JP2010046881A - Foamed laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a foamed laminate which shows heat insulation properties owing to a thick foamed layer, and has excellent smoothness of the surface of the foamed layer and a good appearance of foam. <P>SOLUTION: The laminate includes at least a layer (A), a layer (B), and a substrate layer. The layer (A) consists of a foam made of a polyethylene resin (A), and the layer (B) consists of a foam made of a high-pressure-production low-density polyethylene (B). The laminate meets the following conditions: (a) the melting temperature of the polyethylene resin (A) is higher than that of the high-pressure-production low-density polyethylene (B); and (b) the layer (A) has a thickness of 1-12 μm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a foam laminate having a thick foam layer, excellent foam surface smoothness, and good foam appearance.

  Conventionally, as a container having a heat insulating property, a synthetic resin, in particular, a polystyrene foamed one is often used. However, the expanded polystyrene container has drawbacks such as high environmental load at the time of disposal and poor printability, and alternatives to other materials are being studied. Under such circumstances, a container in which corrugated paper is bonded to the outer peripheral surface of the paper cup body to form a heat insulating layer, a container in which a laminate of pulp nonwoven fabric and coated paper is bonded to the outer peripheral surface of the paper cup, etc. Has been developed and used.

  However, each method has a drawback that it is not easy to process and mold, and the cost is high. Therefore, by laminating and heating a low-melting-point thermoplastic synthetic resin film on at least one surface of the moisture-containing base material, the synthetic resin film is foamed into irregularities using the moisture contained in the base material. Has been devised (see, for example, Patent Documents 1 to 3). However, the material thus obtained has a thin foam layer and insufficient heat insulation.

  Further, as a means for obtaining a foam having a thick foam layer, a technique has been proposed in which at least a part of the foam surface is vacuum-sucked to thicken the foam layer of the foam cell (see, for example, Patent Document 4). The container body member and the bottom plate member are composed of a high-melting point thermoplastic synthetic resin film laminated on the inner wall surface of the base material of the container body member and the bottom plate member, and the low melting point heat is applied to the outer wall surface of the base material of the container body member. There has been proposed a heat-insulating paper container in which a plastic synthetic resin film is laminated and the low-melting thermoplastic synthetic resin film is foamed by heat treatment (see, for example, Patent Document 5).

  However, the method of thickening the foamed layer by vacuum suction has a problem that it is inferior in cost performance because a vacuum suction device is necessary and a step of performing vacuum suction is required in the manufacturing process. Also, in a heat-insulated paper container having a high-melting-point thermoplastic synthetic resin on the inner wall surface, large protrusions are generated on the surface of the foam layer during foaming, foam cell bonding or bubble breakage, and foam cell shrinkage during cooling There is a problem that the surface appearance is likely to deteriorate due to a reason that a large concave portion is formed on the surface for the reason described above.

  Further, as a method of obtaining a foam layer having a good foam appearance, in a paper container composed of a bottom plate member and a body member, foaming of a low melting point thermoplastic resin from the surface side of the paper to at least one wall surface of the body member There has been proposed a heat-insulating container in which a two-layered heat insulating film comprising an inner layer and a non-foamed layer outer layer of a thermoplastic resin having a melting point higher than the melting point of the thermoplastic resin is applied (see, for example, Patent Document 6). ).

  However, the heat insulating container has a problem that the thickness of the foam layer is thin and the heat insulating property is insufficient.

Japanese Patent Publication No. 48-32283 JP-A-57-110439 JP 2001-270571 A JP 2004-58534 A Japanese Patent Laid-Open No. 2007-217024 JP 05-42929 A

  The present invention has been made in view of the above situation, and provides a foamed laminate having a thick foamed layer, showing heat insulation, excellent smoothness of the foamed layer surface, and good foam appearance. It is intended.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific foam laminate has excellent heat insulating properties and excellent foam appearance, and has completed the present invention. .

  That is, the present invention is a laminate comprising at least (A) layer / (B) layer / base material layer, wherein (A) layer is a polyethylene resin (A), and (B) layer is a high-pressure low-density polyethylene. It is composed of a foam made of (B), and the melting temperature measured by JIS K6922-2 (2005) of polyethylene resin (A) is higher than that of high pressure method low density polyethylene (B), The present invention relates to a foam laminate having a thickness of 1 to 12 μm.

  Furthermore, it is related with the foaming laminated body characterized by the (A) layer being comprised from an ethylene-alpha-olefin copolymer (A).

  Moreover, it is related with the foaming laminated body characterized by the (A) layer being comprised from a low-pressure-method ethylene homopolymer (A).

In addition, the polyethylene-based resin (A) used for the layer (A) is at an angular velocity ω (s ⁻¹ ) at which the loss elastic modulus G ″ (Pa) obtained by measuring dynamic viscoelasticity at 190 ° C. is 500 Pa. The foamed laminate is characterized in that the storage elastic modulus G ′ _a (500) is smaller than G ′ _b (500) of the high pressure method low density polyethylene (B) used for the B layer obtained by the same method. .

  Moreover, it is a foaming laminated body which contains the foaming body layer which consists of a high pressure method low density polyethylene (C) as a (C) layer in the other base-material wall surface of the said laminated body and the base material layer of a laminated body.

  The present invention is described in detail below.

  The polyethylene-based resin (A) constituting the laminate of the present invention has a high pressure method low density in which the melting temperature (hereinafter simply referred to as melting temperature) measured by JIS K6922-2 (2005) constitutes the layer (B). A polyethylene resin (A) higher than the melting temperature of polyethylene (B) is used.

  As such a polyethylene resin (A), a low pressure method ethylene homopolymer, a high pressure method low density polyethylene, an ethylene / α-olefin copolymer, an ethylene / vinyl acetate copolymer, an ethylene / ethyl acrylate copolymer, Examples include ethylene / acrylic acid copolymers and ethylene / methacrylic acid copolymers, but the ethylene / α-olefin copolymer (A) and the low-pressure ethylene homopolymer (A) increase the expansion ratio of the B layer. It is particularly preferable because it can be improved and the laminate appearance is excellent.

  Examples of the α-olefin used in the ethylene / α-olefin copolymer (A) include propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-pentene, 1-hexene, 1 -Heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and the like can be mentioned, and one or more of these can be used.

  The method for obtaining such an ethylene / α-olefin copolymer (A) is not particularly limited, and a high / medium / low pressure ion polymerization method using a Ziegler-Natta catalyst, a Phillips catalyst, or a metallocene catalyst is used. It can be illustrated. Such a copolymer can be conveniently selected from commercially available products, but since the laminate has an excellent appearance, an ethylene / α-olefin copolymer obtained by a polymerization method using a Ziegler-Natta catalyst is used. Particularly preferred.

