JP2013075494A - Laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated body which can be suitably used for a beverage container for water, juice, etc. requiring highly low odor characteristics and low offensive taste characteristics.SOLUTION: The laminated body is formed by laminating, on a base material, at least one layer of an ethylene-based resin composition (C) constituted of 50-80 wt.% of an ethylene-α-olefin copolymer (A) satisfying following requirements (1)-(5) and 20-50 wt.% of high-pressure-produced low-density polyethylene (B) having 915-930 kg/mof density and 1-10 g/10 min of MFR and including a small amount of a volatile component, and at least one face of the outermost layer is the layer of the ethylene-based resin composition (C): (1) density is 920-955 kg/m; (2) MFR is 10-50 g/10 min; (3) the number of long-chain branchings having ≥6C is 0.01-0.2 per 1,000C; (4) Mw/Mn is ≥2 and <5; and (5) water solubles relative to n-heptane at 50°C are 0.3 wt.% or smaller.

Description

  The present invention relates to a laminate in which a layer made of an ethylene-based resin composition having good odor and taste and good laminating properties is arranged in the outermost layer.

  Among laminates obtained by extrusion lamination, laminates obtained by laminating at least one layer of polyethylene resin are used in a wide range of application fields such as craft packaging, flexible packaging, photographic paper supports, tapes, and various containers. In particular, in applications such as food packaging and liquid containers, a laminate is used in which a low odor polyethylene resin subjected to a low bromide treatment is arranged in the innermost layer. Conventionally, the low odor polyethylene resin used for laminates used for food packaging, liquid containers and the like has been mainly branched low density polyethylene (LDPE) synthesized by radical polymerization because of its excellent moldability.

  However, since LDPE synthesized by radical polymerization proceeds randomly, the structure of the produced polymer is not uniform, and a wide variety of by-products are generated. These by-products are contained in the processed laminated body as they are or after being oxidized and contained as oxygen-containing compounds, and when they are volatilized, the odor of the laminated body deteriorates and the odor of the packaged contents is impaired. There is. Alternatively, by-products and oxygen-containing compounds generated by the oxidation of the by-products may dissolve in the contents, and the taste of the contents may be impaired.

  On the other hand, linear polyethylene such as linear low density polyethylene (L-LDPE) and linear high density polyethylene (HDPE) is produced by ionic polymerization using a polymerization catalyst, so that the structure is relatively uniform. The generation of by-products is small. Therefore, the odor and taste of the molded laminate are better than those of LDPE. In particular, polyethylene resins produced using a metallocene catalyst, which is a single-site catalyst, are known to have good odor and off-flavor because of their low structural components and low molecular weight content due to their narrow molecular weight distribution. (For example, refer to Patent Document 1).

  However, linear polyethylene has a problem that its melt elasticity is low because it is difficult for the molecules to be entangled with each other. In order to improve the molding processability, it is effective to introduce long chain branching into the molecular structure, but it has been difficult to introduce long chain branching into polyethylene conventionally produced by ionic polymerization because of the production method. As a method for improving molding processability, a method is often used in which a laminate is obtained by extrusion laminating a mixture of linear polyethylene and LDPE (see, for example, Patent Documents 2 to 5). However, there is a concern that the odor of the laminate deteriorates when a large amount of LDPE is added. For this reason, it has been difficult to obtain polyethylene having good odor and taste and good moldability.

Japanese Patent Laid-Open No. 6-320685 JP-A-6-65443 JP-A-6-322189 JP-A-7-92610 JP 2000-73018 A

  The present invention has been made to solve the above-described problems of the prior art, and provides a laminate having good moldability and excellent odor and taste.

The present invention has been found as a result of intensive studies on the above-described object. That is, the present invention is an ethylene-α-olefin copolymer (A) that is obtained by copolymerizing ethylene and an α-olefin having 3 to 6 carbon atoms and satisfies the following requirements (1) to (5): 50 to 80% by weight When the density 915 kg / ^{m 3} or more 930 kg / ^{m 3} or less, MFR1g / 10 min or more 10 g / 10 minutes or less high-pressure low-density polyethylene (B) consists of 20 to 50 wt%, the following requirements (6), (7) Is a laminate formed by laminating at least one layer of an ethylene-based resin composition (C) on a substrate, and at least one side of the outermost layer is a layer of the ethylene-based resin composition (C) It is about.
(1) Density 920 kg / m ³ or more and 955 kg / m ³ or less (2) MFR 10 g / 10 min or more and 50 g / 10 min or less (3) Long chain branching having 6 or more carbon atoms, 0.01 to 0 per 1000 carbon atoms (4) Ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) Mw / Mn is 2 or more and less than 5 (5) Soluble content in n-heptane at 50 ° C. is 0.3% by weight or less (6) The peak number of volatile components is 15 or less when measuring 2 mL of gas in a glass bottle when heated at 140 ° C. for 60 minutes in a 20 mL glass bottle by gas chromatography. (7) 140 ° C. in a 20 mL glass bottle, The concentration obtained by converting the total peak area when measuring 2 mL of gas in a glass bottle when heated for 60 minutes by gas chromatography to a concentration of 7 μg / g or less in terms of n-hexane is described in detail below. To.

  The ethylene-α-olefin copolymer (A) which is a component of the ethylene-based resin composition (C) constituting the laminate of the present invention is composed of a repeating unit derived from ethylene and an α-olefin having 3 to 6 carbon atoms. It is an ethylene-α-olefin copolymer composed of derived repeating units. Examples of the α-olefin having 3 to 6 carbon atoms include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-butene. You may use together at least 2 types of these C3-C6 alpha olefins.

