KR20090117629A - Polyethylene resin composition and laminate thereof - Google Patents

Abstract

PURPOSE: A polyethylene resin composition is provided to improve the appearance of products product obtained by an extrusion laminate, to ensure excellent processability and to be used as a resin for the extrusion laminate. CONSTITUTION: A polyethylene resin composition comprises a low-density polyethylene 1~50 wt% and a polyethylene-based resin 99~50 wt%. The low density polyethylene(A) is obtained by high-pressure radical polymerization. A melt mass flow rate (MRF) measured at 2.16 kg load at 190 °C is 0.5~5.0 g/10 min. The density is 915~935 kg/m.

Description

Polyethylene resin composition and laminated body which consist of this {POLYETHYLENE RESIN COMPOSITION AND LAMINATE THEREOF}

The present invention relates to a polyethylene resin composition and a laminate comprising the same. More specifically, it is related with the polyethylene resin composition which is excellent in the external appearance of the product obtained by extrusion lamination, and is excellent in workability, and the laminated body which consists of this.

Among the laminates obtained by extrusion lamination, a laminate comprising at least one layer of polyethylene resin is used in a wide range of applications such as kraft packaging, soft packaging, photo paper support, tape, and various containers. Conventionally, branched low density polyethylene (LDPE) has been mainly used as a polyethylene resin used for these laminated bodies because of its outstanding moldability. However, the density of LDPE is generally in the range of 0.918 to 0.925 g / cm 3, and it is difficult to change physical properties, for example, heat resistance, rigidity, gas barrier properties, and the like, which are changed with the density. In addition, when LDPE has a high forming speed and a thin laminate thickness, the molten film is likely to break, and under these conditions, poor adhesion of the substrate is likely to occur, and it is difficult to obtain a stable product. 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 depending on the number of short chain branches. It was difficult to obtain the laminated body by lamination processing. Then, the method of obtaining a laminated body by extrusion-laminating a mixture of linear polyethylene and LDPE is reported (for example, refer patent documents 1-4). In this method, however, thermal deterioration occurs in the mixing process of the polyethylene resin, and odor tends to occur in the laminate, and melt unevenness occurs during extrusion molding due to poor mixing of the polyethylene resin, resulting in a surface failure. The smooth laminated body may not be obtained in some cases.

Moreover, by changing the polymerization catalyst of ethylene, the technique which introduces long-chain branching into L-LDPE and HDPE, and does not mix LDPE, and improves moldability is reported (for example, refer patent document 5). However, the melt tension of polyethylene-based resins obtained using these techniques is still insufficient and it is difficult to stably perform extrusion laminate molding. Therefore, the resultant laminated body did not solve the above-mentioned problem.

[Patent Document 1] Japanese Unexamined Patent Publication No. Hei 6-65443

[Patent Document 2] Japanese Unexamined Patent Publication No. Hei 6-322189

[Patent Document 3] Japanese Patent Application Laid-Open No. 7-92610

[Patent Document 4] Japanese Unexamined Patent Publication No. 2000-73018

[Patent Document 5] Japanese Unexamined Patent Publication No. 2006-43911

An object of the present invention is to solve the problems of the prior art as described above, and to provide a polyethylene resin composition which is excellent in appearance of a product obtained by extrusion lamination and has good processability, and a laminate comprising the same.

The present invention has been found as a result of intensive examination to achieve the above object. That is, in 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 to 5.0 g / 10 min. Provided is a polyethylene resin composition comprising 1 to 50% by weight of a low density polyethylene (A) and 99 to 50% by weight of a polyethylene-based resin (B) satisfying the requirements of the following (a) to (c).

(a) density is 910-965 kg / m 3,

(b) from 0.01 to 3.0 carbon atoms with 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 given by the following equation (1)

MS ₁₉₀ > 22 x 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)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The low-density polyethylene (A) obtained by the high pressure radical polymerization method which comprises the polyethylene resin composition for extrusion laminates of this invention has the density in the range of 915-935 kg / m <3>. If the density is less than 915 kg / m 3, the self-adhesion of the film increases, there is a fear that blocking occurs. On the other hand, the density exceeding 935 kg / m <3> has a high melting | fusing point of the low density polyethylene (A), and there exists a possibility that low temperature heat-sealing property may deteriorate.

As for the low density polyethylene (A) used for this invention, the MFR measured by 2.16 kg load (190 degreeC) is the range of 0.5-5.0 g / 10min, It is more preferable to exist in the range of 0.7-3.0 g / 10min. . If the MFR is less than 0.5 g / 10 min, the load on the extruder during melt extrusion increases, and there is a concern that the appearance of the laminate obtained by providing a polyethylene resin composition for extrusion lamination to extrusion lamination processing may deteriorate. On the other hand, if MFR exceeds 5.0 g / 10 minutes, the neck in may increase.

As for the low density polyethylene (A) used for this invention, melt tension (MS ₁₆₀ ) measured at ₁₆₀ degreeC becomes like this. Preferably it is 100 mN or more, More preferably, it is 150 mN or more. When the melt tension is 100 mN or more, the molten film at the time of laminating processing is stabilized, workability is good, roll contamination is reduced, and excellent cleanability is obtained.

The low density polyethylene (A) used for this invention can be obtained by the conventionally well-known high-pressure radical polymerization method, and is selected suitably in the range of this invention.

The density of polyethylene-type resin (B) which comprises the polyethylene resin composition for extrusion laminates of this invention is 910 kg / m <3> or more and 965 kg / m <3> or less. If density is less than 910 kg / m <3>, there exists a possibility that the heat resistance of the laminated body obtained may fall remarkably. On the other hand, when density exceeds 965 kg / m <3>, there exists a possibility that the curl of a laminated body may become remarkable.

The weight average molecular weight of the polyethylene-based linear polyethylene in terms of the resin (B) used in the present invention (M _w) is preferably at least 10,000 and 1,000,000 or less. When _Mw is less than 10,000 or more than 1,000,000, it becomes difficult to perform extrusion laminate molding, and there is a fear that a laminate cannot be obtained.

As for MFR measured at 2.16 kg load (190 degreeC) of the polyethylene-type resin (B) used for this invention, 0.1-100 g / 10min is preferable. If it is less than 0.1g / 10min or exceeds 100g / 10min, it becomes remarkably difficult to perform extrusion laminate molding, and there exists a possibility that a laminated body may not be obtained.

The long-chain branched number of the polyethylene-based resin (B) used in the present invention is 0.01 or more and 3.0 or less per 1,000 carbon atoms. If it is less than 0.01, it becomes remarkably difficult to perform extrusion lamination, and there exists a possibility that a laminated body may not be obtained. Moreover, when more than 3.0 pieces, there exists a possibility that an ethylene-type resin layer may become a laminated body in which mechanical properties are inferior. In addition, a long-chain branched number is the number of the branches more than hexyl group (C6 or more) detected by ¹³ C-NMR measurement.

The melt tension MS ₁₉₀ (mN) measured at 190 ° C of the polyethylene resin (B) used in the present invention and MFR (g / 10 min, 190 ° C) measured at 2.16 kg load (190 ° C) are represented by the following formula (1). )

MS ₁₉₀ > 22 x MFR ^-0.88 (1)

It is in the relationship shown, Preferably it is following formula (1) '

MS ₁₉₀ > 30 x MFR ^-0.88 (1) '

It is in the relationship shown, More preferably, it is following formula (1) ''

MS ₁₉₀ > 5 + 30 × MFR ^-0.88 (1) ''

In relation to When the formula (1) is not satisfied, for example, L-LDPE or HDPE that does not satisfy MS ₁₉₀ > 22 × MFR- ^0.88 becomes significantly difficult to extrude laminate molding, and thus a laminate cannot be obtained. There is concern.

Moreover, MFR (g / 10min, 190 degreeC) measured by melt tension MS160 (mN) and 2.16 kg load (190 degreeC) measured at ₁₆₀ degreeC of the polyethylene-type resin (B) used for this invention is a following formula. (2)

MS ₁₆₀ ＞ 110-110 × log (MFR) (2)

It is in the relationship shown, Preferably it is following formula (2) '

MS ₁₆₀ > 130-110 × log (MFR) (2) '

It is in the relationship shown, More preferably, following formula (2) ''

MS ₁₆₀ > 150-110 × log (MFR) (2) ''

In relation to When the formula (2) is not satisfied, for example, L-LDPE or HDPE which does not satisfy MS ₁₆₀ > 110-110 x log (MFR) becomes significantly difficult to extrude laminate molding, so that a laminate is obtained. There is a fear of losing.