  The low-pressure ethylene homopolymer (A) constituting the present invention can be obtained by a conventionally known low-pressure ion polymerization method.

Such ethylene / α-olefin copolymer (A) and low-pressure ethylene homopolymer (A) are ethylene / α-olefin copolymers (A ′) satisfying the following (i) to (iv): In addition, it is preferable to use ethylene homopolymer (A ′) because the moldability of the laminate is excellent.
(I) The density (hereinafter simply referred to as density) measured according to JIS K6922-1 (1997) is 890 kg / m ³ or more and 970 kg / m ³ or less.
(Ii) The melt mass flow rate (hereinafter abbreviated as MFR) measured according to JIS K6922-1 (1997) is 0.1 g / 10 min or more and 200 g / 10 min or less.
(Iii) Melt tension measured at 160 ° C. (hereinafter abbreviated as MS _{160. The} unit is mN) and MFR satisfy the following formula (1).

MS ₁₆₀ > 83 × MFR ^−0.62 (1)
(Iv) The shrinkage factor (hereinafter abbreviated as g ′ value) evaluated by gel permeation chromatography (GPC) / intrinsic viscometer is 0.1 or more and less than 0.97.

  Such ethylene / α-olefin copolymer (A ′) and ethylene homopolymer (A ′) are preferably Japanese Patent Application Laid-Open Nos. 2004-346304, 2005-248013, and 2006-321991. Can be produced using a method of polymerizing ethylene and optionally an olefin having 3 or more carbon atoms in the presence of a macromonomer or simultaneously with the synthesis of a macromonomer, as described in JP-A-2007-169341. .

  For example, in the presence of the macromonomer or simultaneously with the synthesis of the macromonomer, the general formula (2)

で表される遷移金属化合物［成分（ｉ）］を主成分とする触媒を用いて、エチレンおよび任意に炭素数３以上のオレフィンを重合する方法を用いて製造することができる。成分（ｉ）中のＭ^１はチタニウム原子、ジルコニウム原子またはハフニウム原子であり、Ｘ^１は例えば各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基である。

It can manufacture using the method which superposes ethylene and the olefin of 3 or more carbon atoms arbitrarily using the catalyst which has the transition metal compound [component (i)] represented by these as a main component. M ¹ in the component (i) is a titanium atom, a zirconium atom or a hafnium atom, and X ¹ is, for example, each independently a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

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

R ¹ in component (i) is represented by the general formula (3), (4) or (5)

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

And the substituents R ⁴ are each independently, for example, a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of R ¹ in component (i) include, 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 , Tetrapropylcyclopentadienyl group, butylcyclopentadienyl group, dibutylcyclopentadienyl group, tributylcyclopentadienyl group, tetrabutylcyclopentadienyl group, phenylcyclopentadienyl group, diphenylcyclopentadienyl Base , Naphthylcyclopentadienyl group, methoxycyclopentadienyl group, trimethylsilylcyclopentadienyl group, indenyl group, methylindenyl group, dimethylindenyl group, trimethylindenyl group, tetramethylindenyl group, pentamethylindenyl group 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, pentabuchi Indenyl group, hexa-butyl indenyl group, phenylindenyl group, diphenyl indenyl group, benzoindenyl group, naphthyl indenyl group, a methoxy indenyl group, and a trimethylsilyl indenyl group.

R ² in component (i) is represented by the general formula (6)

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

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

Specific examples of R ⁵ include a fluorenyl group, a methyl fluorenyl group, a dimethyl fluorenyl group, a trimethyl fluorenyl group, a tetramethyl fluorenyl group, a pentamethyl fluorenyl group, and a hexamethyl fluorenyl group. , Heptamethylfluorenyl group, octamethylfluorenyl group, ethylfluorenyl group, diethylfluorenyl group, triethylfluorenyl group, tetraethylfluorenyl group, pentaethylfluorenyl group, hexaethylfluorene group Nyl group, heptaethylfluorenyl group, octaethylfluorenyl group, propylfluorenyl group, dipropylfluorenyl group, tripropylfluorenyl group, tetrapropylfluorenyl group, pentapropylfluorenyl group , Hexapropylfluorenyl group, heptapropylfluorenyl group, Octapropyl fluorenyl group, butyl fluorenyl group, dibutyl fluorenyl group, tributyl fluorenyl group, tetrabutyl fluorenyl group, pentabutyl fluorenyl group, hexabutyl fluorenyl group, heptabutyl fluorene group Nyl group, octabutylfluorenyl group, phenylfluorenyl group, diphenylfluorenyl group, benzylfluorenyl group, dibenzylfluorenyl group, benzofluorenyl group, dimethylaminofluorenyl group, bis ( (Dimethylamino) fluorenyl group, methoxyfluorenyl group, dimethoxyfluorenyl group and the like.

The crosslinking group R ³ for crosslinking R ¹ and R ² in the component (i) is represented by the general formula (7).

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

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

  Specific examples of the general formula (7) include, for example, a methylene group, an ethylidene group, an ethylene group, a propylidene group, a propylene group, a butylidene group, a butylene group, a pentylidene group, a pentylene group, a hexylidene group, an isopropylidene group, and a methylethylmethylene group. , Methylpropylmethylene group, methylbutylmethylene group, bis (cyclohexyl) methylene group, methylphenylmethylene group, diphenylmethylene group, phenyl (methylphenyl) methylene group, di (methylphenyl) methylene group, bis (dimethylphenyl) methylene group Bis (trimethylphenyl) methylene group, phenyl (ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (diethylphenyl) methylene group, phenyl (propylphenyl) methylene group, di (propylphenyl) methylene Len group, bis (dipropylphenyl) methylene group, phenyl (butylphenyl) methylene group, di (butylphenyl) methylene group, phenyl (naphthyl) methylene group, di (naphthyl) methylene group, phenyl (biphenyl) methylene group, di (Biphenyl) methylene group, phenyl (trimethylsilylphenyl) methylene group, bis (trimethylsilylphenyl) methylene group, bis (pentafluorophenyl) methylene group, silanediyl group, disilanediyl group, trisilanediyl group, tetrasilanediyl group, dimethylsilanediyl group, Bis (dimethylsilane) diyl group, diethylsilanediyl group, dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediyl group, etc. Door can be.

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

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

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

  Examples of the olefin having 3 or more carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, α-olefin such as vinylcycloalkane, norbornene, Examples include cyclic olefins such as norbornadiene, dienes such as butadiene or 1,4-hexadiene, and styrene. Two or more of these olefins can be mixed and used.