The ethylene-α-olefin copolymer (A), which is a component of the ethylene resin composition (C) constituting the laminate of the present invention, has a density of 920 kg / m ³ or more and 955 kg / m ³ or less, preferably 920 kg / m ³ or more 945 kg / ^{m 3} or less, and most preferably is of 920 kg / ^{m 3} or more 935 kg / ^{m 3} or less. Here, when the density is less than 920 kg / m ^3, the heat resistance of the ethylene-α-olefin copolymer (A) is lowered, and the odor and taste of the laminate are deteriorated due to the heat history during the molding process, which is not preferable. . On the other hand, when the density is larger than 955 kg / m ³ , the curling of the anti-area layer body in which the heat resistance of the ethylene-α-olefin copolymer (A) is good and the odor and taste of the laminate are good increases, This is not preferable because the secondary processability of bags and the like deteriorates. The density can be measured by a density gradient tube method in accordance with JIS K6760 (1995).

  Further, the ethylene-α-olefin copolymer (A), which is a component of the ethylene resin composition (C) constituting the laminate of the present invention, has a melt flow rate (hereinafter referred to as MFR) of 10 g / 10 min. It is 50 g / 10 min or less, preferably 20 g / 10 min or more and 40 g / 10 min or less. Here, when MFR is less than 10 g / 10 minutes, the load of the extruder at the time of shaping | molding an ethylene-type resin composition (C) becomes large, and productivity falls, and it is unpreferable. On the other hand, when it exceeds 50 g / 10 minutes, the low-molecular weight component contained in the ethylene-α-olefin copolymer (A) increases, so that the odor and taste of the laminate are deteriorated. MFR can be measured by a melt indexer under the conditions of 190 ° C. and 2.16 kg load in accordance with JIS K6760 (1995).

The ethylene-α-olefin copolymer (A), which is a component of the ethylene-based resin composition (C) constituting the laminate of the present invention, has a long chain branch having 6 or more carbon atoms in the structure per 1000 carbon atoms. It has 0.01-0.2 pieces. By having 0.01 to 0.2 long-chain branches per 1000 carbon atoms in the structure, the melt tension of the ethylene-α-olefin copolymer (A) is increased, and the ethylene resin composition (C) Molding processability is improved. When the number of long-chain branches is less than 0.01 per 1000 carbon atoms, the neck-in (width reduction of the molten film) at the time of laminating the ethylene-based resin composition is unfavorable. Further, when the number of long chain branches is more than 0.2 per 1000 carbon atoms, the drawability (high-speed moldability) of the laminate processability of the ethylene-based resin composition is not preferable. In addition, the number of long-chain branches is the number of branches of a hexyl group or more (carbon number of 6 or more) detected by ¹³ C-NMR measurement.

  Furthermore, the ethylene-α-olefin copolymer (A) constituting the ethylene resin composition (C) constituting the laminate of the present invention is an ethylene polymer having a vinyl group at the terminal obtained by polymerizing ethylene. Or a macromonomer comprising an ethylene copolymer obtained by copolymerizing ethylene and an olefin having 3 to 6 carbon atoms and having a vinyl group at the terminal, wherein the number average molecular weight (Mn) is 2000 or more. A polyethylene polymer obtained by polymerizing ethylene or ethylene and an olefin having 3 to 6 carbon atoms is desirable below or simultaneously with the synthesis of the macromonomer.

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

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

  The number average molecular weight (Mn) in terms of linear polyethylene of the macromonomer is preferably 2000 or more, more preferably 5000 or more, and most preferably 10,000 or more. The weight average molecular weight (Mw) in terms of linear polyethylene is 4000 or more, preferably 10,000 or more, more preferably more than 15,000. By increasing the molecular weight of the macromonomer, the length of the long chain branch introduced into the ethylene-α-olefin copolymer (A) is increased, and the melt tension is improved.

  The ethylene-α-olefin copolymer (A), which is a component of the ethylene-based resin composition (C) constituting the laminate of the present invention, has a ratio Mw / weight average molecular weight (Mw) to number average molecular weight (Mn). Mn is 2 or more and less than 5. When Mw / Mn is less than 2, it is not preferable because the extrusion load at the time of molding is higher than necessary and the amount of extrusion at the time of lamination is limited. Moreover, when Mw / Mn is 5 or more, the content ratio of the low molecular weight component in the ethylene-α-olefin copolymer (A) is increased, and the odor and taste derived from the low molecular weight component are deteriorated. This is not preferable because of adverse effects such as roll contamination, stickiness of the surface of the laminated molded product, and heat seal failure. Mw / Mn can be calculated by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn), which are standard polyethylene equivalent values, by gel permeation chromatography (GPC).

  The ethylene-α-olefin copolymer (A), which is a component of the ethylene-based resin composition (C) constituting the laminate of the present invention, has a soluble content of 0.3% by weight or less with respect to n-heptane at 50 ° C. More preferably, it is 0.2% by weight or less. When the soluble content exceeds 0.3% by weight, the content ratio of the low molecular weight component in the ethylene-α-olefin copolymer (A) increases, and the odor and taste derived from the low molecular weight component deteriorate and laminate. This is not preferable because of adverse effects such as roll contamination during molding, stickiness of the surface of the laminated molded product, and poor heat sealing. In addition, the soluble part with respect to n-heptane can be measured from the weight of the component which remain | survives after grind | pulverizing resin to fine powder form, immersing in 50 degreeC n-heptane, and drying a filtrate.

  The ethylene-α-olefin copolymer (A), which is a component of the ethylene-based resin composition (C) constituting the laminate of the present invention, may be obtained by any method. It is possible to arbitrarily create the manufacturing conditions according to the embodiment, or by fine adjustment of the condition factors.