Polyethylene-based resin (B) that satisfies the above requirements (a), (b) and (c) used in the present invention is preferably in the presence of a macromonomer consisting of a polymer or copolymer capable of polymerizing an olefin, or a macro It is a (co) polymer obtained by superposing | polymerizing ethylene simultaneously with the synthesis | combination of a monomer. That is, the macromonomer which consists of an olefin polymer or copolymer which has a vinyl group at the terminal obtained by superposing | polymerizing an olefin, More preferably, copolymerizes the ethylene polymer which has a vinyl group at the terminal obtained by superposingly polymerizing ethylene, or ethylene and an olefin having 3 or more carbon atoms. As a macromonomer which consists of an ethylene copolymer which has a vinyl group in the terminal obtained by

(d) the number average molecular weight (M _n ) is 2,000 or more,

(e) a weight average molecular weight (M _n) to the number average molecular weight ratio (M _w / M _n) of the (M _n) is 2.0 to 5.0

It is an ethylene (co) polymer obtained by polymerizing ethylene alone in the presence of a macromonomer or simultaneously with the synthesis of the macromonomer or by polymerizing ethylene and an olefin having 3 or more carbon atoms.

The polymer of ethylene which has a vinyl group at the terminal used as a macromonomer, or the copolymer of ethylene and a C3 or more olefin which has a vinyl group at the terminal is Unexamined-Japanese-Patent No. 2004-346304, Unexamined-Japanese-Patent No. 2005-248013, Unexamined Japan Japanese Patent Laid-Open No. 2006-321991 and Japanese Laid-Open Patent Publication No. 2007-169341.

For example, polyethylene-based resin (B) is the following general formula (4) in presence of the said macromonomer or simultaneously with the synthesis | combination of the said macromonomer.

It can be manufactured by the method of superposing | polymerizing ethylene independently or copolymerizing ethylene and a C3 or more olefin using the catalyst which has a transition metal compound [component (i)] shown as a main component.

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

As a C1-C20 hydrocarbon group in X <^1> , 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, Phenyl 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, butenyl group, buta A dienyl group, a pentenyl group, a pentadienyl group, a hexenyl group, a hexadienyl group, etc. are mentioned.

Moreover, R <^1> in component (i) is following General formula (5), (6) or (7)

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

Specific examples of R ^{1 in} the component (i) include a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an ethylcyclopentadienyl group, Diethylcyclopentadienyl group, triethylcyclopentadienyl group, tetraethylcyclopentadienyl group, propylcyclopentadienyl group, dipropylcyclopentadienyl group, tripropylcyclopentadienyl group, tetrapropylcyclopentadienyl group, butylcyclo Pentadienyl group, dibutylcyclopentadienyl group, tributylcyclopentadienyl group, tetrabutylcyclopentadienyl group, phenylcyclopentadienyl group, diphenylcyclopentadienyl group, naphthylcyclopentadienyl group, methoxycyclopentadiene Neyl group, trimethylsilylcyclopentadienyl group, indenyl group, methyl indenyl group, dimethyl indenyl group, trimethyl indenyl group, te Lamethyl indenyl group, pentamethyl indenyl 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 indenyl group, hexabutyl And a phenyl indenyl group, diphenyl indenyl group, benzoindenyl group, naphthyl indenyl group, methoxy indenyl group, trimethylsilyl indenyl group, and the like.

R <^2> in component (i) is following General formula (8)

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

As a specific example of R <^2> represented by General formula (8), For example, a fluorenyl group, methyl fluorenyl group, dimethyl fluorenyl group, trimethyl fluorenyl group, tetramethyl fluorenyl group, pentamethyl fluorenyl group, hexa Methyl fluorenyl group, heptamethyl fluorenyl group, octamethyl fluorenyl group, ethyl fluorenyl group, diethyl fluorenyl group, triethyl fluorenyl group, tetraethyl fluorenyl group, pentaethyl fluorenyl group, hexaethyl fluore Neyl group, heptaethyl fluorenyl group, octaethyl fluorenyl group, propyl fluorenyl group, dipropyl fluorenyl group, tripropyl fluorenyl group, tetrapropyl fluorenyl group, pentapropyl fluorenyl group, hexapropyl fluorenyl group, hepta Propyl fluorenyl group, octapropyl fluorenyl group, butyl fluorenyl group, dibutyl fluorenyl group, tributyl fluorenyl group, tetrabutyl fluorenyl group, pentabutyl Luorenyl group, hexabutyl fluorenyl group, heptabutyl fluorenyl group, octabutyl fluorenyl group, phenyl fluorenyl group, diphenyl fluorenyl group, benzyl fluorenyl group, dibenzyl fluorenyl group, benzofluorenyl group, dimethyl Amino fluorenyl group, bis (dimethylamino) fluorenyl group, a methoxy fluorenyl group, a dimethoxy fluorenyl group, etc. are mentioned.

And component (i) represents the formula (4) to the bridging group R ³ is a cross-linked to R ¹ and R ² in the formula (9)

The substituent R ⁶ is, for example, each independently a hydrogen atom, a halogen or a hydrocarbon group having 1 to 20 carbon atoms. Y <^1> is an atom of group 14 of a periodic table, Specifically, a carbon atom, a silicon atom, a germanium atom, a tin atom, etc. are mentioned, Especially, a carbon atom, a silicon atom, etc. are especially preferable, m is 1- Is an integer of 5.

As a specific example of General formula (9), for example, methylene group, ethylidene group, ethylene group, propylidene group, propylene group, butylidene group, butylene group, pentidene group, pentylene group, hexylidene group, iso Propylidene group, 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 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 (tri Methyl silyl phenyl) methylene group, bis (pentafluorophenyl) methylene group, silyl diyl group, disilane diyl group, trisilane diyl group, tetrasilane diyl group, dimethylsilane di diary, bis (dimethylsilane) diyl group, diethyl Silanediyl group, dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediyl group, a silacyclobutanediyl group, a silacyclohexanediyl group, etc. are mentioned.

When a specific compound represented by formula (4), the M ¹ a zirconium atom, a chlorine atom for X ^1, and bridging group R ³ group di-phenyl-methylene, for example, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadiene Yl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (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-cyclophene Dienyl) (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, diphenylmethylene (3-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (9-fluore Nil) 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-cyclopentadie Yl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride , Diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, di Phenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2, 7-dimethyl-9-fluorenyl) 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, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconiumdi Chloride, 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, diphenylmethylene (1- Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, di Nimethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (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 Can be. Moreover, the compound which substituted X <^1> of the said transition metal compound by the fluorine atom, a bromine atom, or an iodine atom can also be illustrated. In addition, R ³ of the 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, and a silacyclohexanediyl group. Compounds can also be exemplified. In addition, the transition may also be mentioned substituted compound to titanium atom or hafnium atom M ² of a metal compound. Two or more of these compounds can also be mixed and used.

As a catalyst which has a component (i) as a main component, the catalyst obtained by making a component (i) contact an activating promoter [component (iii)] can be illustrated.

As the component (iii), all known ones can be used, in particular clay minerals, clay minerals treated with organic compounds, aluminoxanes, ionic compounds, Lewis acids, magnesium chloride, surface treated inorganic oxides or inorganics Halides and the like are preferred.

In the preparation of the preferred polyethylene resin (B), examples of the olefin having 3 or more carbon atoms copolymerized with ethylene include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, and 3-methyl-1. ? -Olefins such as butene or vinylcycloalkane, cyclic olefins such as norbornene or norbornadiene, dienes or styrenes such as butadiene or 1,4-hexadiene can be exemplified. Moreover, these olefins can also be used in mixture of 2 or more types.

A macromonomer is an olefin polymer which has a vinyl group at the terminal, Preferably the ethylene polymer which has a vinyl group at the terminal obtained by superposingly polymerizing ethylene, or the ethylene copolymer which has a vinyl group at the terminal obtained by copolymerizing ethylene and a C3 or more olefin to be. More preferably, among the branches other than the branch derived from the olefin having 3 or more carbon atoms, short-chain branches such as methyl branch, ethyl branch, propyl branch, butyl branch, and pentyl branch are less than 0.01 per 1,000 main chain methylene carbons; Together, a linear ethylene polymer or a linear ethylene copolymer having a vinyl group at the terminal whose long chain branch (that is, a branch of hexyl group or more detected by ¹³ C-NMR measurement) is less than 0.01 per 1,000 carbon methylene carbons to be.

In the synthesis of the macromonomer, examples of the olefin having 3 or more carbon atoms copolymerized with ethylene include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene or vinylcyclo Cyclic olefins such as α-olefins such as alkanes, norbornene or norbornadiene, dienes or styrenes such as butadiene or 1,4-hexadiene can be exemplified. Moreover, these olefins can also be used in mixture of 2 or more types.

If a macromonomer using the ethylene copolymer having a vinyl group in an ethylene polymer or a terminal having a vinyl group at the terminal, the serial number (D) of the chain in terms of polyethylene-average molecular weight (M _n) is at least 2,000, preferably 3,000 Or more, more preferably 5,000 or more. In the case of M _n <2,000, since the formula (1) and / or the formula (2) are not satisfied and extrusion lamination is remarkably difficult, there is a possibility that a laminate cannot be obtained. In addition, (E) the weight ratio (M _w / M _n) of average molecular weight (M _w) to number average molecular weight (M _n) is from 2.0 to 5.0, and preferably from 2.0 to 4.0, more preferably 2.0 to 3.5 to be. If M _w / M _n> 5.0 a, the ethylene-based resin can body there is a fear that the mechanical strength falls laminated. In addition, when M _w / M _n <2.0, since it becomes difficult to perform extrusion laminate molding, there is a possibility that a laminate cannot be obtained.