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

  Examples of the olefin having 3 or more carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, α-olefin such as vinylcycloalkane, norbornene, Examples include cyclic olefins such as norbornadiene, dienes such as butadiene or 1,4-hexadiene, and styrene. Two or more of these olefins can be mixed and used.

  When an ethylene polymer having a vinyl group at the terminal or an ethylene copolymer having a vinyl group at the terminal is used as the macromonomer, the linear polyethylene equivalent (D) number average molecular weight (Mn) is 2,000 or more. Yes, preferably 3,000 or more, more preferably 5,000 or more.

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

  As a specific method for producing a macromonomer, for example, the general formula (8)

で表される遷移金属化合物［成分（ｉｉ）］を主成分とする触媒を用いて、エチレンおよび任意に炭素数３以上のオレフィンを重合する方法を用いて製造することができる。

It can manufacture using the method which superposes | polymerizes ethylene and the olefin of 3 or more carbon atoms arbitrarily using the catalyst which has the transition metal compound [component (ii)] represented by these as a main component.

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

The hydrocarbon group having 1 to 20 carbon atoms in X ^2, can be the same as the example ^{X 1.}

R ⁷ and R ⁸ in component (ii) are represented by the general formula (9), (10) or (11).

で表され、それぞれ同じでも異なっていてもよく、Ｍ^２とともにサンドイッチ構造を形成する。一般式（９）、（１０）または（１１）におけるＲ^１０は例えば各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基である。

In expressed, which may be the same or different, to form a sandwich structure together with M ^2. R ¹⁰ in the general formula (9), (10) or (11) is, for example, each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms of R ^{10 in} the general formula (9), (10) or (11) include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Octyl group, nonyl group, decyl group, norbornyl group, phenyl group, styryl group, biphenylyl group, naphthyl group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group, dipropyl Phenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, diphenylethyl group , Diphenylpropyl group, diph Examples include an butyl group, a vinyl group, a propenyl group, a butenyl group, a butadienyl group, a pentenyl group, a pentadienyl group, a hexenyl group, and a hexadienyl group.

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

In the general formula (8), the bridging group R ⁹ that bridges R ⁷ and R ⁸ is represented by the general formula (12), (13) or (14).

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

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

Formula (12), (13) the hydrocarbon group having 1 to 20 carbon atoms in the ^{R 11} or (14), can be, for example, same as ^{R 10.}

  Specific examples of the general formula (12) include, for example, a methylene group, an ethylidene group, an ethylene group, a propylidene group, a propylene group, a butylidene group, a butylene group, a pentylidene group, a pentylene group, a hexylidene group, an isopropylidene group, and a methylethylmethylene group. , Methylpropylmethylene group, methylbutylmethylene group, bis (cyclohexyl) methylene group, methylphenylmethylene group, diphenylmethylene group, phenyl (methylphenyl) methylene group, di (methylphenyl) methylene group, bis (dimethylphenyl) methylene group Bis (trimethylphenyl) methylene group, phenyl (ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (diethylphenyl) methylene group, phenyl (propylphenyl) methylene group, di (propylphenyl) Tylene group, bis (dipropylphenyl) methylene group, phenyl (butylphenyl) methylene group, di (butylphenyl) methylene group, phenyl (naphthyl) methylene group, di (naphthyl) methylene group, phenyl (biphenyl) methylene group, di (Biphenyl) methylene group, phenyl (trimethylsilylphenyl) methylene group, bis (trimethylsilylphenyl) methylene group, bis (pentafluorophenyl) methylene group, silanediyl group, disilanediyl group, trisilanediyl group, tetrasilanediyl group, dimethylsilanediyl group, Bis (dimethylsilane) diyl group, diethylsilanediyl group, dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediyl group, divinyli Silanediyl group, diallyl silane diyl group, (methyl) (vinyl) silanediyl group, and (allyl) (methyl) silanediyl group.

As specific compounds represented by the general formula (8) used in the present invention, when M ² is a zirconium atom and X ² is a chlorine atom, for example, methylenebis (cyclopentadienyl) zirconium dichloride, isopropylidenebis ( Cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (cyclopentadienyl) zirconium dichloride, diphenylmethylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, methylenebis (methyl) Cyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (methylcyclopentadienyl) di Konium dichloride, diphenylmethylenebis (methylcyclopentadienyl) zirconium dichloride, ethylenebis (methylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclo Pentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (methylcyclopentadiyl) Enyl) zirconium dichloride, ethylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, methylene bis (2,4-dimethyl cyclide) Lopentadienyl) zirconium dichloride, isopropylidenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylmethylenebis (2,4 -Dimethylcyclopentadienyl) zirconium dichloride, ethylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) Zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (indenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (Indenyl) zirconium dichloride, ethylene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, diethylsilanediylbis (cyclopentadienyl) zirconium dichloride, di (n-propyl) ) Silanediylbis (cyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (cyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (cyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride, Di (p-tolyl) silanediylbis (cyclopentadienyl) zirconium dichloride, divinylsilane dii Bis (cyclopentadienyl) zirconium dichloride, diallylsilanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (vinyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (allyl) (methyl) silanediylbis (cyclopentadi) Enyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (cyclopentadi) Enyl) zirconium dichloride, (cyclohexyl) (methyl) bis (cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanedi Irbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (methylcyclopentadiyl) Enyl) zirconium dichloride, diisopropylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, (ethyl) (Methyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) Randiylbis (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, diisopropylsila Diyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) Enyl) zirconium dichloride, (ethyl) (methyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) Zirconium dichloride, (methyl) (isopropyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) (cycline Lopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) Zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (2,4 -Dimethylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanedi Rubis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (2,4- Dimethylcyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (2,4-dimethylcyclopentadienyl) zirconium dichloride (Methyl) (phenyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, di Tylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, di (n-propyl) silanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, diisopropylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, dicyclohexylsilanediyl (Cyclopentadienyl) (indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (2-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (3 -Methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (3-isopropylcyclopenta Dienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (2,3-dimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (2,4-dimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilane Diyl (2,3,4-trimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (2,3,5-trimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) ) (2-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclope) Tadienyl) (7-ethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-phenylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethylindenyl) zirconium Dichloride, dimethylsilanediyl (cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methoxy-7-methylindenyl) zirconium dichloride, dimethylsilanediyl ( Cyclopentadienyl) (2-dimethylamino-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-trimethylsilyl-7-methylindenyl) zirconi Mudichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (7-methylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl ( Cyclopentadienyl) (4-isopropyl-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-phenyl-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) ) (4-methoxy-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-dimethylamino-7-methylindenyl) zirconium dichloride, dimethyl Tylsilanediyl (cyclopentadienyl) (4-trimethylsilyl-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopenta Dienyl) (3,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,3,4,7-tetramethylindenyl) zirconium dichloride, dimethylsilanediyl (3,4) -Dimethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (3,4-bis (trimethylsilyl) cyclopentadienyl) (2,4,7-trimethylindenyl) zirco Um dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4-phenyl-7-methylindenyl) zirconium dichloride , Dimethylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride (1,1,3,3-tetramethyldisiloxane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (1,1,3,3-tetraisopropyldisiloxane-1,3-diyl- Biscyclo Ntadienyl) zirconium dichloride, (1,1,3,3-tetraphenyldisiloxane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl) -Biscyclopentadienyl) zirconium dichloride, (1,1-diisopropyltyl-1-silaethane-1,2-diyl-biscyclopentadienyl) zirconium dichloride, (1,1-diphenyl-1-silaethane-1, 2-diyl-biscyclopentadienyl) zirconium dichloride, (propane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (1,1,3,3-tetramethylpropane-1,3-diyl- Biscyclopentadienyl) zirconium dichloride, (2,2-dimethylpropane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (butane-1,4-diyl-biscyclopentadienyl) zirconium dichloride, (pentane-1,5-diyl- Biscyclopentadienyl) zirconium dichloride, (1,1,2,2-tetramethyldisilane-1,2-diyl-biscyclopentadienyl) zirconium dichloride, (1,1,2,2-tetraphenyldisilane- Examples include 1,2-diyl-biscyclopentadienyl) zirconium dichloride and the like. The compounds obtained by substituting X ² in the transition metal compound a fluorine atom, a bromine atom or an iodine atom can be exemplified. Furthermore, the M ² of the transition metal compound can also be exemplified compounds obtained by replacing the titanium atom or a hafnium atom. These compounds can also be used in combination.