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

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

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

Component (a) and the following general formula (1)
AlR ¹ ₃ (1)
(In the formula, each R1 is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
A catalyst comprising an organoaluminum compound represented by the following (hereinafter referred to as “component (b)”), a catalyst further comprising water,
Component (a) and the following general formula (2)

And / or the following general formula (3)

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

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

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

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

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

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

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

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

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

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

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

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

  When producing the ethylene-α-olefin copolymer (A) which is a component of the ethylene-based resin composition (C) constituting the laminate of the present invention, it is preferably performed at a polymerization temperature of −100 to 120 ° C. In particular, when productivity is taken into consideration, 20 to 120 ° C. is preferable, and it is more preferable to carry out in the range of 60 to 120 ° C. The polymerization time is preferably in the range of 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 300 MPa. The polymerizable monomer is ethylene alone or ethylene and an α-olefin having 3 to 6 carbon atoms. When ethylene is an α-olefin having 3 to 6 carbon atoms, ethylene and α-olefin having 3 to 6 carbon atoms are used. As the olefin supply ratio, ethylene / C3-C6 α-olefin (molar ratio) of 1 to 200, preferably 3 to 100, and more preferably 5 to 50 can be used. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. In addition, the ethylene copolymer can be obtained by separating and recovering from the polymerization solvent by a conventionally known method after the completion of the polymerization and drying.

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

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

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

  The high-pressure method low-density polyethylene (B) that is a component of the ethylene-based resin composition (C) constituting the laminate of the present invention can be obtained by a conventionally known high-pressure radical polymerization method, and is appropriately selected within the scope of the present invention. Is done.

High-pressure low-density polyethylene which is a component of the ethylene-based resin composition constituting the laminate of the present invention (C) (B) has a density of 915 kg / ^{m 3} or more 930 kg / ^{m 3} or less, preferably 915 kg / ^{m 3} or more 925 kg / m ³ or less. When the density is less than 915 kg / m ^3, the heat resistance of the high-pressure low-density polyethylene (B) is lowered, and the odor and taste of the laminate are deteriorated. On the other hand, when the density exceeds 930 kg / m ³ , the density of the ethylene-based resin composition (C) is increased, and the curling of the laminate is increased, so that the secondary workability is deteriorated.

  The high-pressure low-density polyethylene (B) that is a component of the ethylene-based resin composition (C) constituting the laminate of the present invention has an MFR of 1 g / 10 min or more and 10 g / 10 min or less, preferably 1 g / 10 min or more. 5 g / 10 min or less. Here, when MFR is less than 1 g / 10 minutes, the extrusion load at the time of a molding process of the ethylene-based resin composition (C) is increased, which is not preferable. On the other hand, if it exceeds 10 g / 10 minutes, the melt tension becomes small and the neck-in at the time of laminating increases, which is not preferable.

  The ethylene-based resin composition (C) constituting the laminate of the present invention comprises 50 to 80% by weight, preferably 60 to 80% by weight of an ethylene-α-olefin copolymer (A), and a high-pressure low-density polyethylene (B). ) 20 to 50% by weight, preferably 20 to 40% by weight. When the blending amount of the high pressure method low density polyethylene (B) is less than 20% by weight, the laminate processability of the ethylene resin composition (C) is deteriorated, which is not preferable. On the other hand, when the blending amount exceeds 50% by weight, the odor and taste of the laminate deteriorate, which is not preferable.

  The ethylene-based resin composition (C) constituting the laminate of the present invention has a peak of volatile components when 2 mL of gas in a glass bottle when heated at 140 ° C. for 60 minutes in a 20 mL glass bottle is measured by gas chromatography. The number is 15 or less. When the peak number of volatile components is more than 15, the ethylene resin composition (C) is inferior in low odor, and the low odor of the laminate using the ethylene resin composition (C) is also deteriorated. Therefore, it is not preferable. Furthermore, when a part of the volatile component is transferred to the food filled in the container molded using the laminate, the taste of the food deteriorates, which is not preferable.

  In addition, the volatile component in the ethylene-based resin composition (C) can be extracted by placing 0.27 g of the sample in a sealable 20 mL glass bottle and heating at 140 ° C. for 60 minutes. 2 mL of gas in a glass bottle containing a volatile component can be collected with a syringe and introduced into a gas chromatograph to separate the components.

Column: Quadrex VTS-MS
Carrier gas: helium (2 mL / min)
Column temperature: 50 ° C to 250 ° C (temperature rise at 10 ° C / min)
Detector: FID
From the obtained chromatogram, the area was calculated for all peaks, and the number of peaks having an area of 1% or more of the total peak area was taken as the number of peaks of the volatile components of the sample.
The ethylene-based resin composition (C) constituting the laminate of the present invention is a sum of peak areas when 2 mL of gas in a glass bottle when heated at 140 ° C. for 60 minutes in a 20 mL glass bottle is measured by gas chromatography. The concentration in terms of n-hexane is 7 μg / g or less, preferably 5 μg / g or less, more preferably 3 μg / g or less. When the n-hexane equivalent concentration of the volatile component is higher than 7 μg / g, the ethylene-based resin composition (C) is inferior in low odor, and as a result, the laminate body using the ethylene-based resin composition (C) is low. Since odor property also deteriorates, it is not preferable. Furthermore, when a part of the volatile component is transferred to the food filled in the container molded using the laminate, the taste of the food deteriorates, which is not preferable.

  Note that the n-hexane equivalent concentration of the volatile component in the ethylene-based resin composition (C) is calculated after calculating the total peak area of the volatile component by the same method as the method of measuring the peak number of the volatile component, and then the concentration is known. It can calculate by proportional calculation with the area of the peak obtained by measuring n-hexane standard gas similarly.

  The ethylene resin composition (C) constituting the laminate of the present invention preferably has a melt tension measured at 160 ° C. of 10 to 100 mN, more preferably 20 to 80 mN. When the melt tension is within this range, the balance between neck-in and draw-down at the time of laminating becomes good, and it can be suitably used for extrusion lamination molding.

  In the ethylene-based resin composition (C) constituting the laminate of the present invention, other polyethylene-based resins can be blended as necessary without departing from the gist of the present invention. Examples of the polyethylene resin include high-density polyethylene and ethylene-α-olefin copolymers other than (A).