Although there is no limitation in particular about the manufacturing method of the macromonomer in this invention, For example, Unexamined-Japanese-Patent No. 2005-281676, Unexamined-Japanese-Patent No. 2006-28326, Unexamined-Japanese-Patent No. 2006-315999, Japan Unexamined-Japanese-Patent It can manufacture using the method of Unexamined-Japanese-Patent No. 2007-169340, Unexamined-Japanese-Patent No. 2007-246433, and Unexamined-Japanese-Patent No. 2008-50278.

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

It can be manufactured using the method which superposes | polymerizes ethylene independently or copolymerizes ethylene and a C3 or more olefin using the catalyst which has a transition metal compound [component (ii)] shown as a main component.

M <^2> in component (ii) is a titanium atom, a zirconium atom, or a hafnium atom, X <^2> is respectively independently a hydrogen atom, a halogen, a C1-C20 hydrocarbon group.

As a C1-C20 hydrocarbon group in X <^2> , 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, a phenyl group is mentioned, for example. , 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, tri Propyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group, vinyl group, propenyl group, butenyl group, butadiene And a nil group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like.

R <^7> and R <^8> in component (ii) is following General formula (11), (12) or (13)

These may be the same or different, respectively, and form a sandwich structure with M <^2> . R <^10> in General formula (11), (12) or (13) is respectively independently a hydrogen atom, a halogen atom, and a C1-C20 hydrocarbon group.

As a C1-C20 hydrocarbon group of R <^10> in General formula (11), (12) or (13), a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Octyl, nonyl, decyl, norbornyl, phenyl, styryl, biphenylyl, naphthyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, dimethylphenyl, diethylphenyl, dipropylphenyl, dibutyl Phenyl 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, diphenyl A butyl group, a vinyl group, a propenyl group, butenyl group, butadienyl group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group, etc. are mentioned.

As a specific example of R <^7> and R <^8> in General formula (10), For example, a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, Ethylcyclopentadienyl group, diethylcyclopentadienyl group, triethylcyclopentadienyl group, tetraethylcyclopentadienyl group, propylcyclopentadienyl group, dipropylcyclopentadienyl group, tripropylcyclopentadienyl group, tetrapropyl Cyclopentadienyl group, butylcyclopentadienyl group, dibutylcyclopentadienyl group, tributylcyclopentadienyl group, tetrabutylcyclopentadienyl group, phenylcyclopentadienyl group, diphenylcyclopentadienyl group, naphthylcyclopentadiene Neyl group, methoxycyclopentadienyl group, trimethylsilylcyclopentadienyl group, indenyl group, methyl indenyl group, dimethyl indenyl group, t Methyl indenyl group, tetramethyl indenyl group, pentamethyl indenyl group, hexamethyl indenyl group, ethyl indenyl group, diethyl indenyl group, triethyl indenyl group, tetraethyl indenyl group, pentaethyl indenyl group, hexaethyl indenyl group, propyl Neyl 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 indenyl group , Hexabutyl indenyl group, phenyl indenyl group, diphenyl indenyl group, benzoindenyl group, naphthyl indenyl group, methoxy indenyl group, trimethylsilyl indenyl group, and the like.

In addition, R in the formula (10) ^7, bridging group R ⁹ to R ⁸ is a cross-linked to Formula (14), (15) or (16)

In these formulas (14), (15) and (16), the substituents R ¹¹ are each independently a hydrogen atom, a halogen or a hydrocarbon group having 1 to 20 carbon atoms. Moreover, Y <^2> is an atom of group 14 of a periodic table, Specifically, a carbon atom, a silicon atom, a germanium atom, a tin atom, etc. are mentioned, Especially, a carbon atom and a silicon atom are preferable, n is It is an integer of 1-5.

Hydrocarbon group of 1 to 20 carbon atoms in the R ¹¹ of the general formula 14, 15 or 16, for example, may be mentioned hydrocarbon groups of 1 to 20 carbon atoms in R ¹⁰ are the same.

As a specific example of General formula (14), for example, methylene group, ethylidene group, ethylene group, propylidene group, propylene group, butylidene group, butylene group, pentidene group, pentylene group, hexylidene group, iso Propylidene group, 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 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 Methyl silyl phenyl) methylene group, bis (pentafluorophenyl) methylene group, silyl diyl group, disilane diyl group, trisilane diyl group, tetrasilane diyl group, dimethyl silandi di group, bis (dimethylsilane) diyl group, diethyl Silanediyl group, dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediyl group, divinylsilanediyl group, diallyl silandiyl group, (methyl) ( And vinyl) silanediyl groups, (allyl) (methyl) silanediyl groups, and the like.

As a specific example of General formula (15), it is a 1,1,3,3- tetramethyldisiloxane-1,3-diyl group, 1,1,3,3- tetraethyldisiloxane-1,3, for example. -Diyl group, 1,1,3,3-tetraisopropyldisiloxane-1,3-diyl group, 1,1,3,3-tetraphenyldisiloxane-1,3-diyl group, etc. are mentioned.

As a specific example of General formula (16), it is a 1,1- dimethyl- 1-sila ethane- 1, 2- diyl group, a 1, 1- diethyl- 1-sila ethane- 1, 2- diyl group, for example. And 1,1-diisopropyl-1-silaethane-1,2-diyl group and 1,1-diphenyl-1-silaethane-1,2-diyl group.

Specific compounds represented by the following formula (10) used in the present invention, when the M ² chlorine atoms zirconium atom, X ^2, for example, methylene bis (cyclopentadienyl) zirconium dichloride, isopropylidene-bis ( Cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (cyclopentadienyl) zirconium dichloride, diphenylmethylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl Zirconium dichloride, methylenebis (methylcyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (methylcyclopentadienyl) zirconium dichloride Chloride, diphenylmethylenebis (methylcyclopentadienyl) zirconium dichloride, ethylenebis (methylcyclopentadienyl) zirconium dichlora Methylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopenta Dienyl) (methylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium di Chloride, methylenebis (2,4-dimethylcyclopentadienyl) 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 dichlori De, 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 di Chloride, 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 ( Clopentadienyl) zirconium dichloride, divinylsilanediylbis (cyclopentadienyl) zirconium dichloride, diallylsilanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (vinyl) silanediyl Bis (cyclopentadienyl) zirconium dichloride, (allyl) (methyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (cyclopentadienyl) zirconium dichloride (Methyl) (n-propyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl ) Bis (cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diethyl Silandi dibis ( Methylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dicy Chlohexylsilanediylbis (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, diisopropylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediyl (cyclopentadienyl) (methylcyclopentadiene Nil) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silandiyl (cyclopentadienyl) (methylcyclopentadienyl) Zirconium Dichloride, (methyl) (n-propyl) silandidiyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediyl (cyclopentadienyl) (methyl Cyclopentadienyl) zirconium deckle Ride, (cyclohexyl) (methyl) (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silandiyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium di Chloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, di (n-propyl) sil Landiylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (2, 4-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (2,4-dimethylcyclo Pentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediyl (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, diethylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, di (n-propyl) silanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, Diisopropylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, dicyclohexyldidi (cyclopentadienyl) (indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl ) (Indenyl) zirconium dichloride, dimethylsilanediyl (2-methylcyclo Pentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilandiyl (3-isopropylcyclopentadienyl) (indenyl ) Zirconium dichloride, dimethylsilanediyl (2,3-dimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (2,4-dimethylcyclopentadienyl) (indenyl) zirconium dichloride Dimethylsilanediyl (2,3,4-trimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethyldimethyldiyl (2,3,5-trimethylcyclopentadienyl) (indenyl) zirconium dichloride , Dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopenta Dienyl) (7-ethylindenyl) zirconium dichloride, dimethylsilanedi (Cyclopentadienyl) (7-phenylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethylindenyl) zirconium dichloride, dimethylsilandiyl (cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methoxy-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) ( 2-dimethylamino-7-methylindenyl) zirconium dichloride, dimethylsilandiyl (cyclopentadienyl) (2-trimethylsilyl-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopenta Dienyl) (7-methylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) ( 4-isopropyl-7-methylindenyl) zirconium dichloride, dimethylsilanedi (Cyclopentadienyl) (4-phenyl-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-methoxy-7-methylindenyl) zirconium dichloride, dimethylsilanedi 1 (cyclopentadienyl) (4-dimethylamino-7-methylindenyl) zirconium dichloride, dimethylsilandiyl (cyclopentadienyl) (4-trimethylsilyl-7-methylindenyl) zirconium dichloride, dimethyl Silanediyl (cyclopentadienyl) (2,4,7-trimethylinyl) zirconium dichloride, dimethyldimethyldiyl (cyclopentadienyl) (3,4,7-trimethylindenyl) zirconium dichloride, dimethyl Silanediyl (cyclopentadienyl) (2,3,4,7-tetramethylindenyl) zirconium dichloride, dimethylsilanediyl (3,4-dimethylcyclopentadienyl) (2,4,7-trimethyl Indenyl) zirconium dichloride, dimethylsilandiyl (3,4-bis (trimethylsilyl) cyclopentadienyl) (2,4,7-trimethylindenyl) zirco Znium dichloride, dimethylsilandiyl (tetramethylcyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4-phenyl-7-methylindenyl Zirconium Dichloride, Dimethylsilandiyl (tetramethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium Dichloride, Dimethylsilandiyl (tetramethylcyclopentadienyl) (2,4,7 -Trimethylindenyl) zirconium dichloride, (1,1,3,3-tetramethyldisiloxane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (1,1,3,3-tetraiso Propyldisiloxane-1,3-diyl-biscyclopentadienyl) 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-diisopropyl-1-silaethane-1,2- Mono-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, etc. can be illustrated. Moreover, the compound which substituted X <^1> of the said transition metal compound by the fluorine atom, a bromine atom, or an iodine atom can also be illustrated. In addition, the transition may also be mentioned substituted compound to titanium atom or hafnium atom M ² of a metal compound. These compounds can also be used in mixture of multiple.

