation; density 919 kg / m ³ , MFR _1.6 g / 10 min, MS ₁₆₀ 295 mN) (hereinafter referred to as (A-1)). 15% by weight, 85% by weight of the polyethylene resin (B-3) shown in Synthesis Example 3 was premixed in a tumbler mixer, and then adjusted to a cylinder temperature of 180 ° C. PDA-50) was melt kneaded and granulated to obtain polyethylene resin composition pellets. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 3.

Example 2
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 205 manufactured by Tosoh Corporation; density 924 kg / m ³ , MFR ³ g / 10 min, MS _{160 160} mN) (A-2) 5% by weight, Synthesis Example 2 After 95% by weight of the indicated polyethylene resin (B-2) was premixed with a tumbler mixer, it was melt kneaded with a single-screw extruder (model PDA-50, manufactured by Plako Co., Ltd.) adjusted to a cylinder temperature of 180 ° C. Granulation was performed to obtain polyethylene resin composition pellets. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 3.

Example 3
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 360 manufactured by Tosoh Corporation; density 919 kg / m ³ , MFR _1.6 g / 10 min, MS ₁₆₀ 295 mN) (A-1) 50% by weight, synthesis example 50% by weight of the polyethylene resin (B-2) shown in 2 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. The mixture was kneaded and granulated to obtain polyethylene resin composition pellets. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 3.

Example 4
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 205 manufactured by Tosoh Corporation; density 924 kg / m ³ , MFR ³ g / 10 min, MS _{160 160} mN) (A-2) 15% by weight, Synthesis Example 1 85% by weight of the indicated polyethylene resin (B-1) was premixed with a tumbler mixer, and then melt-kneaded with a single screw extruder (model PDA-50, manufactured by Plako Co., Ltd.) adjusted to a cylinder temperature of 180 ° C. Granulation was performed to obtain polyethylene resin composition pellets. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 3.

Example 5
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 360 manufactured by Tosoh Corporation; density 919 kg / m ³ , MFR _1.6 g / 10 min, MS ₁₆₀ 295 mN) (A-1) 25% by weight, synthesis example 75% by weight of the polyethylene resin (B-4) shown in Fig. 4 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. The mixture was kneaded and granulated to obtain polyethylene resin composition pellets. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 3.

Example 6
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, MS ₁₆₀ 295 mN) (A-1) 10% by weight, synthesis example 90% by weight of the polyethylene resin (B-5) shown in Fig. 5 was premixed with a tumbler mixer, and then melted with a single screw extruder adjusted to a cylinder temperature of 180 ° C (model PDA-50, manufactured by Plako). The mixture was kneaded and granulated to obtain polyethylene resin composition pellets. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 3.

Example 7
Low-density polyethylene obtained by a high-pressure radical polymerization method (trade name Petrocene 360 manufactured by Tosoh Corporation); density 919 kg / m ³ , MFR _1.6 g / 10 min, MS ₁₆₀ 295 mN) (A-1) 2.5% by weight, A single-screw extruder (model PDA, manufactured by Plako Co., Ltd.) was prepared by premixing 97.5% by weight of the polyethylene resin (B-6) shown in Synthesis Example 6 with a tumbler mixer and adjusting the cylinder temperature to 180 ° C. 50) was melt-kneaded and granulated to obtain pellets of a polyethylene resin composition. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 3.

Example 8
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 205 manufactured by Tosoh Corporation; density 924 kg / m ³ , MFR ³ g / 10 min, MS _{160 160} mN) (A-2) 7.5% by weight, synthesis example A single-screw extruder (model PDA-50, manufactured by Plako Co., Ltd.) after premixing 92.5% by weight of the polyethylene resin (B-7) shown in No. 7 with a tumbler mixer and adjusting the cylinder temperature to 180 ° C. And kneaded and granulated to obtain pellets of polyethylene resin composition. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 3.