  In the ethylene-based resin composition (C) constituting the laminate of the present invention, a stabilizer, a lubricant, a flame retardant, a dispersant, a filler, and a foaming agent are included in the range not departing from the gist of the present invention. , A foam nucleating agent, a crosslinking agent, an ultraviolet ray inhibitor, an antioxidant, a colorant and the like can be contained.

  As a method for producing the ethylene-based resin composition (C) constituting the laminate of the present invention, it is possible to use a method usually used as a resin composition. For example, as a melting / mixing method, a single-screw extruder, Known methods such as extrusion kneading using a twin screw extruder, roll kneading, and the like can be mentioned, and it can be obtained by melt kneading using this method.

  Although there is no restriction | limiting in particular in the method to reduce the volatile component density | concentration of the ethylene-type resin composition (C) which comprises the laminated body of this invention, For example, an air current of 40 degreeC or more and 70 degrees C or less is used for ethylene-type resin composition (C) Among them, a heat treatment method of 12 hours or more and less than 120 hours can be given. By heating in an air stream and increasing the diffusion rate of the volatile component in the ethylene resin composition (C), it can be efficiently discharged out of the resin.

  When the heating temperature is less than 40 ° C., the diffusion rate of the volatile component is low and the volatile component cannot be sufficiently removed. On the other hand, when the heating temperature exceeds 70 ° C., the ethylene resin composition (C) begins to oxidize, which may cause changes in resin physical properties such as MFR.

  If the heating time is less than 12 hours, the movement of the volatile components inside the ethylene resin composition (C) is not sufficient, and the volatile components cannot be removed sufficiently. On the other hand, when the heating time exceeds 120 hours, the ethylene-based resin composition (C) starts to oxidize, which may cause changes in resin physical properties such as MFR.

The laminate of the present invention is a laminate formed by laminating at least one layer of an ethylene-based resin composition (C) on a base material, and at least one side of the outermost layer is made of an ethylene-based resin composition (C). There is no restriction | limiting in particular except being a layer, Lamination | stacking of three or more layers is also possible. Specifically, substrate / ethylene resin composition (C) layer, ethylene resin composition (C) layer / substrate / ethylene resin composition (C) layer, resin layer / base other than (C) Examples include a material / ethylene-based resin composition (C) layer.
Examples of the resin other than (C) include high-density polyethylene, low-density polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, and polypropylene.

  The method for molding the laminate of the present invention is not particularly limited, and examples of the molding method include an extrusion laminate molding method, a dry laminate molding method, a coextrusion T-die molding method, and a coextrusion inflation molding method. In particular, the extrusion lamination method is preferable from the viewpoint of production efficiency.

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 laminating process, it is preferable to extrude from a die at a temperature of 250 to 350 ° C. in order to obtain a laminate having good adhesion between the substrate and the ethylene polymer composition layer. Further, at least the surface where the molten film of the ethylene polymer composition is in contact with the substrate may be oxidized with air or ozone gas. When the oxidation reaction with air proceeds, it is preferable to extrude from a die at a temperature of 270 ° C. or higher, and when the oxidation reaction with ozone gas proceeds, it is preferable to extrude at 250 ° C. or higher. In addition, it is preferable that the processing amount of ozone gas is 0.5 mg or more per 1 m ^{2 of} the film extruded from the die. Moreover, in order to improve adhesiveness with a base material, you may perform well-known surface treatments, such as an anchor-coat agent process, a corona discharge process, a flame process, and a plasma process, to the adhesion surface of a base material.

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

  The laminate of the present invention uses a paperboard as a base material, and is a liquid packaging paper container molded so that the outermost layer of the ethylene-based resin composition (C) is the inner surface of the container. And can be suitably used as a beverage container for water, juice, etc., which are required to have good taste and low taste. In addition, by forming a bag molded so that the outermost layer of the ethylene-based resin composition (C) is on the inner surface, water for dried foods such as snacks and instant noodles, soup, miso, pickles, sauces, beverages, etc. It can be suitably used for applications that require low odor and low taste, such as food and beverage packaging, medicine, and pharmaceutical packaging such as infusion bags.

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

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

~ Measurement of MFR ~
MFR of the ethylene-α-olefin copolymer (A), the high-pressure method low-density polyethylene (B) and the ethylene polymer composition was measured with a melt indexer in accordance with JIS K6760 (1995).

-Measurement of molecular weight and molecular weight distribution-
The weight average molecular weight (Mw), number average molecular weight (Mn), and ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) of the macromonomer and the ethylene-α-olefin copolymer (A) are gel permeation Measured by chromatography (GPC). Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC apparatus, Tosoh Co., Ltd. TSKgel GMHhr-H (20) HT is used as the column, the column temperature is set to 140 ° C., and 1 is used as the eluent. Measurement was performed using 2,4-trichlorobenzene. A measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The calibration curve of molecular weight is calibrated using a polystyrene sample having a known molecular weight. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.

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

Number of long chain branches = IAα / (3 × IAtot) (4)
[Wherein, IAα is the integrated intensity of a long-chain branched α-carbon peak (chemical shift: 34.6 ppm) above the hexyl group, and IAtot is the integrated intensity of the main chain methylene carbon peak (30.0 ppm). . ]
~ Measurement of soluble n-heptane ~
The measurement of the n-heptane soluble content of the ethylene-α-olefin copolymer (A) is performed by freezing the resin to be measured with liquid nitrogen and then using a Willet grinder (W-50 manufactured by Ikeda Rika Co., Ltd.). It was pulverized mechanically into a fine powder. 4 g of finely divided resin was precisely weighed, 400 mL of n-heptane was added thereto, and extraction was performed for 2 hours while heating to 50 ° C. in a water bath. After the extraction, the mixture was filtered, and the filtrate was evaporated to dryness, followed by further drying in an inert oven for 1 hour. The weight of the evaporation residue was measured, and the extraction rate was determined from the ratio to the weight of the resin used for extraction.