As a catalyst which has the component (ii) represented by Formula (10) as a main component, the catalyst obtained by making the component (ii) and the activating promoter component (iii) contact can be illustrated. As a specific example of component (iii), the thing similar to the said component (iii) used in combination with component (i) about the catalyst which has component (i) as a main component is mentioned.

Although the specific manufacturing method of the polyethylene-type resin (B) of this invention is not specifically limited, (1) After synthesize | combining a ethylene and an olefin and optionally an C3 or more olefin using the catalyst which has component (ii) as a main component, and synthesize | combined a macromonomer, A method of producing polyethylene-based resin (B) by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms using a catalyst containing component (i) as a main component in the presence of the obtained macromonomer; And (2) a method of polymerizing ethylene and optionally an olefin having at least 3 carbon atoms using a catalyst composed mainly of components (i) and (ii) to produce a polyethylene resin (B) simultaneously with the synthesis of a macromonomer. can do.

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

The polyethylene-based resin (B) of the present invention can be produced by any of gas phase polymerization, slurry polymerization and solution polymerization. When slurry polymerization is performed, a polyethylene-based resin having excellent particle form can be produced. Can be.

Although there is no restriction | limiting in particular about superposition | polymerization conditions, such as superposition | polymerization temperature, superposition | polymerization time, superposition | polymerization pressure, and monomer concentration in the synthesis | combination of a macromonomer and manufacture of a polyethylene-type resin (B), superposition | polymerization temperature considers -100-120 degreeC and productivity is considered. It is preferable to carry out in 20-120 degreeC of lower surface, further, 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. Moreover, it is also possible to adjust molecular weight using hydrogen etc. at the time of superposition | polymerization. The polymerization may be carried out by any of batch, semi-continuous, and continuous methods, and may be carried out by dividing the polymerization conditions into two or more steps.

The polyethylene-based resin (B) that satisfies the requirements of (a) to (c) above can be arbitrarily produced according to the production conditions of the examples described later or minor variations in the conditional factors. Specific examples of the variation of the conditional factor are described in terms of the structure of the component (ii) and the component (i) to be used, the amount of the component (i) to the component (ii), the type of the cocatalyst component to be used, and the like. In addition, it can also manufacture separately according to superposition | polymerization conditions control, such as polymerization temperature, ethylene partial pressure, the quantity of molecular weight modifiers, such as hydrogen to coexist, and the quantity of the comonomer to add. It is also possible to expand the range of physical properties in combination with multistage polymerization.

More specifically, it is possible to reduce the number of terminal vinyls by, for example, lowering the ethylene partial pressure, decreasing the amount of comonomer addition, changing the structure of component (ii), and the like. Further, the melt tension may include changing the structure of component (ii), increasing the number of terminal vinyls, changing the structure of component (i), decreasing the ethylene partial pressure, increasing the long chain branching number, It is possible to increase by long chain branch length, by changing the amount of component (i) relative to component (ii), by increasing M _w / M _n and the like. In addition, the activation energy (E _a ) of the flow includes the structure of the component (ii), the number of terminal vinyls, the structure of the component (i), the ethylene partial pressure, the long chain branch number, the long chain branch length, and the component (ii) with respect to the component (ii) It is possible to control according to the amount of i).

The polyethylene resin composition which blended the low-density polyethylene (A) and polyethylene-type resin (B) with specific amount which satisfy | fills the said requirement is excellent in the external appearance of the product obtained by extrusion lamination, and becomes workability favorable. The polyethylene resin composition of this invention is 1-50 weight% of low-density polyethylene (A), Preferably 1-30 weight%, More preferably, 1-20 weight%, 99-50 weight% of polyethylene-type resins (B), Preferably it is 99-70 weight%, More preferably, it consists of 99-80 weight%. When the compounding quantity of low density polyethylene (A) is less than 1 weight%, there exists a possibility that it may become difficult to carry out extrusion lamination molding stably. On the other hand, when the compounding quantity of a low density polyethylene (A) exceeds 50 weight%, there exists a possibility that it may become difficult to thin laminate thickness.

As for the density of the polyethylene resin composition of this invention, 915-965 kg / m <3> is preferable, More preferably, it is 920-960 kg / m <3>. When the density is in the range of 915 to 965 kg / m 3, both heat resistance and sealability of the laminate product can be achieved.

As for the polyethylene resin composition of this invention, 3.0-30.0 g / 10min of MFR measured at 2.16 kg load (190 degreeC) is preferable, More preferably, it is 4.0-20 g / 10min. When the MFR is in the range of 3.0 to 30.0 g / 10 minutes, the laminate thickness can be made thin and extrusion laminate molding can be stably performed.

As for the polyethylene resin composition of this invention, melt tension (MS ₁₆₀ ) measured at ₁₆₀ degreeC is 30 mN or more, More preferably, it is 40 mN or more. When melt tension (MS ₁₆₀ ) is 30 mN or more, it becomes possible to carry out extrusion lamination stably.

The low density polyethylene (A) and the polyethylene-based resin (B) which comprise the polyethylene resin composition for extrusion lamination of this invention may respectively be 1 type, or 2 or more types of mixtures.

Although the polyethylene resin composition of this invention may dry-blend low density polyethylene (A) and polyethylene-type resin (B), it is melt-kneaded by conventionally well-known methods, such as a single screw extruder, a twin screw extruder, a kneader, and a Banbury mixer. It is preferable to obtain a composition having stable quality. In view 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, weather stabilizer, antistatic agent, antifoaming agent, antiblocking agent, slip agent, lubricant, nucleating agent, pigment, tackifier, carbon black, talc, glass powder, glass fiber and the like. Known additives such as inorganic fillers or reinforcing agents, organic fillers or reinforcing agents, flame retardants, neutron shielding agents and the like. Moreover, it can also mix and use with another thermoplastic resin. Examples thereof include 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 maleic anhydride graft thereof may be exemplified.

The laminated body of this invention is obtained by laminating and / or coating various base materials with the extrusion resin molding which forms the polyethylene-type resin composition which forms at least 1 layer. The extrusion laminate molding method may be any of single laminate, tandem laminate, coextrusion laminate, and sandwich laminate, and is not particularly limited. Moreover, when performing an extrusion lamination process, in order to obtain the laminated body with favorable adhesiveness of a base material and a polyethylene-type resin layer, it is preferable to extrude from a die at the temperature of 250-350 degreeC.

In addition, the surface where the molten film of a polyethylene-type resin composition contacts at least the base material may be oxidized by air or ozone gas. When advancing the oxidation reaction with air, it is preferable to extrude from a die at the temperature of 270 degreeC or more, and when advancing the oxidation reaction with ozone gas, it is preferable to extrude at 250 degreeC or more. Moreover, as a throughput of ozone gas, it is preferable that it is 0.5 mg or more per 1 m <2> of films extruded from die | dye. Moreover, in order to improve adhesiveness with a base material, you may perform well-known surface treatment, such as an anchor coat agent treatment, a corona discharge treatment, a frame treatment, and a plasma treatment, with respect to the adhesive surface of a base material.

Examples of the substrate include synthetic polymer polymer films and sheets, woven fabrics, nonwoven fabrics, metal foils, papers, cellophane, and the like. For example, films, sheets, etc. which consist of synthetic high molecular polymers, such as polyethylene terephthalate, a polyamide, polyvinyl alcohol, polycarbonate, polyethylene, and a polypropylene, are mentioned. In addition, these high molecular polymer films and sheets may be aluminum vapor deposition, alumina vapor deposition, or silicon dioxide vapor deposition. Moreover, these polymeric polymer films and sheets may be printed using urethane ink or the like. Examples of the metal foil include aluminum foil, copper foil and the like, and examples of paper include cardboard such as kraft paper, stretch paper, fine paper, glassine paper, cup paper or photo paper.