  Examples of the catalyst having component (ii) as a main component include a catalyst obtained by bringing component (ii) and component (iii) into contact with each other.

  A specific method for producing such an ethylene / α-olefin copolymer (A ′) and an ethylene homopolymer (A ′) is not particularly limited, but a catalyst containing component (ii) as a main component is used. After synthesizing a macromonomer by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms, ethylene and optionally having 3 or more carbon atoms are used in the presence of the obtained macromonomer using a catalyst mainly composed of component (i). Simultaneously synthesizing macromonomers by polymerizing olefins and polymerizing ethylene and optionally olefins having 3 or more carbon atoms using a catalyst mainly composed of component (i) and component (ii) A method for producing an ethylene polymer can be exemplified.

  Such ethylene / α-olefin copolymer (A ′) and ethylene homopolymer (A ′) can be produced by any of gas phase polymerization, slurry polymerization, and solution polymerization. In the case of the above, an ethylene polymer having an excellent particle form can be produced.

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

MS ₁₆₀ of such ethylene / α-olefin copolymer (A ′) and ethylene homopolymer (A ′) is a capillary viscometer with a barrel diameter of 9.55 mm (Toyo Seiki Seisakusho, trade name: Capillograph). the length is 8 mm, diameter 2.095 mm, the inflow angle mounting orifices 90 °, the piston descending speed 10 mm / min, is the measured value under the condition of draw ratio is _{47, MS 160} and MFR Is the following formula (1)
MS ₁₆₀ > 83 × MFR ^−0.62 (1)
Meet. Furthermore, the following formula (15)
MS ₁₆₀ > 95 × MFR ^−0.60 (15)
It is preferable that the relationship satisfies the above condition because it is excellent in moldability.

  Such ethylene / α-olefin copolymer (A ′) and ethylene homopolymer (A ′) were measured under the following conditions using gel permeation chromatography (hereinafter abbreviated as GPC). Then, a universal calibration curve was measured with monodisperse polystyrene, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated as the molecular weight of linear polyethylene was in the range of 2-7. It is preferable because the mechanical strength of the molded product and stable extrusion moldability can be compatible.

Model: Waters 150C ALC / GPC
Solvent: 1,2,4-trichlorobenzene Flow rate: 1 mL / min Temperature: 140 ° C
Measurement concentration: 30 mg / 30 mL
Injection volume: 100 μL
Column: 3 TSKgel GMH HR-H manufactured by Tosoh Moreover, such an ethylene / α-olefin copolymer (A ′) and an ethylene homopolymer (A ′) are contraction factors evaluated by a GPC / intrinsic viscometer ( g ′ value) is 0.1 or more and less than 0.97, preferably 0.3 or more and less than 0.95, and more preferably 0.4 or more and less than 0.9. The shrinkage factor (g ′ value) in the present invention is a parameter representing the degree of long-chain branching, and is measured by the intrinsic viscosity method of the component having a molecular weight of 300,000 (g / mol) determined by GPC. This is the ratio between the intrinsic viscosity of an ethylene polymer and the intrinsic viscosity at the same molecular weight of linear polyethylene having no branching.

In addition, the ethylene / α-olefin copolymer (A ′) and the ethylene homopolymer (A ′) have a long chain branch number of 0.01 to 3 per 1000 carbon atoms. This is preferable because stable extrusion can be performed. In addition, the number of long-chain branches is the number of branches of a hexyl group or more (carbon number of 6 or more) detected by ¹³ C-NMR measurement.

  When the MFR of the polyethylene-based resin (A) constituting the laminate of the present invention is in the range of 0.1 to 100 g / 10 min, more preferably 3 to 50 g / 10 min, processing is performed when the laminate is molded. It becomes easy.

  The ethylene / α-olefin copolymer (A) and the low-pressure ethylene homopolymer (A) constituting the present invention may be blended with other polyolefins such as high-pressure low-density polyethylene and polypropylene, The blending ratio of these other polyolefins is preferably 1 to 30% by weight from the viewpoint of laminate moldability and laminate appearance.

  Furthermore, the polyethylene-based resin (A) constituting the present invention includes additives generally used for polyolefin resins, such as an antioxidant, a light stabilizer, an antistatic agent, a lubricant, and an antiblocking agent, as necessary. May be added within a range not impairing the object of the present invention.

  The high pressure low density polyethylene (B) constituting the laminate of the present invention can be obtained by a conventionally known high pressure method radical polymerization method.

  The MFR of the high-pressure method low-density polyethylene (B) is preferably in the range of 4 to 100 g / 10 minutes because of excellent foamability.

The density of the high-pressure method low density polyethylene (B) is preferably 870 to 935 kg / m ³ , more preferably 890 to 935 kg / m ³ , and even more preferably 890 to 910 kg / m ³ because of its excellent foamability. ³ range.