~ Measurement of melt tension ~
The melt tension of the ethylene-based resin composition (C) was 8 mm in length, 2.095 mm in diameter, and 90 ° inflow angle on a capillary viscometer (Toyo Seiki Seisakusho, trade name: Capillograph) with a barrel diameter of 9.55 mm. A die was mounted and measured. For the melt tension, the temperature was set to 160 ° C., the piston lowering speed was set to 10 mm / min, the stretch ratio was set to 47, and the load (mN) required for take-up was measured. When the maximum draw ratio was less than 47, the load (mN) required for taking-up at the highest draw ratio that did not break was taken as the melt tension.

-Measurement of peak number of volatile components-
The peak number of volatile components in the ethylene-based resin composition (C) is about 0.27 g of a sample placed in a sealable 20 mL glass bottle, heated at 140 ° C. for 60 minutes to extract volatile components, and the gas in the glass bottle 2 mL was collected with a syringe and introduced into a gas chromatograph to separate the components.

Column: Quadrex VTS-MS
Carrier gas: helium (2 mL / min)
Column temperature: 50 ° C to 250 ° C (temperature rise at 10 ° C / min)
Detector: FID
From the obtained chromatogram, the area was calculated for all peaks, and the number of peaks having an area of 1% or more of the total peak area was taken as the number of peaks of the volatile components of the sample.

-Measurement of n-hexane equivalent concentration of volatile components-
The n-hexane equivalent concentration of the volatile component of the ethylene-based resin composition (C) was calculated by calculating the total peak area of the volatile component in the same manner as described above. It calculated by proportional calculation with the area of the peak obtained by measuring standard gas similarly.

~ Measurement of neck-in ~
The ethylene-based resin composition (C) is supplied to an extruder of an extrusion laminator (manufactured by Musashinokikai Co., Ltd.) having a 90 mmφ screw, extruded from a T-die having an opening width of 600 mm at a resin temperature of 320 ° C., and an air gap length of 130 mm When the substrate take-up speed is 200 m / min, and the extrusion die is laminated on the kraft paper substrate having a basis weight of 50 g / m ² so that the ethylene resin composition has a thickness of 10 μm, The difference from the coating width of the ethylene resin composition was defined as neck-in, and the value was measured.

-Low odor (sensory evaluation)-
The ethylene-based resin composition (C) is supplied to an extruder of an extrusion laminator (manufactured by Musashinokikai Co., Ltd.) having a 90 mmφ screw, extruded from a T-die having an opening width of 600 mm at a resin temperature of 320 ° C., and an air gap length of 130 mm The laminate was obtained by extruding and laminating the ethylene resin composition (C) to a thickness of 20 μm on a paperboard having a basis weight of 270 g / m ^{2 at} a substrate take-up speed of 100 m / min.

  20 g of this laminate was sealed in a 200 mL glass bottle and heated at 50 ° C. for 1 hour, after which the panelist sniffed the air in the glass bottle. Compared to a paperboard (20 g) and heated at 50 ° C. for 1 hour (comparative control sample), the odor intensity was judged by a panel. Judgment criteria were three levels of 1: equivalent, 2: slightly smelled, and 3: smelled clearly, and the evaluation was made based on the average value of five panelists.

~ Taste (sensory evaluation) ~
~ Low odor (sensory evaluation) ~ Use the same laminate as the one used in the evaluation to make a 100mm x 300mm bag so that the ethylene resin composition (C) becomes the inner surface, and contain 50mL of mineral water And it heated at 50 degreeC for 1 hour. The mineral water after the heat treatment was used as sample water, and the sample water was drunk by a panelist. Compared to untreated mineral water (comparative control sample), the taste of the sample water was judged by a panelist. Judgment criteria were three levels of 1: Equivalent, 2: Slightly bad, 3: Clearly bad, and evaluated by the average value of five panelists.

Synthesis example 1
[Preparation of modified hectorite]
After adding 3 L of ethanol and 100 mL of 37% concentrated hydrochloric acid to 3 L of water, 585 g (1.1 mol) of N-methyl-dioleylamine was added to the resulting solution and heated to 60 ° C. to prepare a hydrochloride solution. did. 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 polyethylene resin production catalyst]
500 g of the modified hectorite was suspended in 1.7 L of hexane, and 8.25 g (20.0 mmol) of dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride and a hexane solution of triisobutylaluminum (0 .714M) 2.8 L (2 mol) of a mixed solution was added, and the mixture was stirred at 60 ° C. for 3 hours, and then left to stand to remove the supernatant, and a hexane solution of triisobutylaluminum (0.15 M) was added. A macromonomer synthesis catalyst (100 g / L) was used.

In the macromonomer synthesis catalyst prepared above, 10 mol% of isopropylidene (1-cyclopentadienyl) (2,7-di-) with respect to dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride is used. 1.21 g (2.22 mmol) of t-butyl-9-fluorenyl) zirconium dichloride was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a 100 g / L polyethylene resin production catalyst.
[Production of ethylene-α-olefin copolymer (A-1)]
In a polymerization vessel having an internal volume of 540 L, the above-mentioned [145 kg / hour of hexane, 33.0 kg / hour of ethylene, 4.9 kg / hour of butene-1, 20 NL / hour of hydrogen and 30 kg / hour of polymer production] The polyethylene resin production catalyst prepared in [Preparation of polyethylene resin production catalyst] was continuously supplied, and the polymerization reaction was continuously carried out while maintaining the total pressure at 3,000 kPa and the polymerization vessel internal temperature at 60 ° C. The slurry was continuously extracted from the polymerization vessel to remove unreacted hydrogen, ethylene, and butene-1, and then separated and dried to obtain an ethylene-α-olefin copolymer (A-1) powder. This was melt-kneaded using a 50 mm diameter single screw extruder set at 200 ° C. and pelletized to obtain ethylene-α-olefin copolymer (A-1) pellets. The density of the obtained ethylene-α-olefin copolymer (A-1) pellets is 925 kg / m ³ , MFR is 24.1 g / 10 min, the number of long-chain branches is 0.13 per 1000 carbon atoms, weight average The ratio Mw / Mn between the molecular weight (Mw) and the number average molecular weight (Mn) was 3.8. The n-heptane soluble content was 0.12% by weight.

