JP2007030446A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in puncture strength and deformation recovery property, and a stretched film or stretched sheet obtained by stretching the laminate.
A laminate comprising at least one of the following layers [I], [II] and [III] and comprising at least three layers, and a stretched film or stretched sheet.
Layer [I]: Copolymer of ethylene and ethylenically unsaturated ester, copolymer of ethylene and unsaturated carboxylic acid, copolymer of ethylene and unsaturated carboxylic anhydride, ethylene and unsaturated carboxylic acid At least one ethylene-based copolymer layer [II] selected from the group consisting of metal salts of copolymers with anhydrides [II]: ethylene-α-olefin copolymer layer [III]: amorphous that satisfies specific requirements Resin composition containing 1 to 99% by weight of a crystalline or low crystalline α-olefin polymer and 99 to 1% by weight of a crystalline propylene polymer (provided that the total resin composition is 100% by weight). )
[Selection figure] None

Description

  The present invention relates to a laminate and a stretched film or stretched sheet. More specifically, the present invention relates to a laminate having excellent puncture strength and deformation recovery, and a stretched film or stretched sheet obtained by stretching the laminate.

In recent years, films such as fruits and vegetables, fresh fish, fresh meat, side dishes, books, stationery, sundries, etc., or films that are packaged directly from trays or boxes, have a beautiful appearance by heat shrinking after packaging. In addition, a heat-shrinkable film having a multi-layer structure is used that hardly deforms even when the film is pressed with a finger or the like. For example, Patent Document 1 describes a polyolefin-based heat-shrinkable laminated film in which an outer layer made of crystalline polypropylene or ethylene resin is laminated on a layer made of a resin composition containing amorphous polyolefin and crystalline polypropylene. Patent Document 2 uses an ethylene-vinyl acetate copolymer as a surface layer, and has at least one layer made of an ethylene-α-olefin copolymer and a layer made of a polypropylene resin as an inner layer. A multilayer shrink film is described.
Japanese Patent Laid-Open No. 7-232417 Japanese Patent No. 3606611

However, in the polyolefin-based heat-shrinkable laminated film of Patent Document 1, the resistance to puncture (puncture strength) when pressure is applied to the film by a projection or the like is not sufficient, or the film is deformed by being pressed with a finger or the like. In some cases, the film was not sufficiently easy to restore the shape before deformation (deformability recovery). Also, in the multilayer shrink film of Patent Document 2, although the puncture strength is improved, it cannot be said that the deformation recovery property is still sufficient.
Under such circumstances, the problem to be solved by the present invention, that is, the object of the present invention is to provide a laminate excellent in puncture strength and deformation recovery, and a stretched film or stretched sheet obtained by stretching the laminate. It is in.

That is, the present invention relates to a laminate comprising at least one layer [I], layer [II] and layer [III] described below, and comprising at least three layers, and a stretched film or stretched sheet.
Layer [I]: Copolymer of ethylene and ethylenically unsaturated ester, copolymer of ethylene and unsaturated carboxylic acid, copolymer of ethylene and unsaturated carboxylic anhydride, ethylene and unsaturated carboxylic acid At least one ethylene copolymer (A) selected from the group consisting of metal salts of copolymers with anhydrides
Layer [II]: ethylene-α-olefin copolymer (B)
Layer [III]: 1 to 99% by weight of an amorphous or low crystalline α-olefin polymer (C) satisfying the following requirements (c1), (c2) and (c3), and a crystalline propylene polymer ( D) Resin composition (E) containing 99 to 1% by weight (provided that the whole resin composition (E) is 100% by weight)
(C1) The content of monomer units derived from ethylene is 60 mol% or less (provided that the entire polymer is 100 mol%).
(C2) The molecular weight distribution is 3 or less.
(C3) The crystal melting heat quantity obtained by measuring in the range of −50 ° C. to 200 ° C. by differential scanning calorimetry (DSC) is 30 J / g or less.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in puncture strength and a deformation | transformation recovery property, and the stretched film or stretched sheet formed by extending | stretching it are provided.