The laminated body of this invention is dried foods, such as snack confectionery, instant ramen, soup, miso, pickled foods, wet food packaging, such as sauce, beverage, medicine packaging, such as medicine, sap bag, shampoo, cosmetics, diaper It can be used as a film, a container, a tape, a support body for a wide range of items such as a toy sheet, a backing paper support, a paper container and a cover, a paper plate, a release paper and a release tape, an easily dissociable film, and a semi-retort pack made of paper. have.

The polyethylene resin composition of this invention is excellent in the external appearance of the product obtained by extrusion lamination, and also has a favorable workability, and is useful as resin for extrusion lamination.

EXAMPLES Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

All the physical properties of the polyethylene resin in the synthesis example, the Example, and the comparative example were measured by the method shown below.

<Molecular weight, molecular weight distribution>

The weight average molecular weight (M _w ) and the number average molecular weight (M _n ) were measured by gel permeation chromatography (GPC). HLC-8121GPC / HT manufactured by Tosoh Corporation was used as the GPC apparatus, TSK gel GMHhr-H (20) HT manufactured by Tosoh Corporation was used as the column, and the column temperature was set to 140 ° C. Measured using 1,2,4-trichlorobenzene. The measurement sample was prepared at the concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The calibration curve of the molecular weight is calibrated using a polystyrene sample with known molecular weight. In addition, M _w and M _n were determined as the values of linear polyethylene conversion.

<Long chain divergence>

The long-chain branch number measured the number of long-chain branches more than hexyl group by ¹³ C-NMR using the Varian-made VNMRS-400 type nuclear magnetic resonance apparatus. The solvent is tetra chloroethane-d ₂ . It was calculated | required from following formula (4) described in "Macromolecules" volume 31, 25, pages 8677-8683 (1998) as a number per 1,000 main chain methylene carbons.

Long Chain Branch Count = IA _α / (3 × IA _tot ) (4)

[Wherein, IA _α is the integral intensity of the α-carbon peak (chemical shift: 34.6 ppm) of the long-chain branch of hexyl group or more, and IA _tot is the integral intensity of the peak (30.0 ppm) of the main chain methylene carbon]

The terminal structure of polymers, such as a vinyl terminal and a saturated terminal, was measured by ¹³ C-NMR using the Varian-made VNMRS-400 type nuclear magnetic resonance apparatus. The solvent is tetrachloroethane-d ₂ . The number of vinyl terminals was calculated | required from the average value of the peak of 114 ppm and 139 ppm as number per 1,000 principal chain methylene carbons (chemical shift: 30 ppm). In addition, the saturated terminal number was similarly calculated | required from the average value of the peak of 32.3 ppm, 22.9 ppm, and 14.1 ppm. From this vinyl terminal number (X) and saturated terminal number (Y), the content rate Z (= X / (X + Y) * 2) of a vinyl terminal was calculated | required.

<Density>

Density was measured by the density gradient tube method based on JISK6760 (1995).

<MFR>

MFR was measured at 190 degreeC and a 2.16 kg load based on JISK6760 (1995).

<Melt tension>

The polyethylene used for the measurement of the melt tension (MS) was added to 1,500 ppm of Irganox 1010 ^TM (manufactured by Chiba Specialty Chemicals) and 1,500 ppm of Irgafos 168 ^TM (manufactured by Chiba Specialty Chemicals) as a heat stabilizer in advance. Using an internal mixer (manufactured by Toyo Seiki Co., Ltd., trade name: Labo Plast Mill), the mixture was kneaded for 3 minutes at 190 ° C and a rotation speed of 30 rpm under a nitrogen stream. The melt tension (MS) is a die 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 ° on a capillary viscometer (Toyo Seiki Co., Ltd., trade name: Capillograph). Measured by mounting. MS ₁₆₀ set the temperature to 160 degreeC, set the piston descending speed to 10 mm / min, and the draw ratio to 47, and measured the load (mN) required for take-out. MS ₁₉₀ set the temperature to 190 degreeC, set the piston descending speed to 10 mm / min, and the draw ratio to 47, and measured the load (mN) required for take-out.

<Neck-in>

The polyethylene resin composition was supplied to an extruder of an extrusion laminator (manufactured by Musashinokikai Co., Ltd.) having a screw of 90 mm Φ, extruded from a T die having an opening width of 600 mm at a temperature of 315 ° C, and the take-out speed of the substrate was 200 m /. The difference between the T die opening width and the coat width of the polyethylene resin composition when the resin composition for extrusion lamination is 20 µm thick on a kraft paper substrate having a basis weight of 50 g / m 2 as powder It was made into the neck-in and the value was measured. At this time, the case where the neck in was smaller than the high-pressure method low density polyethylene (Toso Co., Ltd. product name Petrosene 203) laminated by the same conditions was made (circle), and many cases were made into (circle) and the case where it was equivalent.

<Minimum film thickness>

The polyethylene resin composition was supplied to an extruder of an extrusion laminator (manufactured by Musashinokikai Co., Ltd.) having a screw of 90 mm Φ, extruded from a T die having an opening width of 600 mm at a temperature of 315 ° C, and the take-out speed of the substrate was 200 m /. As a powder, extrusion lamination was carried out on the 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 100 m or more of continuous extrusion extrusion molding was impossible was determined as the minimum film thickness, and the value thereof was measured. At this time, the case where the minimum film thickness was thinner than the high-pressure method low density polyethylene (Tosoh Co., Ltd. brand name Petrocene 203) laminated by the same conditions as (circle) and thick case was made into (circle) and the case where it was equivalent.

<Appearance of the molten film>

The polyethylene resin composition was supplied to an extruder of an extrusion laminator (manufactured by Musashinokikai Co., Ltd.) having a screw of 90 mm Φ, 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. Observed. At this time, (circle) the case where external appearance was better than the high-pressure method low density polyethylene (Tosoh Co., Ltd. brand name Petrocene 203) laminated by the same conditions was made into (circle), and the case where it was poor was made into (triangle | delta).

<Contamination of the surface of the cooling roll>

The polyethylene resin composition was supplied to an extruder of an extrusion laminator (manufactured by Musashinokikai Co., Ltd.) having a screw of 90 mm Φ, extruded from a T die having an opening width of 600 mm at a temperature of 315 ° C, and the take-out speed of the substrate was 20 m /. As a powder, extrusion lamination was performed for 500 m continuously on a kraft paper base material having a basis weight of 50 g / m 2 so that the resin composition for extrusion lamination had a thickness of 20 µm. After laminate molding, the deposit on the surface of the cooling roll was measured. At this time, the case where the cooling roll surface was better than the high pressure method low density polyethylene (Toso Co., Ltd. brand name Petrocene 203) laminate-molded on the same conditions as (circle), and the case where it was poor were made into (triangle | delta) and the case where it was equivalent. In addition, the cooling roll used the mirror roll and roll cooling temperature was 45 degreeC.

In addition, preparation of a modified hectorite, preparation of a catalyst, manufacture of polyethylene-type resin, and solvent purification were all performed in inert gas atmosphere. As the preparation of the modified hectorite, the preparation of the catalyst, the solvent used for the preparation of the polyethylene resin, and the like, all of which had been purified, dried, and deoxygenated by a known method in advance, were used. 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 (cyclopenta) Dienyl) zirconium dichloride and diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride were synthesized and identified by a known method. As a hexane solution (0.714M) of triisobutylaluminum, the Toso Finechem Co., Ltd. product was used.

Synthesis Example 1

[Preparation of modified hectorite]

After adding 3 liters of water to 3 liters of ethanol and 100 milliliters of 37% concentrated hydrochloric acid, 330 g (1.1 mol) of N, N-dimethyl-octadecylamine was added to the obtained solution, and the hydrochloride solution was prepared by heating to 60 degreeC. . 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. Thereafter, the resultant was dried for 24 hours at 60 ° C. at 10 ⁻³ torr and pulverized with a jet mill to obtain modified hectorite having an average particle diameter of 5.2 μm.

[Preparation of catalyst (p)]

500 g of the modified hectorite was suspended in 1.7 liters of hexane, and a hexane solution of 8.25 g (20.0 mmol) of dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride and triisobutylaluminum (0.714M ) After adding 2.8 liter (2 mol) of mixed liquid, stirring at 60 degreeC for 3 hours, it was made to stand still, the supernatant was removed, and the hexane solution of triisobutylaluminum (0.15M) was further added, and a catalyst precursor was added. It was set as the slurry (100 g / L).

10 mol% of isopropylidene (1-cyclopentadienyl) (2,7-di 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 the mixture was stirred at room temperature for 6 hours. After standing still, the supernatant was removed, and a hexane solution of triisobutylaluminum (0.15M) was further added to finally obtain a catalyst slurry of 100 g / L.