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

Reference example 1
[Synthesis of macromonomer]
In Synthesis Example 1 [Production of ethylene-α-olefin copolymer (A-1)], the macromonomer synthesis catalyst prepared in Synthesis Example 1 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. Except having used, it carried out similarly to the synthesis example 1, and obtained the macromonomer pellet. Mn of the obtained macromonomer pellet was 15000 and Mw / Mn was 2.5. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1000 carbons was 0.07.

Synthesis example 2
[Preparation of polyethylene resin production catalyst]
500 g of the modified hectorite prepared in Synthesis Example 1 [Preparation of Modified Hectorite] was suspended in 1.7 L of hexane, and dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride 8 .81 g (20.0 mmol) and a mixed solution of triisobutylaluminum in hexane (0.714 M) 2.8 L (2 mol) were added, stirred at 60 ° C. for 3 hours, and then allowed to stand to remove the supernatant. Further, a hexane solution (0.15 M) of triisobutylaluminum was added to obtain a macromonomer synthesis catalyst (100 g / L).

The macromonomer synthesis catalyst prepared above was mixed with 5 mol% of diphenylmethylene (1-cyclopentadienyl) (9- 9%) based on dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride. Fluorenyl) zirconium dichloride (0.58 g, 1.05 mmol) was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a 100 g / L polyethylene resin production catalyst.
[Production of ethylene-α-olefin copolymer (A-2)]
In Synthesis Example 1 [Production of ethylene-α-olefin copolymer (A-1)], butene-1 was changed from 4.9 kg / hour to 5.3 kg / hour, and the hydrogen supply amount was changed from 20 NL / hour to 5 NL / hour. The ethylene-α-olefin copolymer (A-2) was prepared in the same manner as in Synthesis Example 1 except that the catalyst was changed to the polyethylene resin production catalyst prepared in [Preparation of polyethylene resin production catalyst]. Obtained. The density of the obtained ethylene-α-olefin copolymer (A-2) is 920 kg / m ³ , MFR is 12.7 g / 10 min, the number of long-chain branches is 0.10 per 1000 carbon atoms, and the weight average molecular weight The ratio Mw / Mn between (Mw) and the number average molecular weight (Mn) was 4.2. The n-heptane soluble content was 0.18% by weight.

Reference example 2
[Synthesis of macromonomer]
In Synthesis Example 2 [Production of ethylene-α-olefin copolymer (A-2)], the macromonomer synthesis catalyst prepared in Synthesis Example 2 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. A macromonomer pellet was obtained in the same manner as in Synthesis Example 2 except that it was used. Mn of the obtained macromonomer pellet was 20000, and Mw / Mn was 2.8. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1000 carbons was 0.05.

Synthesis example 3
[Production of ethylene-α-olefin copolymer (A-3)]
In Synthesis Example 1 [Production of ethylene-α-olefin copolymer (A-1)], butene-1 was changed from 4.9 kg / hour to 5.3 kg / hour, and the hydrogen supply amount was changed from 20 NL / hour to 30 NL / hour. The ethylene-α-olefin copolymer (A-3) was prepared in the same manner as in Synthesis Example 1 except that the catalyst was changed to the polyethylene resin production catalyst prepared in Synthesis Example 2 [Preparation of Polyethylene Resin Production Catalyst]. ) The density of the obtained ethylene-α-olefin copolymer (A-3) is 920 kg / m ³ , MFR is 39.2 g / 10 min, the number of long chain branches is 0.12 per 1000 carbon atoms, and the weight average molecular weight The ratio Mw / Mn between (Mw) and the number average molecular weight (Mn) was 4.1. The n-heptane soluble content was 0.25% by weight.

Reference example 3
[Synthesis of macromonomer]
In Synthesis Example 3 [Production of ethylene-α-olefin copolymer (A-3)], the macromonomer synthesis catalyst prepared in Synthesis Example 2 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. A macromonomer pellet was obtained in the same manner as in Synthesis Example 3 except that it was used. Mn of the obtained macromonomer pellet was 10000 and Mw / Mn was 3.0. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1000 carbons was 0.05.

Synthesis example 4
[Preparation of polyethylene resin production catalyst]
500 g of the modified hectorite prepared in Synthesis Example 1 [Preparation of Modified Hectorite] was suspended in 1.7 L of hexane, and 7.85 g (20.0 mmol) of bis (indenyl) zirconium dichloride and a hexane solution of triisobutylaluminum (0 .714M) 2.8 L (2 mol) of a mixed solution was added, and the mixture was stirred at 60 ° C. for 3 hours, and then left to stand to remove the supernatant, and a hexane solution of triisobutylaluminum (0.15 M) was added. A macromonomer synthesis catalyst (100 g / L) was used.

In the macromonomer synthesis catalyst prepared above, 5 mol% of isopropylidene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was added to bis (indenyl) zirconium dichloride. 57 g (1.05 mmol) was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a 100 g / L polyethylene resin production catalyst.
[Production of ethylene-α-olefin copolymer (A-4)]
In Synthesis Example 1 [Production of ethylene-α-olefin copolymer (A-1)], butene-1 is 4.9 kg / hour to 0.5 kg / hour, hydrogen supply amount is 20 NL / hour to 5 NL / hour, Except that the polymerization temperature was changed from 60 ° C. to 85 ° C. and the catalyst was changed to the polyethylene resin production catalyst prepared in [Preparation of polyethylene resin production catalyst], ethylene-α- An olefin copolymer (A-4) was obtained. The resulting ethylene-α-olefin copolymer (A-4) has a density of 955 kg / m ³ , an MFR of 11.3 g / 10 min, a long-chain branch number of 0.03 per 1000 carbon atoms, and a weight average molecular weight. The ratio Mw / Mn of (Mw) to the number average molecular weight (Mn) was 2.4. The n-heptane soluble component was 0.09% by weight.