  Examples of the ethylene copolymer (A) used in the layer [I] of the present invention include a copolymer of ethylene and an ethylenically unsaturated ester, a copolymer of ethylene and methyl acrylate, and ethylene and acrylic. Copolymers with ethyl acrylate, copolymers with ethylene butyl acrylate, copolymers of ethylene and methyl methacrylate, copolymers of ethylene and ethyl methacrylate, copolymers of ethylene and butyl methacrylate , Copolymer of ethylene and vinyl acetate, copolymer of ethylene and unsaturated carboxylic acid, copolymer of ethylene and acrylic acid, copolymer of ethylene and methacrylic acid, ethylene and unsaturated carboxylic acid Copolymers with anhydrides, copolymers of ethylene and maleic anhydride, metal salts of copolymers of ethylene and unsaturated carboxylic anhydrides, ethylene and acrylic acid Metal salt of a copolymer of a metal salt of a copolymer of ethylene and methacrylic acid. Among them, more preferably, a copolymer of ethylene and methyl acrylate, a copolymer of ethylene and ethyl acrylate, a copolymer of ethylene butyl acrylate, a copolymer of ethylene and methyl methacrylate, Preferred is a copolymer of ethylene and ethyl methacrylate, a copolymer of ethylene and butyl methacrylate, a copolymer of ethylene and vinyl acetate, a copolymer of ethylene and methyl methacrylate, and ethylene and vinyl acetate. It is a copolymer.

  The content of the monomer unit derived from ethylene of the ethylene-based copolymer (A) used in the layer [I] of the present invention is not particularly limited, but is usually 50 from the viewpoint of balance between puncture strength and deformation recovery. It is -99 weight%, Preferably it is 60-97 weight%, More preferably, it is 70-95 weight%, More preferably, it is 75-93 weight%.

  The melt flow rate of the ethylene-based copolymer (A) used in the layer [I] of the present invention is preferably 0.1 to 20 g / 10 minutes, more preferably from the viewpoint of the balance between extrusion torque and puncture strength. Is 0.5 to 10 g / 10 min, more preferably 1.0 to 5 g / 10 min. The melt flow rate is measured at a temperature of 190 ° C. and a load of 21.18 N according to the method defined in JIS K7210.

  The durometer A hardness of the ethylene copolymer (A) used in the layer [I] of the present invention is preferably 55 to 98, more preferably 60 to 60, from the viewpoint of the balance between puncture strength and deformation recovery. 97, more preferably 70 to 96, and particularly preferably 80 to 95. The durometer A hardness is measured according to JIS K6253.

  The ethylene copolymer (A) used in the layer [I] of the present invention may be a mixture of two or more different ethylene copolymers.

  As a method for producing the ethylene copolymer (A) used in the layer [I] of the present invention, a known polymerization method using a known olefin polymerization catalyst is used. For example, slurry polymerization method, solution polymerization method, bulk polymerization method, gas phase polymerization method, or radical initiator using complex catalyst such as Ziegler-Natta catalyst, metallocene complex or nonmetallocene complex Examples include a bulk polymerization method and a solution polymerization method.

  The ethylene-α-olefin copolymer (B) used in the layer [II] of the present invention is a copolymer of ethylene and one or more α-olefins having 3 to 12 carbon atoms. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene and 4-methyl-1-pentene. 4-methyl-1-hexene, vinylcyclohexane, vinylcyclohexene, styrene, norbornene, butadiene, isoprene and the like. The content of the monomer unit derived from the α-olefin in the ethylene-α-olefin copolymer (B) is usually 40 mol% or less when the entire copolymer is 100 mol%.

  The monomer of the monomer unit derived from the α-olefin contained in the ethylene-α-olefin copolymer (B) used in the layer [II] of the present invention is from the viewpoint of availability and puncture strength. 1-hexene, 1-octene and 4-methyl-1-pentene are preferable.

The ethylene-α-olefin copolymer (B) used for the layer [II] of the present invention preferably satisfies the following requirements (b1) and (b2).
(B1) The melt flow rate is 0.5 to 30 g / 10 minutes.
(B2) The density is 870 to 910 kg / m ³ .

  If the melt flow rate of the ethylene-α-olefin copolymer (B) used in the layer [II] of the present invention is below the above range, the extrusion torque may be high, and if it exceeds the above range, the puncture strength is reduced. There is a case. More preferably, it is 1-20 g / 10min, More preferably, it is 1.5-10 g / 10min. The melt flow rate is measured at a temperature of 190 ° C. and a load of 21.18 N according to the method defined in JIS K7210.

When the density of the ethylene-α-olefin copolymer (B) used in the layer [II] of the present invention is below the above range, the puncture strength may be deteriorated, and when it exceeds the above range, the deformation recovery property is deteriorated. There is a case. More preferably, it is 880-905 kg / m < ³ >, More preferably, it is 885-900 kg / m < ³ >. The density is measured according to the method defined in JIS K6760-1981.