  In the high-pressure low-density polyethylene (B) constituting the laminate of the present invention, an antioxidant, a light stabilizer, an antistatic agent, a lubricant, an antiblocking agent and the like are generally used for polyolefin resins as necessary. The additives may be added within a range not impairing the object of the present invention.

  Furthermore, other polyolefins may be mixed with the high pressure method low density polyethylene (B). At this time, since the foamability is excellent, the mixing ratio is preferably 50 to 99% by weight for the high pressure method low density polyethylene (B) and 1 to 50% by weight for the other polyolefins.

Examples of the polyolefin to be mixed with the high-pressure method low-density polyethylene (B) include ethylene / α-olefin copolymers, polypropylene, polybutene, and the like. Since the foam has excellent foamability, the density is 850 kg / m ³ or more and 920 kg / m. An ethylene / α-olefin copolymer (B) of less than ³ is preferred.

  Examples of the α-olefin used in the ethylene / α-olefin copolymer (B) include propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-pentene, 1-pentene, Examples include hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and the like, and one or more of these are used.

  Furthermore, the method for obtaining the ethylene / α-olefin copolymer (B) is not particularly limited, and examples thereof include a high / medium / low pressure ion polymerization method using a Ziegler-Natta catalyst, a Philips catalyst, or a metallocene catalyst. Such a copolymer can be conveniently selected from commercially available products.

  When mixing the polyolefin with the high-pressure low-density polyethylene (B) constituting the laminate of the present invention, even if the pellet mixture is a mixture of high-pressure low-density polyethylene (B) pellets and polyolefin pellets in a solid state. Although a mixture obtained by melt-kneading with a single screw extruder, twin screw extruder, kneader, Banbury or the like is preferable, a product with stable quality can be obtained. When using a melt-kneading apparatus, the melting temperature is preferably about the melting point of polyethylene resin to about 300 ° C.

Further, the loss elastic modulus G ″ (Pa) required by measuring the dynamic viscoelasticity at 190 ° C. of the polyethylene resin (A) constituting the laminate of the present invention using a cone-disk rheometer is The storage elastic modulus G ′ _a (500) at an angular velocity ω (s ⁻¹ ) of 500 Pa is higher than G ′ _b (500) of the high pressure method low density polyethylene (B) used for the B layer obtained by the same method. A small value is preferable because stable extrusion molding is possible and an excellent foam appearance can be obtained, and G ′ _b (500) of 95 Pa or less is preferable because an excellent foam appearance can be obtained.

  The thickness of the polyethylene resin (A) constituting the laminate of the present invention is 1 to 12 μm in order to obtain a good foam thickness and foam appearance. When the thickness of the A layer is less than 1 μm, it is not preferable because the smoothness of the surface of the laminate is inferior, and when it exceeds 12 μm, the foaming ratio of the B layer is inferior.

  The thickness of the foam made of the high-pressure method low-density polyethylene (B) constituting the laminate of the present invention is preferably 300 μm or more in order to obtain good heat insulation.

The moisture contained in the base material constituting the laminate of the present invention is to foam the (B) layer and the (C) layer by heating, and the moisture content is 20 to 30 g / m ^{2, which} is the expansion ratio of the B layer. It is preferable because it is excellent in appearance of the laminate, and more preferably 20 to 28 g / m ² .

As the base material constituting the laminate of the present invention, paper made of natural pulp such as high-quality paper and kraft paper (hereinafter simply referred to as paper), synthetic fiber or synthetic resin film is made pseudo-paper. So-called synthetic paper, foamed sheets, sheets made of porous inorganic materials such as zeolite, and the like can be exemplified, and paper is preferable because it is relatively easy to adjust the amount of water contained in the substrate. The substrate may be printed with colored ink or the like by a conventionally known technique. When using paper substrate, since the easy adjustment of water content, it is preferred that the basis weight 150~500g / ^{m 2,} more preferably from 200 to 400 g / ^{m 2.}

  Another layer (C) may be laminated on the other substrate wall surface of the substrate constituting the laminate of the present invention. In the layer (C), a foamed layer may be formed or a non-foamed layer may be formed, but it is preferable to form a foamed layer because of excellent heat insulation. Examples of the material used for the layer (C) include high pressure method low density polyethylene, low pressure method ethylene homopolymer, ethylene / α-olefin copolymer, and polyolefin such as polypropylene. Process low density polyethylene (C) is preferred.

  Such a high pressure method low density polyethylene (C) can be obtained by a conventionally known high pressure method radical polymerization method.

  The MFR of the high-pressure method low-density polyethylene (C) is preferably in the range of 4 to 100 g / 10 minutes because of excellent foamability.

The density of the high-pressure method low density polyethylene (C) is preferably 870 to 935 kg / m ³ , more preferably 890 to 935 kg / m ³ , and even more preferably 890 to 910 kg / m ³ because of its excellent foamability. ³ range.

  In the high-pressure low-density polyethylene (C) constituting the laminate of the present invention, an antioxidant, a light stabilizer, an antistatic agent, a lubricant, an antiblocking agent and the like are generally used for polyolefin resins as necessary. Additives may be added as long as the object of the present invention is not impaired.

  Furthermore, other polyolefins may be mixed with the high pressure method low density polyethylene (C). At this time, since the foamability is excellent, the mixing ratio is preferably 50 to 99% by weight for the high pressure method low density polyethylene (C) and 1 to 50% by weight for the other polyolefins.

Examples of the polyolefin mixed with the high-pressure low-density polyethylene (C) include ethylene / α-olefin copolymers, polypropylene, polybutene, and the like. Since the foam has excellent foamability, the density is 850 kg / m ³ or more and 920 kg / m. An ethylene / α-olefin copolymer (C) of less than ³ is preferred.

  Examples of the α-olefin used in the ethylene / α-olefin copolymer (C) include propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-pentene, 1-pentene, Examples include hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and the like, and one or more of these are used.

  Furthermore, the method for obtaining such an ethylene / α-olefin copolymer (C) is not particularly limited, and a high / medium / low pressure ion polymerization method using a Ziegler-Natta catalyst, a Philips catalyst, or a metallocene catalyst. Such a copolymer can be conveniently selected from commercially available products.

  When mixing polyolefin with the high-pressure method low-density polyethylene (C) constituting the laminate of the present invention, a pellet mixture in which pellets of the high-pressure method low-density polyethylene (C) and polyolefin pellets are mixed in a solid state. Although a mixture obtained by melt-kneading with a single screw extruder, twin screw extruder, kneader, Banbury or the like is preferable, a product with stable quality can be obtained. When using a melt-kneading apparatus, the melting temperature is preferably about the melting point of polyethylene resin to about 300 ° C.