[Production of Polyethylene Resin (B-1)]

300 liters of hexane and 5.9 liters of 1-butene were introduced into an internal volume of 540 liters of polymerization, and the internal temperature of the autoclave was raised to 70 ° C. 120 milliliters of the said catalyst (p) was added to this autoclave, ethylene / hydrogen mixed gas (containing hydrogen: 500 ppm) was introduced until partial pressure became 0.9 Mpa, and superposition | polymerization was started. During the polymerization, ethylene / hydrogen mixed gas (containing hydrogen: 500 ppm) was continuously introduced so that the partial pressure was maintained at 0.9 MPa. Moreover, polymerization temperature was controlled at 70 degreeC. After 90 minutes from the start of the polymerization, the internal pressure of the polymerization reactor was depressurized, and then the contents were filtered and dried to obtain 54 kg of polyethylene resin powder. As for the density of obtained polyethylene-type resin (B-1), 924 kg / m <3> and MFR were 25 g / 10min, long chain branch number was 0.13 piece per 1000 carbon atoms, MS ₁₉₀ was 22 mN, and MS ₁₆₀ was 34 mN.

In addition, in this manufacture example, manufacture of the macromonomer shown to the following reference example 1, and manufacture of the polyethylene-type resin (B-1) by copolymerization of ethylene and 1-butene are carried out in the coexistence of this macromonomer.

Reference Example 1

[Production of Macromonomer]

In the same manner as in Synthesis Example 1 [Preparation of Polyethylene Resin (B-1)], except that 120 milliliters of the catalyst precursor slurry prepared in Synthesis Example 1 [Preparation of catalyst (p)] was added instead of the catalyst (p). The polymerization was carried out to obtain an ethylene copolymer powder. Mn = 15,500, Mw / Mn = 2.25 and Z = 0.28 of the obtained ethylene copolymer. Moreover, long chain branching was not detected.

Synthesis Example 2

[Production of Polyethylene Resin (B-2)]

5.6 liters of 1-butene was introduced, 131 milliliters of the catalyst (p) prepared in Synthesis Example 1 [Preparation of catalyst (p)] was added, and Synthesis Example 1 [polyethylene was used except that only ethylene was used instead of the ethylene / hydrogen mixed gas. Manufacture of system resin (B-1)] was carried out in the same manner as to obtain 57 kg of polyethylene resin powder. As for the density of obtained polyethylene-type resin (B-2), 924 kg / m <3> and MFR were 15 g / 10min, long chain branch number was 0.13 piece per 1000 carbon atoms, MS ₁₉₀ was 24 mN, and MS ₁₆₀ was 38 mN.

Moreover, in this manufacture example, manufacture of the macromonomer shown to the following reference example 2, and manufacture of the polyethylene-type resin (B-1) by copolymerization of ethylene and 1-butene are carried out in the coexistence of this macromonomer.

Reference Example 2

[Production of Macromonomer]

Polymerization was carried out in the same manner as in Synthesis Example 2 [Preparation of Polyethylene Resin (B-2)], except that 131 milliliters of the catalyst precursor slurry prepared in Synthesis Example 1 [Preparation of catalyst (p)] was added instead of catalyst (p). Was carried out to obtain an ethylene copolymer powder. Mn = 16,000, Mw / Mn = 2.35 and Z = 0.28 of the obtained ethylene copolymer. Moreover, long chain branching was not detected.

Synthesis Example 3

[Preparation of catalyst (q)]

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

[Production of Polyethylene Resin (B-3)]

5.2 liters of 1-butene was introduced, 106 milliliters of the catalyst (q) was added instead of the catalyst (p), and ethylene was used instead of the ethylene / hydrogen mixed gas. Synthesis Example 1 [Polyethylene-based resin (B-1) Manufacture] was carried out in the same manner as to obtain 55 kg of polyethylene-based resin powder. As for the density of obtained polyethylene-type resin (B-3), 924 kg / m <3> and MFR were 5 g / 10min, long chain branch number was 0.10 per 1000 carbon atoms, MS ₁₉₀ was 44 mN, and MS ₁₆₀ was 66 mN.

Moreover, in this manufacture example, manufacture of the macromonomer shown to the following reference example 3, and manufacture of the polyethylene-type resin (B-3) by copolymerization of ethylene and 1-butene are carried out in the coexistence of this macromonomer.

Reference Example 3

[Production of Macromonomer]

Polymerization was carried out in the same manner as in Synthesis Example 3 [Preparation of Polyethylene-Based Resin (B-3)], except that 106 milliliters of the catalyst precursor slurry prepared in Synthesis Example 3 [Preparation of catalyst (q)] was added instead of the catalyst (q). Was carried out to obtain an ethylene copolymer powder. Mn = 19,000, Mw / Mn = 2.50 and Z = 0.25 of the obtained ethylene copolymer. Moreover, long chain branching was not detected.

Synthesis Example 4

[Preparation of catalyst (r)]

Dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride 7.43 g (18.0 mmol) and 1 instead of dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride 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 Prepared in the same manner as in to obtain a catalyst slurry of 100 g / L.

[Production of Polyethylene Resin (B-4)]

6.4 liter of 1-butene was introduced, 133 milliliters of the catalyst (r) was added instead of the catalyst (p), and ethylene / hydrogen mixed gas (containing hydrogen: 1000 ppm) instead of ethylene / hydrogen mixed gas (containing hydrogen: 500 ppm) Except for the same), polymerization was carried out in the same manner as in Synthesis example 1 [Manufacture of polyethylene-based resin], and 53 kg of polyethylene-based resin powder was obtained. As for the density of obtained polyethylene-type resin (B-4), 924 kg / m <3> and MFR were 15 g / 10min, long chain branch number was 0.12 per 1000 carbon atoms, MS ₁₉₀ was 27 mN, and MS ₁₆₀ was 40 mN.

Moreover, in this manufacture example, manufacture of the macromonomer shown to the following reference example 4, and manufacture of the polyethylene-type resin (B-4) by copolymerization of ethylene and 1-butene are carried out in the coexistence of this macromonomer.

Reference Example 4

[Production of Macromonomer]

Polymerization was carried out in the same manner as in Synthesis Example 4 [Preparation of polyethylene-based resin (B-4)], except that 133 milliliters of the catalyst precursor slurry prepared in Synthesis Example 4 [Preparation of catalyst (r)] was added instead of the catalyst (r). Was carried out to obtain an ethylene copolymer powder. Mn = 16,000, Mw / Mn = 2.75 and Z = 0.27 of the obtained ethylene copolymer. Moreover, long chain branching was not detected.

Synthesis Example 5

[Preparation of catalyst (s)]

6.83 g (16.0 mmol) of dimethylsilanediyl (cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride Was added, and diphenylmethylene (1-cyclopentadienyl) (2 instead of isopropylidene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride (2 100 g / L, prepared in the same manner as in Synthesis example 1 [Preparation of catalyst (p)], except that 2.68 g (4.0 mmol) of, 7-di-t-butyl-9-fluorenyl) zirconium dichloride was added. The catalyst slurry of was obtained.

[Production of Polyethylene Resin (B-5)]

Synthesis was carried out except that 7.6 liter of 1-butene was introduced, 135 milliliters 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 to 60 ° C. Example 1 It superposed | polymerized by the method similar to [production of polyethylene-type resin (B-1)], and obtained 54 kg of polyethylene-type resin powder. As for the density of obtained polyethylene-type resin (B-5), 918 kg / m <3>, MFR were 5 g / 10min, long chain branch number was 0.10 per 1000 carbon atoms, MS ₁₉₀ was 49 mN, and MS ₁₆₀ was 70 mN.

Moreover, in this manufacture example, manufacture of the macromonomer shown to the following Reference Example 5, and manufacture of the polyethylene-type resin (B-5) by copolymerization of ethylene and 1-butene are carried out in the coexistence of this macromonomer.

Reference Example 5

[Production of Macromonomer]

Polymerization was carried out in the same manner as in Synthesis Example 5 [Preparation of polyethylene-based resin (B-5)], except that 135 milliliters of the catalyst precursor slurry prepared in Synthesis Example 5 [Preparation of catalyst (s)] was added instead of the catalyst (s). Was carried out to obtain an ethylene copolymer powder. Mn = 21,000, Mw / Mn = 2.48 and Z = 0.25 of the obtained ethylene copolymer. Moreover, long chain branching was not detected.

Synthesis Example 6

[Preparation of catalyst (t)]

Synthesis Example 1 [0096] 500 g of modified hectorite prepared in [Preparation of Modified Hectorite] was suspended in 1.8 liters of hexane, 2.9 liters of hexane solution of triisobutylaluminum (0.714M) was added, and the mixture was stirred at room temperature for 1 hour to modify the modified hectorite. And a contact product of triisobutylaluminum were obtained. On the other hand, what melt | dissolved 6.97 g (20 mmol) of dimethylsilane diyl bis (cyclopentadienyl) zirconium dichlorides in toluene was added, and the catalyst slurry (100 g / L) was obtained by stirring at room temperature overnight.