Reference example 4
[Synthesis of macromonomer]
In Synthesis Example 4 [Production of ethylene-α-olefin copolymer (A-4)], the macromonomer synthesis catalyst prepared in Synthesis Example 4 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. Except having used, it carried out similarly to the synthesis example 4, and obtained the macromonomer pellet. Mn of the obtained macromonomer pellet was 20000, and Mw / Mn was 2.2. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1000 carbons was 0.02.

Synthesis example 5
[Production of ethylene-α-olefin copolymer (A-5)]
In Synthesis Example 1 [Production of ethylene-α-olefin copolymer (A-1)], butene-1 is 4.9 kg / hour to 0.5 kg / hour, hydrogen supply amount is 20 NL / hour to 30 NL / hour, The polymerization temperature was changed from 60 ° C. to 85 ° C., and the catalyst was changed to the polyethylene resin production catalyst prepared in Synthesis Example 4 [Preparation of polyethylene resin production catalyst]. An α-olefin copolymer (A-5) was obtained. The resulting ethylene-α-olefin copolymer (A-5) has a density of 955 kg / m ³ , an MFR of 38.4 g / 10 min, a long-chain branch number of 0.03 per 1000 carbon atoms, and a weight average molecular weight. The ratio Mw / Mn between (Mw) and the number average molecular weight (Mn) was 2.3. The n-heptane soluble content was 0.11% by weight.

Reference Example 5
[Synthesis of macromonomer]
In Synthesis Example 5 [Production of ethylene-α-olefin copolymer (A-5)], the macromonomer synthesis catalyst prepared in Synthesis Example 4 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. A macromonomer pellet was obtained in the same manner as in Synthesis Example 5 except that it was used. Mn of the obtained macromonomer pellet was 17000, and Mw / Mn was 2.3. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1000 carbons was 0.02.

Synthesis Example 6
[Production of ethylene-α-olefin copolymer (A-6)]
Polymerization was carried out using a reactor equipped for high temperature and high pressure polymerization. First, ethylene and 1-butene were continuously injected into the reactor, the total pressure was set to 900 kg / cm2, and the 1-butene concentration was set to 39.4 mol%. The reactor was then stirred at 1500 rpm.

  In a separate container, a toluene solution of triisobutylaluminum was added to a toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride so that the aluminum was 250-fold mol per zirconium. Further, a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added thereto so that boron was 1 mol per zirconium to obtain a catalyst solution.

Then, the obtained catalyst solution was supplied to the reactor, the temperature of the reactor was set to 190 ° C., and polymerization was continuously performed to obtain an ethylene-α-olefin copolymer (A-6). It was. The density of the obtained ethylene-α-olefin copolymer (A-6) was 923 kg / m ³ , MFR was 20.4 g / 10 min, and the ratio Mw / weight average molecular weight (Mw) to number average molecular weight (Mn). Mn was 1.5. Long chain branching was not detected. The n-heptane soluble content was 0.44% by weight.

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

Example 1
75% by weight of the ethylene-α-olefin copolymer (A-1) shown in Synthesis Example 1, low-density polyethylene obtained by a high-pressure radical polymerization method (trade name Petrocene 360 manufactured by Tosoh Corp .; density 919 kg / m ³ , MFR 1.6 g / 10 min) (hereinafter referred to as (B-1)) 25 wt% was premixed with a tumbler mixer and then adjusted to a cylinder temperature of 180 ° C. (made by Plako Co., Ltd.) It was melt-kneaded with a model PDA-50) and pelletized. A small silo with heat insulation on the outer wall (inner diameter: 590mm, height: 1300mm, upper part is cylindrical, lower part is conical) is filled with 50kg of this pellet and the dry air kept at 60 ° C from the bottom of the small silo is 60L / The mixture was heat-treated for 24 hours to obtain an ethylene-based resin composition (C). About the obtained ethylene-type resin composition (C), the density, MFR, melt tension, the peak number of a volatile component, and n-hexane conversion density | concentration of a volatile component were measured by the method as described in an Example. Further, the obtained ethylene-based resin composition (C) was laminated by the method described in Examples, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 3.

Example 2
Except having changed the mixture ratio of the composition into A-1 50 weight% and B-1 50 weight%, it carried out similarly to Example 1, and obtained the pellet of the ethylene-type resin composition (C). In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 3.

Example 3
Except having changed the compounding ratio of the composition into A-1 80 weight% and B-1 20 weight%, it carried out similarly to Example 1, and obtained the pellet of the ethylene-type resin composition (C). In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 3.

Example 4
An ethylene-based resin composition (as in Example 1) except that the ethylene-α-olefin copolymer A-2 shown in Synthesis Example 2 was used instead of A-1 as the ethylene-α-olefin copolymer. C) pellets were obtained. In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 3.
Example 5
An ethylene resin composition (as in Example 1) except that the ethylene-α-olefin copolymer A-3 shown in Synthesis Example 3 was used instead of A-1 as the ethylene-α-olefin copolymer. C) pellets were obtained. In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 3.

Example 6
An ethylene-based resin composition (as in Example 1) except that the ethylene-α-olefin copolymer A-4 shown in Synthesis Example 4 was used instead of A-1 as the ethylene-α-olefin copolymer. C) pellets were obtained. In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 3.

Example 7
An ethylene-based resin composition (as in Example 1) except that the ethylene-α-olefin copolymer A-5 shown in Synthesis Example 5 was used instead of A-1 as the ethylene-α-olefin copolymer. C) pellets were obtained. In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 3.