  As a technique for obtaining the laminate of the present invention, a technique obtained by extrusion laminating a polyethylene-based resin (A) and a high-pressure method low-density polyethylene (B) on a base material and heating and foaming, and (B) a foam to be a layer Can be exemplified by a method in which a polyethylene resin (A) is obtained by extrusion lamination. Since processing is easy, the method obtained by carrying out the co-extrusion lamination process which forms simultaneously a polyethylene-type resin (A) and a high pressure method low density polyethylene (B), and heat-foaming is preferable.

  Examples of the method for obtaining a laminate by an extrusion laminate molding method include various extrusion lamination methods such as a single lamination method, a tandem lamination method, a sandwich lamination method, and a coextrusion lamination method. The temperature of the resin in the extrusion laminating method is preferably in the range of 260 to 350 ° C, and the surface temperature of the cooling roll is preferably in the range of 10 to 50 ° C.

Also, in extrusion laminating, immediately after the high-pressure low-density polyethylene (B) is formed into an extruded layer in the molten state, the substrate adhesive surface of the layer is exposed to an oxygen-containing gas or an ozone-containing gas, and bonded to the substrate. Is preferably used because of its excellent adhesiveness to the base material layer. When the adhesion between the high-pressure method low-density polyethylene (B) and the substrate is improved by the ozone-containing gas, the amount of ozone gas treated is 1 m ^{2 of the} film made of the high-pressure method low-density polyethylene (B) extruded from the die. It is preferable to spray 0.5 mg or more of ozone per hit.

  The extrusion laminating method in the method of obtaining the laminate of the present invention by heat foaming further improves the adhesiveness between the high pressure method low density polyethylene (B) and the base material layer, so that the high pressure method low density polyethylene (B) is foamed. The heat treatment can be performed for 10 hours or more at a temperature that does not occur, for example, 30 ° C. to 60 ° C. Moreover, you may perform well-known surface treatments, such as a corona treatment, a flame treatment, and a plasma treatment, with respect to the adhesive surface of a base material as needed. If necessary, an anchor coating agent may be applied to the substrate.

  As a heating method in the method of obtaining the laminate of the present invention by heat foaming, in addition to hot air, electric heat, and electron beam, the laminate is formed into a container shape, and a high-temperature object is filled to use the heat of the filling. Any means can be used. Heating can be performed by a batch method in an oven, a continuous method using a conveyor, or the like.

  The heating temperature and the heating time vary depending on the substrate to be used and the type of the thermoplastic resin, but the heating temperature is generally 110 ° C. to 200 ° C., and the heating time is 10 seconds to 5 minutes. .

  The foamed laminate of the present invention is suitably used for containers that require heat insulation, such as paper containers for high-temperature beverages such as coffee and soup, and containers for instant foods such as instant noodles.

  The foamed laminate of the present invention is a foamed laminate that exhibits excellent heat insulation, has excellent smoothness on the surface of the foamed layer, and has a good surface appearance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  Further, the ethylene / α-olefin copolymer (A3) and the ethylene homopolymer (A4) used in the examples are produced by the production methods shown below.

Furthermore, the preparation of the modified hectorite, the preparation of the catalyst, the production of the polyethylene polymer and the solvent purification were all carried out under an inert gas atmosphere. Solvents and the like used for the preparation of modified hectorite, catalyst, and polyethylene polymer were all purified, dried and deoxygenated in a known manner. Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, propane-1,3-diylbis (cyclopentadienyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilanediyl (Cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, 1,1,3,3-tetramethyldisiloxane-1,3-diylbis (cyclopentadienyl) zirconium dichloride, diphenylmethylene (1- Indenyl) (9-fluorenyl) zirconium dichloride was synthesized and identified by a known method. A hexane solution (0.714M) of triisobutylaluminum was manufactured by Tosoh Finechem Corporation.
[Production Method of Ethylene / α-Olefin Copolymer (A3)]
[Preparation of modified hectorite]
After adding 3 liters of ethanol and 100 ml of 37% concentrated hydrochloric acid to 3 liters of water, 330 g (1.1 mol) of N, N-dimethyl-octadecylamine was added to the resulting solution and heated to 60 ° C. A hydrochloride solution was prepared. 1 kg of hectorite was added to this solution. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 50 L of 60 ° C. water. Then, it dried at 60 degreeC and 10 < ^-3 > torr for 24 hours, and the modified | denatured hectorite with an average particle diameter of 5.2 micrometers was obtained by grind | pulverizing with a jet mill.
[Preparation of catalyst (p1)]
500 g of the modified hectorite was suspended in 1.7 liters of hexane, and 8.25 g (20.0 mmol) of dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride and a hexane solution of triisobutylaluminum ( 0.714M) Add 2.8 liters (2 mol) of mixture, stir at 60 ° C. for 3 hours, let stand and remove supernatant, add triisobutylaluminum in hexane (0.15M) Thus, a catalyst precursor slurry (100 g / L) was obtained.