[Production of Macromonomer]

7.6 liters of 1-butene was introduced, 135 milliliters of the catalyst (t) was added instead of the catalyst (p), ethylene was used instead of the ethylene / hydrogen mixed gas, the ethylene partial pressure was controlled to 1.2 MPa, and the polymerization temperature was Polymerization was carried out in the same manner as in Synthesis example 1 [Manufacture of polyethylene-based resin (B-1)] except having controlled at 85 degreeC. Mn = 10,950, Mw / Mn = 2.61 and Z = 0.57 of the macromonomer taken out from this polymerizer. Moreover, long chain branching was not detected.

[Production of Polyethylene Resin (B-6)]

In an internal 540 liter polymerizer containing the macromonomer prepared above, 1-butene is 0.22 liter of 1-butene, a hexane solution of triisobutylaluminum (0.714 mol / l) and 0.75 liter of diphenylmethylene (1-indenyl) ( 3.75 mmol of 9-fluorenyl) zirconium dichloride was introduced and the internal temperature of the autoclave was raised to 85 ° C. Ethylene / hydrogen mixed gas (22,000 ppm of hydrogen) was introduced until the partial pressure became 0.2 MPa to initiate polymerization. During the polymerization, the ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure was maintained at 0.2 MPa. Moreover, polymerization temperature was controlled at 85 degreeC. 90 minutes after the start of the polymerization, the internal pressure of the autoclave was depressurized, and the contents were suction filtered. After drying, 54 kg of polyethylene-based resin was obtained. As for the density of obtained polyethylene-type resin (B-6), 948 kg / m <3> and MFR were 30 g / 10min, long chain branch number was 0.15 per 1000 carbon atoms, MS ₁₉₀ was 21 mN, and MS ₁₆₀ was 30 mN.

Synthesis Example 7

[Production of Polyethylene Resin (B-7)]

Except not adding 1-butene, it superposed | polymerized by the method similar to the synthesis example 6 [production of polyethylene-type resin (B-6)], and 50 kg of polyethylene-type resin was obtained. As for the density of obtained polyethylene-type resin (B-7), 963 kg / m <3> and MFR were 15 g / 10min, long chain branch number was 0.12 per 1000 carbon atoms, MS ₁₉₀ was 30 mN, and MS ₁₆₀ was 55 mN.

Table 1 shows the properties of the macromonomers in the synthesis examples 1 to 7 and the properties of the polyethylene resins (B-1) to (B-7).

Table 2 shows the properties of the low density polyethylene used in the following Examples and Comparative Examples.

Example 1

15% by weight of 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) (hereinafter referred to as (A-1)) And 85% by weight of the polyethylene resin (B-3) shown in Synthesis Example 3 were premixed with a tumbler mixer, and then melted with a single screw extruder (Placo Co., Ltd., Model PDA-50) adjusted to a cylinder temperature of 180 ° C. Kneading and granulation were carried out to obtain pellets of a polyethylene resin composition. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 3 shows the results of these evaluations.

Example 2

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 205; density 924 kg / m <3>, MFR 3g / 10min, MS ₁₆₀ 160mN) (A-2) 5 weight%, The polyethylene shown in the synthesis example 2 After pre-mixing 95% by weight of the resin (B-2) with a tumbler mixer, melt kneading and assembling with a single screw extruder (Placo Co., Ltd., Model PDA-50) adjusted to a cylinder temperature of 180 ° C. to obtain a polyethylene resin composition. Pellets were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 3 shows the results of these evaluations.

Example 3

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 360; density 919 kg / m <3>, MFR 1.6g / 10min, MS ₁₆₀ 295mN) (A-1) 50 weight%, shown to the synthesis example 2 After premixing 50% by weight of polyethylene resin (B-2) with a tumbler mixer, melt kneading and assembling with a single screw extruder (Placo Co., Ltd., Model PDA-50) adjusted to a cylinder temperature of 180 ° C. Pellets of the composition were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 3 shows the results of these evaluations.

Example 4

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 205; density 924 kg / m <3>, MFR 3g / 10min, MS ₁₆₀ 160mN) (A-2) 15weight%, The polyethylene shown by the synthesis example 1 After pre-mixing 85% by weight of the resin (B-1) with a tumbler mixer, melt-kneading and assembling with a single screw extruder (Placo Co., Ltd., Model PDA-50) adjusted to a cylinder temperature of 180 ° C to obtain a polyethylene resin composition. Pellets were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 3 shows the results of these evaluations.

Example 5

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 360; density 919 kg / m <3>, MFR 1.6g / 10min, MS ₁₆₀ 295mN) (A-1) 25 weight%, shown to the synthesis example 4 After premixing 75% by weight of polyethylene resin (B-4) with a tumbler mixer, melt kneading and assembling with a single screw extruder (Placo Co., Ltd., PDA-50) adjusted to a cylinder temperature of 180 ° C Pellets of the composition were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 3 shows the results of these evaluations.

Example 6

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 360; density 919 kg / m <3>, MFR 1.6g / 10min, MS ₁₆₀ 295mN) (A-1) 10 weight%, shown to the synthesis example 5 After premixing 90% by weight of polyethylene resin (B-5) with a tumbler mixer, melt kneading and assembling with a single screw extruder (Placo, Model PDA-50) adjusted to a cylinder temperature of 180 ° C Pellets of the composition were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 3 shows the results of these evaluations.

Example 7

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 360; density 919 kg / m <3>, MFR 1.6g / 10min, MS ₁₆₀ 295mN) (A-1) 2.5 weight%, shown to the synthesis example 6 97.5% by weight of polyethylene resin (B-6) was premixed with a tumbler mixer, followed by melt kneading and assembling with a single screw extruder (Placo Co., Ltd., Model PDA-50) adjusted to a cylinder temperature of 180 ° C. Pellets of the composition were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 3 shows the results of these evaluations.

Example 8

Low-density polyethylene obtained by the high pressure radical polymerization method (Tosoh Corporation make brand name Petrocene 205; density 924 kg / m <3>, MFR 3g / 10min, MS ₁₆₀ 160mN) (A-2) 7.5weight%, The polyethylene shown by the synthesis example 7 After pre-mixing 92.5% by weight of the system resin (B-7) with a tumbler mixer, melt-kneading and assembling with a single screw extruder (Placo Co., Ltd., Model PDA-50) adjusted to a cylinder temperature of 180 ° C to obtain a polyethylene resin composition. Pellets were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 3 shows the results of these evaluations.

Example 9

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 217; density 923 kg / m <3>, MFR 4.5g / 10min, MS ₁₆₀ 160mN) (A-3) 25 weight%, shown to the synthesis example 4 After premixing 75% by weight of polyethylene resin (B-4) with a tumbler mixer, melt kneading and assembling with a single screw extruder (Placo Co., Ltd., PDA-50) adjusted to a cylinder temperature of 180 ° C Pellets of the composition were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 3 shows the results of these evaluations.

Example 10

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 3M04A; density 924.5 kg / m <3>, MFR 4.5g / 10min, MS ₁₆₀ 110mN) (A-4) 25 weight%, shown to the synthesis example 4 After premixing 75% by weight of polyethylene resin (B-4) with a tumbler mixer, melt kneading and assembling with a single screw extruder (Placo Co., Ltd., PDA-50) adjusted to a cylinder temperature of 180 ° C Pellets of the composition were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 3 shows the results of these evaluations.

Comparative Example 1

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 360; density 919 kg / m <3>, MFR 1.6g / 10min, MS ₁₆₀ 295mN) (A-1) 0.5 weight%, shown to the synthesis example 3 After premixing 99.5% by weight of polyethylene-based resin (B-3) with a tumbler mixer, melt-kneading and assembling with a single screw extruder (Placo, Model PDA-50) adjusted to a cylinder temperature of 180 ° C Pellets of the composition were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 4 shows the results of these evaluations.

When the obtained polyethylene resin composition was extruded and laminated, the neck in was significantly worse than the high pressure method low density polyethylene (Tosoh Co., Ltd. brand name Petrocene 203) laminated by the same conditions.

Comparative Example 2

Low density polyethylene obtained by the high pressure radical polymerization method (Tosoh Corporation make brand name Petrocene 360; density 919 kg / m <3>, MFR 1.6g / 10min, MS ₁₆₀ 295mN) (A-1) 55 weight%, shown to the synthesis example 3 After premixing 45% by weight of polyethylene resin (B-3) with a tumbler mixer, melt kneading and assembling with a single screw extruder (Placo Co., Ltd., PDA-50) adjusted to a cylinder temperature of 180 ° C Pellets of the composition were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 4 shows the results of these evaluations.

When the obtained polyethylene resin composition was extruded and laminated, the minimum film thickness was not thinner than the high pressure method low density polyethylene (Toso Corporation make brand name Petrocene 203) laminated by the same conditions, and it was defect.

Comparative Example 3

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 205; density 924 kg / m <3>, MFR 3g / 10min, MS ₁₆₀ 160mN) (A-2) 0.5 weight%, The polyethylene shown in the synthesis example 2 After pre-mixing 99.5% by weight of the resin (B-2) with a tumbler mixer, melt-kneading and assembling with a single screw extruder (Placo Co., Ltd., Model PDA-50) adjusted to a cylinder temperature of 180 ° C to obtain a polyethylene resin composition. Pellets were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 4 shows the results of these evaluations.