Example 9
Low-density polyethylene obtained by high-pressure radical polymerization method (trade name Petrocene 217 manufactured by Tosoh Corporation); density 923 kg / m ³ , MFR 4.5 g / 10 min, MS _{160 160} mN) (A-3) 25 wt%, synthesis example 75% by weight of the polyethylene resin (B-4) shown in Fig. 4 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. The mixture was kneaded and granulated to obtain polyethylene resin composition pellets. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 3.

Example 10
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 3M04A manufactured by Tosoh Corporation; density 924.5 kg / m ³ , MFR 4.5 g / 10 min, MS _{160 110} mN) (A-4) 25% by weight, A single screw extruder (model PDA-50, manufactured by Plako Co., Ltd.) after 75% by weight of the polyethylene resin (B-4) shown in Synthesis Example 4 was premixed with a tumbler mixer and then adjusted to a cylinder temperature of 180 ° C. And kneaded and granulated to obtain pellets of polyethylene resin composition. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 3.

比較例１
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、ＭＳ_１６０２９５ｍＮ）（Ａ−１）０．５重量％、合成例３に示したポリエチレン系樹脂（Ｂ−３）９９．５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、ポリエチレン樹脂組成物のペレットを得た。得られたペレットは、ポリエチレン系樹脂の評価方法に示した方法によりラミネート成形した。

Comparative Example 1
Low-density polyethylene obtained by a high-pressure radical polymerization method (trade name Petrocene 360 manufactured by Tosoh Corporation); density 919 kg / m ³ , MFR _1.6 g / 10 min, MS ₁₆₀ 295 mN) (A-1) 0.5% by weight, After premixing 99.5% by weight of the polyethylene resin (B-3) shown in Synthesis Example 3 with a tumbler mixer, a single screw extruder adjusted to a cylinder temperature of 180 ° C. (Model: PDA, manufactured by Placo) 50) was melt-kneaded and granulated to obtain pellets of a polyethylene resin composition. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 4.

  When the obtained polyethylene resin composition was extrusion laminated, the neck-in was larger and poorer than that of the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) laminated and molded under the same conditions.

Comparative Example 2
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 360 manufactured by Tosoh Corporation; density 919 kg / m ³ , MFR _1.6 g / 10 min, MS ₁₆₀ 295 mN) (A-1) 55 wt%, synthesis example 45% by weight of the polyethylene resin (B-3) shown in 3 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. The mixture was kneaded and granulated to obtain polyethylene resin composition pellets. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 4.

  When the obtained polyethylene resin composition was extrusion-laminated, the minimum film thickness could not be made thinner than the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corp.) laminated under the same conditions. It was.

Comparative Example 3
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 205 manufactured by Tosoh Corporation; density 924 kg / m ³ , MFR ³ g / 10 min, MS _{160 160} mN) (A-2) 0.5% by weight, synthesis example A single-screw extruder (model PDA-50, manufactured by Plako Co., Ltd.) prepared by premixing 99.5% by weight of the polyethylene resin (B-2) shown in 2 with a tumbler mixer and then adjusting the cylinder temperature to 180 ° C. And kneaded and granulated to obtain pellets of polyethylene resin composition. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 4.

  When the obtained polyethylene resin composition was extrusion laminated, the neck-in was larger and poorer than that of the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) laminated and molded under the same conditions.

Comparative Example 4
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 360 manufactured by Tosoh Corporation; density 919 kg / m ³ , MFR _1.6 g / 10 min, MS ₁₆₀ 295 mN) (A-1) 55 wt%, synthesis example After premixing 45% by weight of the polyethylene resin (B-2) shown in No. 2 with a tumbler mixer, it was melted with a single-screw extruder (model PDA-50, manufactured by Plako Co., Ltd.) adjusted to a cylinder temperature of 180 ° C. The mixture was kneaded and granulated to obtain polyethylene resin composition pellets. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 4.

  When the obtained polyethylene resin composition was extrusion-laminated, the minimum film thickness could not be made thinner than the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corp.) laminated under the same conditions. It was.