10 mol% of isopropylidene (1-cyclopentadienyl) (2,7-di-) with respect to dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride was added to the catalyst precursor slurry prepared above. 1.21 g (2.22 mmol) of t-butyl-9-fluorenyl) zirconium dichloride was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and a hexane solution (0.15M) of triisobutylaluminum was further added to finally obtain a catalyst slurry of 100 g / L.
[Manufacture of macromonomer]
Into a polymerization vessel having an internal volume of 540 liters, 300 liters of hexane and 7.6 liters of 1-butene were introduced, and the internal temperature of the autoclave was raised to 85 ° C. To the autoclave, 135 ml of the catalyst (p1) was added, and ethylene gas was introduced until the ethylene partial pressure reached 1.2 MPa to initiate polymerization. The polymerization temperature was controlled at 85 degrees. During the polymerization, ethylene gas was continuously introduced so that the partial pressure was maintained at 1.2 MPa. 90 minutes after the start of polymerization, the internal pressure of the polymerization vessel was released to obtain a macromonomer. The macromonomer extracted from the polymerization vessel had Mn = 10,950 and Mw / Mn = 2.61. Further, no long chain branching was detected.
[Production of ethylene / α-olefin copolymer (A3)]
In the polymerization vessel containing the macromonomer produced above and having an internal volume of 540 liters, 0.22 liter of 1-butene, 0.75 liter of a hexane solution of triisobutylaluminum (0.714 mol / L) and diphenylmethylene (1- Indenyl) (9-fluorenyl) zirconium dichloride (3.75 mmol) was introduced, and the internal temperature of the autoclave was raised to 85 ° C. Polymerization was started by introducing an ethylene / hydrogen mixed gas (hydrogen 22,000 ppm) until the partial pressure reached 0.2 MPa. During the polymerization, an ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure was maintained at 0.2 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 54 kg of ethylene / α-olefin copolymer (A3) was obtained. The density of the obtained ethylene / α-olefin copolymer (A3) was 924 kg / m ³ , MFR was 15 g / 10 min, the number of long chain branches was 0.13 per 1000 carbon atoms, MS ₁₆₀ was 38 mN, g ′ Was 0.89.
[Method for producing ethylene homopolymer (A4)]
[Preparation of catalyst (p2)]
Suspend 500 g of the modified hectorite prepared in [Preparation of modified hectorite] in 1.8 liters of hexane, add 2.9 liters of hexane solution of triisobutylaluminum (0.714M), and stir at room temperature for 1 hour. As a result, a contact product of modified hectorite and triisobutylaluminum was obtained. On the other hand, a catalyst slurry (100 g / L) was obtained by adding a solution obtained by dissolving 6.97 g (20 mmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride in toluene and stirring at room temperature overnight. .
[Production of ethylene homopolymer (A4)]
Except that 1-butene was not added and that 115 ml of catalyst (p2) was added instead of catalyst (p1), the same method as [Production method of ethylene / α-olefin copolymer (A3)] was used. Polymerization was performed to obtain 50 kg of an ethylene homopolymer (A4). The density of the resulting ethylene homopolymer (A4) is 963 kg / m ³ , MFR is 15 g / 10 min, the number of long chain branches is 0.12 per 1000 carbon atoms, MS ₁₆₀ is 55 mN, and g ′ is 0.88. Met.

  Below, the evaluation method of each physical property is shown.

Various physical properties of the ethylene polymer were measured by the following methods.
(1) Density Density was measured according to JIS K6922-1 (1997).
(2) Melt mass flow rate (MFR)
MFR was measured according to JIS K6922-1 (1997).
(3) Melting temperature It measured based on JISK6922-2 (2005).
(4) Number of long-chain branches The number of long-chain branches was determined by measuring the number of branches having 6 or more carbon atoms (hexyl group) by ¹³ C-NMR using a Varian VNMRS-400 nuclear magnetic resonance apparatus. The solvent is tetrachloroethane -d _2. The number per 1000 main chain methylene carbons was determined from the following formula (16). In the formula, IA _α is an integrated intensity of a branched α-carbon peak of a hexyl group or higher (chemical shift: 34.6 ppm), and IA _tot is an integrated intensity of a main chain methylene carbon peak (30.0 ppm). is there.

Number of long chain branches = IA _α / (3 × IA _tot ) (16)
(5) Melt tension For melt tension, a capillary viscometer (Toyo Seiki Seisakusho, trade name: Capillograph) with a barrel diameter of 9.55 mm is fitted with an orifice with a length of 8 mm, a diameter of 2.095 mm, and an inflow angle of 90 °. And measured. The temperature was set to 160 ° C., the piston lowering speed was set to 10 mm / min, the stretch ratio was set to 47, and the load (mN) required for take-up was MS ₁₆₀ .
(6) Molecular weight distribution The molecular weight distribution (Mw / Mn) was measured by gel permeation chromatography (GPC). Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC apparatus, Tosoh Co., Ltd. TSKgel GMHhr-H (20) HT is used as the column, the column temperature is set to 140 ° C., and 1 is used as the eluent. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined using 2,4-trichlorobenzene. A measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The molecular weight calibration curve was calibrated using a polystyrene sample having a known molecular weight, and Mw and Mn were determined as values in terms of linear polyethylene.
(7) Moisture content of base material Measurement was carried out using a Karl Fischer method moisture measuring device (trade name CA-05, manufactured by Mitsubishi Chemical Corporation) at a measurement temperature of 165 ° C.
(8) Contractile factor (g 'value)
The shrinkage factor (g ′ value) is a method of measuring the intrinsic viscosity ([η]) of polyethylene fractionated by GPC, and the [η] at a molecular weight of 300,000 of the polyethylene resin (A) used in the examples is It is a value divided by [η] at the same molecular weight of linear polyethylene having no branching. Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC device, Tosoh Co., Ltd. TSKgel GMHhr-H (20) HT is used as the column, the column temperature is set to 145 ° C., and 1 is used as the eluent. Measurement was performed using 2,4-trichlorobenzene. A measurement sample was prepared at a concentration of 2.0 mg / mL, and 0.3 mL was injected and measured. As a viscometer, a capillary differential pressure viscometer 210R ⁺ manufactured by Viscotek was used.
(9) G ′ (500)
Using a cone-disk rheometer (trade name: SR2000, manufactured by Rheometrics), storage elastic modulus G ′ at an angular velocity ω (s ⁻¹ ) with a loss elastic modulus G ″ (Pa) of 500 Pa at 190 ° C. ( Pa) was determined.
(10) Thickness of foam layer The laminates obtained in the examples were cut into 20 cm × 30 cm, allowed to stand for 240 seconds in a small oven (made by Werner Mathis AG) heated to 115 ° C., then taken out and air-cooled at room temperature. Until cooled. Samples of the laminate after foaming and the laminate laminate before foaming as a blank were taken, and cross-sectional photographs were taken with an optical microscope. The thickness of the foam layer was measured from the cross-sectional photograph, and the average thickness measured at five locations was defined as the thickness of the (B) layer and (C) layer. The total thickness of the (B) layer and (C) layer was defined as the total thickness of the foamed layer.
(11) State of foam surface The laminate obtained in the example was cut into 20 cm × 30 cm, left standing in a small oven (made by Werner Mathis AG) heated to 115 ° C. for 240 seconds, then taken out and room temperature in air Until cooled. The smoothness of the surface of the obtained foam was visually observed. The case where the smoothness of the surface was excellent was evaluated as ◎, the case where it was slightly inferior but good as the appearance was good, the case where it was still inferior, but the case where there was no problem in use as a paper container was indicated as Δ, and the case where it was defective was indicated as x.