When the obtained polyethylene resin composition was extruded and laminated, the neck in was significantly worse than the high pressure method low density polyethylene (Tosoh Co., Ltd. brand name Petrocene 203) laminated by the same conditions.

Comparative Example 4

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 360; density 919 kg / m <3>, MFR 1.6g / 10min, MS ₁₆₀ 295mN) (A-1) 55 weight%, shown to the synthesis example 2 After pre-mixing 45% by weight of polyethylene-based resin (B-2) with a tumbler mixer, melt-kneading and assembling with a single screw extruder (Placo, Model PDA-50) adjusted to a cylinder temperature of 180 ° C Pellets of the composition were obtained. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 4 shows the results of these evaluations.

When the obtained polyethylene resin composition was extruded and laminated, the minimum film thickness was not thinner than the high pressure method low density polyethylene (Toso Corporation make brand name Petrocene 203) laminated by the same conditions, and it was defect.

Comparative Example 5

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 205; density 924 kg / m <3>, MFR 3g / 10min, MS ₁₆₀ 160mN) (A-2) 15 weight%, with a metallocene type catalyst The obtained linear low-density polyethylene (trade name Niporon Z 04P66A; Density 917 kg / m 3, MFR 15 g / 10 min) (C-1) 85 wt% of the obtained linear low density polyethylene was premixed with a tumbler mixer, and then the cylinder temperature was 180 °. It melt-kneaded and granulated by the single screw extruder (Placo Co., Ltd., model PDA-50) adjusted to ° C, and pelletized the polyethylene resin composition. The obtained pellet was laminated by the method shown in the evaluation method of polyethylene-type resin.

Density, MFR, MS were measured with the obtained polyethylene resin composition, and the minimum film thickness which is neck at the time of extrusion laminate molding, the external appearance of a molten film, and the contamination of the cooling roll surface were evaluated. Table 4 shows the results of these evaluations.

When the obtained polyethylene resin composition was extruded and laminated, only the neck shape equivalent to the high-pressure method low density polyethylene (Toso Corporation make brand name Petrocene 203) laminated by the same conditions was obtained, and the external appearance of a molten film was inferior.

Comparative Example 6

Low-density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 205; density 924 kg / m <3>, MFR 3g / 10min, MS ₁₆₀ 160mN) (A-2) 100 weight% of evaluation method of a polyethylene-type resin Lamination molding was carried out by the method shown in.

MS was measured and contamination at the neck, the minimum film thickness, the appearance of a molten film, and the surface of a cooling roll at the time of extrusion laminate molding were evaluated. Although these evaluation results are shown in Table 4, only the external appearance of the molten film which is the neck equivalent to the high-pressure method low density polyethylene (Toso Corporation make brand name Petrosene 203) laminated by the same conditions, and the contamination of the surface of a cooling roll are obtained. , The minimum film thickness was bad, was thick.

Comparative Example 7

100 weight% of polyethylene-type resins (B-4) shown in the synthesis example 4 were laminated by the method shown to the evaluation method of polyethylene-type resin.

MS was measured and contamination at the neck, the minimum film thickness, the appearance of a molten film, and the surface of a cooling roll at the time of extrusion laminate molding were evaluated. Although these evaluation results are shown in Table 4, compared with the high-pressure method low-density polyethylene (Tosoh Co., Ltd. brand name Petrocene 203) laminated by the same conditions, the neck in was large and was bad.

Comparative Example 8

Linear low-density polyethylene obtained by a metallocene catalyst (trade name Niporon Z 04P66A manufactured by Tosoh Corporation; density 917 kg / m 3, MFR 15 g / 10 min) (C-1) 100% by weight of polyethylene resin evaluation It laminate-formed by the method shown to the method.

MS was measured and extrusion laminate molding was attempted, but the molten film was not stable and a laminated body could not be obtained. Moreover, although the evaluation result of the external appearance of a molten film and the contamination of the cooling roll surface is shown in Table 4, only the performance equivalent to the high pressure method low density polyethylene (Tosoh Corporation make brand name Petrosene 203) evaluated on the same conditions was obtained.

Comparative Example 9

Low-density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 360; density 919 kg / m <3>, MFR 1.6g / 10min, MS ₁₆₀ 295mN) (A-1) 100 weight% of evaluation of a polyethylene-type resin It laminate-formed by the method shown to the method.

MS was measured and extrusion laminate molding was attempted, but the take-out rate of a base material could not be raised and a laminated body could not be obtained. Moreover, although the evaluation result of the external appearance of a molten film and the contamination of the cooling roll surface is shown in Table 4, only the performance equivalent to the high pressure method low density polyethylene (Tosoh Corporation make brand name Petrosene 203) evaluated on the same conditions was obtained.

Comparative Example 10

Low-density polyethylene obtained by the high-pressure radical polymerization method (Tosoh Corporation make brand name Petrocene 217; density 923 kg / m <3>, MFR 4.5g / 10min, MS ₁₆₀ 160mN) (A-3) 100 weight% of evaluation of a polyethylene-type resin It laminate-formed by the method shown to the method.

MS was measured and contamination at the neck, the minimum film thickness, the appearance of a molten film, and the surface of a cooling roll at the time of extrusion laminate molding were evaluated. Although these evaluation results are shown in Table 4, only the external appearance of the molten film which is the neck equivalent to the high-pressure method low density polyethylene (Toso Corporation make brand name Petrosene 203) laminated by the same conditions, and the contamination of the surface of a cooling roll are obtained. , The minimum film thickness was bad, was thick.

Comparative Example 11

Low-density polyethylene obtained by the high pressure radical polymerization method (Tosoh Corporation make brand name Petrocene 3M04A; density 924.5 kg / m <3>, MFR 4.5g / 10min, MS ₁₆₀ 110mN) (A-4) 100 weight% of evaluation of a polyethylene-type resin It laminate-formed by the method shown to the method.

MS was measured and contamination at the neck, the minimum film thickness, the appearance of a molten film, and the surface of a cooling roll at the time of extrusion laminate molding were evaluated. Although these evaluation results are shown in Table 4, only the external appearance of the molten film equivalent to the high-pressure method low density polyethylene (Tosoh Co., Ltd. brand name Petrocene 203) laminated by the same conditions, and the contamination of the surface of a cooling roll are obtained, Was large and the minimum film thickness was also bad.

Comparative Example 12

Low density polyethylene obtained by the high pressure radical polymerization method (Toso Corporation make brand name Petrocene 203; density 919 kg / m <3>, MFR 8g / 10min, MS ₁₆₀ 70mN) (A-5) 100 weight% of evaluation method of a polyethylene-type resin Lamination molding was carried out by the method shown in.

MS was measured and contamination at the neck, the minimum film thickness, the appearance of a molten film, and the surface of a cooling roll at the time of extrusion laminate molding were evaluated. Table 4 shows the results of these evaluations.

Claims (6)

Low density polyethylene (A) whose density obtained by the high pressure radical polymerization method is 915-935 kg / m <3>, and the melt mass flow rate (henceforth MFR) measured at 2.16 kg load (190 degreeC) is 0.5-5.0 g / 10min. A polyethylene resin composition comprising 1 to 50% by weight and 99 to 50% by weight of polyethylene-based resin (B) satisfying the requirements of the following (a) to (c). (a) density is 910-965 kg / m 3, (b) from 0.01 to 3.0 carbon atoms with 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 given by the following equation (1) MS ₁₉₀ > 22 x 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) The method of claim 1, As a macromonomer which consists of an ethylene polymer which has a vinyl group at the terminal obtained by superposing | polymerizing ethylene, or the ethylene copolymer which has a vinyl group at the terminal obtained by copolymerizing ethylene and a C3 or more olefin, (d) the number average molecular weight (M _n ) is 2,000 or more, (e) a weight average molecular weight (M _n) to the number average molecular weight ratio (M _w / M _n) of the (M _n) is 2.0 to 5.0 A polyethylene resin composition using as a polyethylene resin (B) a polyethylene resin obtained by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms in the presence of a macromonomer or simultaneously with the synthesis of the macromonomer. The method according to claim 1 or 2, The polyethylene resin composition which satisfy | fills the requirements of following (f)-(h). (f) Density 915-965㎏ / ㎥ (g) MFR measured at 2.16 kg load (190 ° C) of 3.0-30.0 g / 10 min, (h) Melt tension (MS ₁₆₀ ) measured at 160 ° C is 30 mN or more. The method according to claim 1 or 2, Polyethylene resin composition for extrusion laminate. The laminated body which has at least 1 layer or more of layers which consist of the polyethylene resin composition of Claim 1 or 2. The method according to claim 1 or 2, The low density polyethylene (A) whose melt tension (MS ₁₆₀ ) measured at ₁₆₀ degreeC is 150 mN or more, The polyethylene resin composition for extrusion laminates characterized by the above-mentioned.