Comparative Example 5
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 205, manufactured by Tosoh Corporation); density 924 kg / m ³ , MFR ³ g / 10 min, MS _{160 160} mN) (A-2) 15 wt%, with metallocene catalyst After preliminarily mixing 85 wt% of the obtained linear low density polyethylene (trade name Nipolon Z 04P66A; density 917 kg / m ³ , MFR 15 g / 10 min) (C-1) manufactured by Tosoh Corporation with a tumbler mixer, The mixture was melt-kneaded and granulated with a single screw extruder (model PDA-50, manufactured by Plako Co., Ltd.) adjusted to a cylinder temperature of 180 ° C. to obtain pellets of a polyethylene resin composition. The obtained pellets were laminated by the method shown in the polyethylene resin evaluation method.

  The polyethylene resin composition thus obtained was measured for density, MFR, and MS, and evaluated for neck-in, minimum film thickness, appearance of the molten film, and contamination of the cooling roll surface during extrusion lamination molding. These evaluation results are shown in Table 4.

  When the obtained polyethylene resin composition is extrusion-laminated, only a neck-in equivalent to the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) laminated under the same conditions can be obtained, and the appearance of the molten film is It was inferior.

Comparative Example 6
Low-density polyethylene (trade name Petrocene 205 manufactured by Tosoh Corp .; density 924 kg / m ³ , MFR ³ g / 10 min, MS _{160 160} mN) (A-2) 100% by weight of polyethylene resin obtained by high-pressure radical polymerization method Lamination was performed by the method shown in the evaluation method.

  MS was measured and evaluated for neck-in, minimum film thickness, appearance of molten film, and contamination on the surface of the cooling roll during extrusion lamination molding. These evaluation results are shown in Table 4. Neck-in equivalent to the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) laminated and molded under the same conditions, the appearance of the molten film, and contamination of the surface of the cooling roll only The minimum film thickness was not obtained and was poor.

Comparative Example 7
100% by weight of the polyethylene resin (B-4) shown in Synthesis Example 4 was laminated by the method shown in the evaluation method for polyethylene resin.

  MS was measured and evaluated for neck-in, minimum film thickness, appearance of molten film, and contamination on the surface of the cooling roll during extrusion lamination molding. These evaluation results are shown in Table 4, and the neck-in was greatly poor compared to the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) laminated by the same conditions.

Comparative Example 8
Linear low-density polyethylene (trade name Nipolon-Z 04P66A manufactured by Tosoh Corp .; density 917 kg / m ³ , MFR 15 g / 10 min) (C-1) (C-1) 100% by weight of polyethylene resin obtained by metallocene catalyst Lamination was performed by the method shown in the evaluation method.

  MS was measured and extrusion laminate molding was attempted, but the molten film was not stable and a laminate could not be obtained. In addition, although the evaluation result of the external appearance of a molten film and the contamination of the surface of a cooling roll is shown in Table 4, only the performance equivalent to the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) evaluated under the same conditions is obtained. There wasn't.

Comparative Example 9
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 360, manufactured by Tosoh Corporation); density 919 kg / m ³ , MFR _1.6 g / 10 min, MS ₁₆₀ 295 mN) (A-1) 100% by weight is polyethylene-based Laminate molding was carried out by the method shown in the resin evaluation method.

  Although MS was measured and extrusion laminate molding was attempted, the take-up speed of the substrate could not be increased, and a laminate could not be obtained. In addition, although the evaluation result of the external appearance of a molten film and the contamination of the surface of a cooling roll is shown in Table 4, only the performance equivalent to the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) evaluated under the same conditions is obtained. There wasn't.

Comparative Example 10
Low-density polyethylene obtained by high-pressure radical polymerization (trade name Petrocene 217 manufactured by Tosoh Corporation); density 923 kg / m ³ , MFR 4.5 g / 10 min, MS _{160 160} mN) (A-3) 100% by weight based on polyethylene Laminate molding was carried out by the method shown in the resin evaluation method.

  MS was measured and evaluated for neck-in, minimum film thickness, appearance of molten film, and contamination on the surface of the cooling roll during extrusion lamination molding. These evaluation results are shown in Table 4. Neck-in equivalent to the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) laminated and molded under the same conditions, the appearance of the molten film, and contamination of the surface of the cooling roll only The minimum film thickness was not obtained and was poor.