Example 1
As the polyethylene resin (A), an ethylene / 1-butene copolymer having an MFR of 20 g / 10 min, a density of 920 kg / m ³ , a melting temperature of 122 ° C., and G ′ (500) of 18 Pa (Tosoh Corporation) Product name Nipolon-L M65) (A1) is polyethylene resin (B), MFR is 13 g / 10 min, density is 919 kg / m ³ , melting temperature is 107 ° C., and G ′ (500) is 92 Pa. High pressure method low density polyethylene (trade name Petrocene 212 manufactured by Tosoh Corporation) (B1) was used. Further, on the opposite side of the paper to the resin layer, high-pressure low-density polyethylene (Tosoh) having a MFR of 13 g / 10 min, a density of 919 kg / m ³ and a melting temperature of 107 ° C. as high-pressure low-density polyethylene (C). (Trade name) Petrocene 212) (C1) manufactured by Corporation was used.

First, (C1) is supplied to a single screw extrusion laminator (made by Musashinokikai Co., Ltd.) having a screw having a diameter of 90 mmφ, extruded from a T die at a temperature of 310 ° C., has a water content of 24 g / m ² , and has a basis weight of 300 g. / ^m take-off speed is 70m / min on a ^two and a paper substrate, was performed as extrusion lamination molding air gap length a thickness of 60μm at 135mm. Further, (A1) is supplied to a single screw extruder (Musashi no Kikai Co., Ltd.) having a screw with a diameter of 65 mmφ, and (B1) is supplied to a single screw extruder (Musashi Nokikai Co., Ltd.) having a screw with a diameter of 90 mmφ. (C1) resin layer of the laminate so that the thickness of (A1) is 10 μm and the thickness of (B1) is 40 μm at a temperature of 320 ° C., a take-up speed of 70 m / min, an air gap length of 165 mm. Co-extrusion lamination is performed on the back side of the base material layer, and the ethylene / 1-butene copolymer (A1), the high pressure method low density polyethylene (B1), the paper base material, and the high pressure method low density polyethylene (C1) are laminated in this order. Thus obtained laminate was obtained. This laminate was heated and foamed, and the thickness of the foam layer and the state of the foam surface were evaluated. The results of foamability evaluation are shown in Table 1.

Example 2
A laminate was obtained in the same manner except that the polyethylene resin used in Example 1 was used, and the thickness of (A1) was 2 μm and the thickness of (B1) was 48 μm. This laminate was heated and foamed, and the thickness of the foam layer and the state of the foam surface were evaluated. The results are shown in Table 1.

Example 3
(A) The high-pressure low-density polyethylene (Made by Tosoh Corporation) having a MFR of 3 g / 10 min, a density of 924 kg / m ³ , a melting temperature of 113 ° C., and G ′ (500) of 102 Pa as the resin for the layer (A) Laminate molding was performed in the same manner as in Example 1 except that the name Petrocene 205) (A2) was used, and the laminate was foamed to evaluate the thickness of the foamed layer and the state of the foamed surface. The results of foamability evaluation are shown in Table 1. In addition, when co-extrusion laminate molding was performed, the instability of extrusion partially occurred.

Example 4
(A) As the resin of the layer, except that the ethylene / α-olefin copolymer (A3) was used, laminate molding was performed in the same manner as in Example 1, the laminate was foamed, the thickness of the foam layer, the foam surface The condition was evaluated. The results of foamability evaluation are shown in Table 1.

Example 5
(A) The laminate was molded in the same manner as in Example 1 except that the ethylene homopolymer (A4) was used as the resin for the layer, and the laminate was foamed to evaluate the thickness of the foamed layer and the state of the foamed surface. . The results of foamability evaluation are shown in Table 1.

比較例１
（Ａ１）層の厚みを４０μｍ、（Ｂ１）層の厚みを１０μｍとした以外は実施例１と同様にして、ラミネート成形を行い、積層体を発泡させ発泡層の厚み、発泡表面の状態を評価した。発泡性評価の結果を表２に示す。発泡表面の状態は良好であったが、発泡後の発泡層の厚みが不十分であった。

Comparative Example 1
(A1) Except that the thickness of the layer was 40 μm and the thickness of the (B1) layer was 10 μm, laminate molding was performed, and the laminate was foamed to evaluate the thickness of the foamed layer and the state of the foamed surface. did. The results of foamability evaluation are shown in Table 2. The state of the foamed surface was good, but the thickness of the foamed layer after foaming was insufficient.

Comparative Example 2
Instead of the (A) layer / (B) layer type 2 layer co-extrusion laminate molding, the resin (B1) is supplied to a single screw extrusion laminator (manufactured by Musashinokikai Co., Ltd.) having a screw with a diameter of 90 mm, and 310 ° C. A polyethylene resin was obtained in the same manner as in Example 1 except that extrusion extrusion molding was performed so as to obtain a thickness of 50 μm by extrusion from a T die at a temperature of 5 ° C., and the thickness of the foamed layer and the state of the foamed surface were obtained by foaming the laminate. Evaluated. The results of foamability evaluation are shown in Table 2. Although the thickness of the foamed layer after foaming was good, the surface smoothness was insufficient.

Comparative Example 3
(A) High-pressure low-density polyethylene (Made by Tosoh Corporation) having an MFR of 8 g / 10 min, a density of 918 kg / m ³ , a melting temperature of 105 ° C., and G ′ (500) of 108 Pa as the resin of the layer (A) Laminate molding was performed in the same manner as in Example 1 except that petrocene 213) (A5) was used, and the laminate was foamed to evaluate the thickness of the foamed layer and the state of the foamed surface. The results of foamability evaluation are shown in Table 2. Both the thickness of the foamed layer after foaming and the smoothness of the surface were insufficient.

Claims (5)

A laminate comprising at least (A) layer / (B) layer / base material layer, wherein (A) layer is a polyethylene resin (A), and (B) layer is a high pressure method low density polyethylene (B). A foam laminate comprising the body and satisfying the following requirements (a) to (b).
(A) The melting temperature of the polyethylene resin (A) measured by JIS K6922-2 (2005) is higher than that of the high pressure method low density polyethylene (B). (B) The thickness of the (A) layer is 1 to 12 μm. The foam laminate according to claim 1, wherein the layer (A) is composed of an ethylene / α-olefin copolymer (A). The foam laminate according to claim 1, wherein the layer (A) comprises a low-pressure ethylene homopolymer (A). (A) Polyethylene resin (A) used for the layer has a storage elasticity at an angular velocity ω (s ⁻¹ ) at which the loss elastic modulus G ″ (Pa) obtained by measuring dynamic viscoelasticity at 190 ° C. is 500 Pa. The ratio G ′ _a (500) is smaller than G ′ _b (500) of the high-pressure low-density polyethylene (B) used for the B layer obtained by the same method. A foam laminate according to crab. A foam laminate comprising the laminate according to any one of claims 1 to 4 and a foam layer made of high-pressure low-density polyethylene (C) as the (C) layer on the other substrate wall surface of the substrate layer of the laminate. body.