Example 8
Implemented except using high pressure method low density polyethylene C-2 (trade name Petrocene 205; density 924 kg / m ³ , MFR 3.1 g / 10 min, manufactured by Tosoh Corporation) instead of C-1 as high pressure method low density polyethylene In the same manner as in Example 1, pellets of the ethylene resin composition (C) were obtained. In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 3.

Example 9
Implemented except that high pressure method low density polyethylene C-3 (trade name Petrocene 203 manufactured by Tosoh Corp .; density 919 kg / m ³ , MFR 7.9 g / 10 min) was used as the high pressure method low density polyethylene instead of C-1. In the same manner as in Example 1, pellets of the ethylene resin composition (C) were obtained. In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 3.

Comparative Example 1
A pellet of the ethylene-based resin composition (C) was obtained in the same manner as in Example 1 except that the high-pressure method low-density polyethylene (B) was not blended and the blending ratio was changed to 100% by weight of A-1. In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 4.

  The obtained laminate had a large neck-in and inferior moldability as compared with the Examples.

Comparative Example 2
An ethylene-based resin composition (C) pellet was obtained in the same manner as in Example 1 except that the ethylene-α-olefin copolymer (A) was not blended and the blending ratio was changed to 100% by weight of C-2. . In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 4.

  The obtained ethylene polymer had many volatile components and was inferior in odor and taste.

Comparative Example 3
The high-pressure method low density polyethylene (B) was not blended, and the ethylene-α-olefin copolymer A-6 shown in Synthesis Example 6 was used instead of A-1 as an ethylene-α-olefin copolymer. In the same manner as in Example 1, pellets of the ethylene-based resin composition (C) were obtained. In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 4.

  The obtained laminate had a very large neck-in and inferior moldability as compared with the Examples. In addition, since the ethylene-α-olefin copolymer (A) has a high n-heptane-soluble content and a large amount of low molecular weight components, the volatile component of the laminate has a small number of peaks but a large amount of generation, and odor due to sensory And the taste evaluation was poor.

Comparative Example 4
An ethylene-based resin composition (as in Example 1) except that the ethylene-α-olefin copolymer A-6 shown in Synthesis Example 6 was used instead of A-1 as the ethylene-α-olefin copolymer. C) pellets were obtained. In the same manner as in Example 1, the obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, and n-hexane equivalent concentration of volatile components. In addition, laminate molding was performed in the same manner as in Example 1, and neck-in measurement and sensory odor and taste were evaluated. These evaluation results are shown in Table 4.

  The obtained laminate had a large neck-in and inferior moldability as compared with the Examples. In addition, since the ethylene-α-olefin copolymer (A) has a high n-heptane-soluble content and a large amount of low molecular weight components, the volatile component of the laminate has a small number of peaks but a large amount of generation, and odor due to sensory And the taste evaluation was poor.

Comparative Example 5
Except that the heat treatment using a small silo was not performed, the pellets of the ethylene-based resin composition (C) were obtained in the same manner as in Example 1. The obtained pellets were measured for density, MFR, melt tension, peak number of volatile components, n-hexane equivalent concentration of volatile components, and neck-in as in Example 1. These evaluation results are shown in Table 4.

  The obtained laminate had a high concentration of volatile components in terms of n-hexane as compared with Example 1, and the odor due to sensuality was poor.

Claims (6)

50 to 80% by weight of an ethylene-α-olefin copolymer (A) which is obtained by copolymerizing ethylene and an α-olefin having 3 to 6 carbon atoms and satisfies the following requirements (1) to (5), and a density of 915 kg / m ³ or more 930 kg / ^{m 3} or less, MFR1g / 10 min or more 10 g / 10 minutes or less high pressure method consists 20-50 wt% low density polyethylene (B), the following requirement (6), the ethylene-based resin satisfying (7) A laminated body obtained by laminating at least one layer of the composition (C) on a base material, and at least one side of the outermost layer is a layer of the ethylene-based resin composition (C).
(1) Density 920 kg / m ³ or more and 955 kg / m ³ or less (2) MFR 10 g / 10 min or more and 50 g / 10 min or less (3) Long chain branching having 6 or more carbon atoms, 0.01 to 0 per 1000 carbon atoms (4) Ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) Mw / Mn is 2 or more and less than 5 (5) Soluble content in n-heptane at 50 ° C. is 0.3% by weight or less (6) The peak number of volatile components is 15 or less when measuring 2 mL of gas in a glass bottle when heated at 140 ° C. for 60 minutes in a 20 mL glass bottle by gas chromatography. (7) 140 ° C. in a 20 mL glass bottle, Concentration converted to n-hexane is 7 μg / g or less when the total peak area when measuring 2 mL of gas in a glass bottle when heated for 60 minutes by gas chromatography The laminate according to claim 1, wherein the melt tension of the ethylene-based resin composition (C) measured at 160 ° C. is 10 to 100 mN. It is a macromonomer comprising an ethylene polymer having a vinyl group at the end obtained by polymerizing ethylene or an ethylene copolymer having a vinyl group at the end obtained by copolymerizing ethylene and an olefin having 3 to 6 carbon atoms. In the presence of a macromonomer having a number average molecular weight (Mn) of 2000 or more, or simultaneously with the synthesis of the macromonomer, a polyethylene-based polymer obtained by polymerizing ethylene or ethylene and an olefin having 3 to 6 carbon atoms. The laminate according to claim 1 or 2, wherein the coalescence is used as an ethylene-α-olefin copolymer (A). The laminate according to any one of claims 1 to 3, wherein a paperboard is used as a substrate of the laminate. A paper container molded using the laminate according to claim 4 so that the outermost layer of the ethylene-based resin composition (C) is an inner surface of the container. The bag shape | molded so that the layer of the ethylene-type resin composition (C) which is an outermost layer might become the inner surface of a bag using the laminated body in any one of Claims 1-3.