Comparative Example 11
Low-density polyethylene (trade name Petrocene 3M04A manufactured by Tosoh Corporation); density 924.5 kg / m ³ , MFR 4.5 g / 10 min, MS _{160 110} mN) (A-4) 100% by weight obtained by high-pressure radical polymerization method Laminate molding was performed by the method shown in the evaluation method of polyethylene resin.

  MS was measured and evaluated for neck-in, minimum film thickness, appearance of molten film, and contamination on the surface of the cooling roll during extrusion lamination molding. These evaluation results are shown in Table 4, but only the appearance of the molten film equivalent to the high-pressure method low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation) laminated under the same conditions, and contamination of the surface of the cooling roll can be obtained. The neck-in was large and the minimum film thickness was too thick.

Comparative Example 12
Low-density polyethylene (trade name Petrocene 203 manufactured by Tosoh Corporation); density 919 kg / m ³ , MFR 8 g / 10 min, MS ₁₆₀ 70 mN) (A-5) 100% by weight of polyethylene resin obtained by high-pressure radical polymerization method Lamination was performed by the method shown in the evaluation method.

  MS was measured and evaluated for neck-in, minimum film thickness, appearance of molten film, and contamination on the surface of the cooling roll during extrusion lamination molding. These evaluation results are shown in Table 4.

Claims (6)

The density obtained by the high-pressure radical polymerization method is 915 to 935 kg / m ³ , and the melt mass flow rate (hereinafter referred to as MFR) measured at 2.16 kg load (190 ° C.) is 0.5 to 5.0 g / 10. Low-density polyethylene (A) 1 to 50% by weight and polyethylene resin composition (B) 99 to 50% by weight satisfying the following requirements (a) to (c): .
(A) A density of 910-965 kg / m ³ ,
(B) 0.01 to 3.0 long chain branches having 1,000 or more carbon atoms per 1,000 carbon atoms,
(C) Melt tension (MS ₁₉₀ ) (mN) measured at 190 ° C. and MFR (g / 10 min) measured at 2.16 kg load (190 ° C.) are expressed by the following formula (1)
MS ₁₉₀ > 22 × MFR ^−0.88 (1)
In addition, the melt tension (MS ₁₆₀ ) (mN) measured at 160 ° C. and the MFR (g / 10 minutes) measured at 2.16 kg load (190 ° C.) satisfy the following formula (2).
MS ₁₆₀ > 110-110 × log (MFR) (2) A macromonomer comprising an ethylene polymer having a vinyl group at the terminal obtained by polymerizing ethylene, or an ethylene copolymer having a vinyl group at the terminal obtained by copolymerizing ethylene and an olefin having 3 or more carbon atoms. There,
(D) the number average molecular weight (M _n ) is 2,000 or more,
(E) a weight average molecular weight _{(M n)} and the number average molecular weight in the presence of _{(M n)} and the ratio _(M w / _{M n)} is 2.0 to 5.0 macromonomer, or of the macromonomer The polyethylene resin composition according to claim 1, wherein a polyethylene resin obtained by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms is used as the polyethylene resin (B) simultaneously with the synthesis. The polyethylene resin composition according to claim 1 or 2, wherein the following requirements (f) to (h) are satisfied.
(F) Density is 915 to 965 kg / m ³
(G) MFR measured under 2.16 kg load (190 ° C.) is 3.0 to 30.0 g / 10 min.
(H) Melt tension (MS ₁₆₀ ) measured at 160 ° C. is 30 mN or more It is an object for extrusion lamination, The polyethylene resin composition in any one of Claims 1-3 characterized by the above-mentioned. The polyethylene resin composition for extrusion lamination according to any one of claims 1 to 4, wherein a low density polyethylene (A) having a melt tension (MS ₁₆₀ ) measured at 160 ° C of 150 mN or more is used. A laminate comprising at least one layer comprising the polyethylene resin composition according to claim 1.