The composition distribution variation coefficient (Cx) of the ethylene-α-olefin copolymer (B) used in the layer [II] of the present invention is preferably 0.5 or less, more preferably from the viewpoint of deformation recovery. 0.4 or less, more preferably 0.3 or less. Here, the composition distribution variation coefficient (Cx) is a value defined by the following (Equation 1), and is calculated from a composition distribution curve obtained by a temperature rising elution fractionation method.
Cx = σ / SCB _ave (Formula 1)
Cx: variation coefficient of composition σ: standard deviation of composition distribution SCB _ave : average value of the degree of short chain branching per 1000 carbon atoms (unit: 1/1000 C)

  The production method of the ethylene-α-olefin copolymer (B) used in the layer [II] of the present invention includes a slurry polymerization method using a metallocene polymerization catalyst or a polymerization catalyst having a vanadium compound, a solution polymerization method, a bulk weight Examples thereof include a combination method and a gas phase polymerization method.

  Examples of the metallocene polymerization catalyst include, for example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, JP-A-60-. No. 35008, No. 61-130314, No. 3-163088, No. 4-268307, No. 9-12790, No. 9-87313, No. 11-80233 And the catalyst described in JP-T-10-508055.

Specifically, the metallocene polymerization catalyst is represented by the general formula R ¹ _k R ² _l R ³ _m R ⁴ _n M (where M represents a zirconium atom, a titanium atom, a hafnium atom or a vanadium atom, and R ¹ represents a cyclopentadiene form. R ² , R ³ and R ⁴ each represents a group having a cyclopentadiene anion skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom or And a catalyst having a metallocene compound and an organoaluminum oxide compound represented by the following formula: a hydrogen atom, k and l being an integer of 1 or more, and k + 1 + m + n = 4.

  Examples of the metallocene compounds represented by the above general formula include bis (cyclopentadienyl) diethyltitanium, bis (cyclopentadienyl) dimethyltitanium, bis (pentamethylcyclopentadienyl) titanium, and bis (cyclo Pentadienyl) dichlorotitanium, bis (cyclopentadienyl) titanium monochloride monohydride, bis (indenyl) titanium monochloride monohydride, bis (indenyl) titanium dichloride, ethylenebis (indenyl) dimethyltitanium, ethylenebis (indenyl) Methyl titanium chloride, ethylene bis (indenyl) titanium dichloride, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) titanium dichloride, ethylene bis (4 , 6,7-tetrahydro-1-indenyl) dimethyltitanium, ethylenebis (4-methyl-1-indenyl) titanium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) titanium dichloride, bis (cyclopentadienyl) ) Diethyltitanium, bis (cyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) zirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) monochlorolide monohydride, bis (indenyl) ) Zirconium monochloride monohydride, bis (indenyl) zirconium dichloride, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) methylzirconium dichloride, ethyl Bis (indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylzirconium, ethylenebis ( 4-methyl-1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, and the like.

  Examples of the organoaluminum oxide compound include tetramethyldialuminoxane, tetraethyldiaminooxane, tetrabutyldialuminoxane, tetrahexyldialuminoxane, methylaluminoxane, ethylaluminoxane, butylaluminoxane, and hexylaluminoxane.

Examples of the polymerization catalyst having a vanadium compound include a catalyst composed of a vanadium compound and an organoaluminum compound. The vanadium compound of general formula _{VO (OR) n X 3-} n ( wherein, R represents a hydrocarbon group, X represents a halogen atom, n represents represents. A number that is 0 to 3) represented by Compounds, specifically, VOCl ₃ , VO (OCH ₃ ) Cl ₂ , VO (OCH ₃ ) ₂ Cl, VO (OCH ₃ ) ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (OC ₂ H ₅ ) ₃ , VO (OC ₃ H ₇ ) Cl ₂ , VO (OC ₃ H ₇ ) ₂ Cl, VO (OC ₃ H ₇ ) ₃ or a mixture thereof. . Among these vanadium compounds, a compound in which n is 0 to 1 is preferable.

The organoaluminum compound is represented by the general formula R ′ _m AlX _3-m (where R ′ represents a hydrocarbon group, X represents a halogen atom, and m represents a number of 1 to 3). Specifically, (C ₂ H ₅ ) ₂ AlCl, (C ₄ H ₉ ) ₂ AlCl, (C ₆ H ₁₃ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , _{(C 4 H 9) 1.5 AlCl} 1.5, include _{(C 6 H 13) 1.5 AlCl} 1.5, C 2 H 5 AlCl 2, C 4 H 9 AlCl 2, C 6 H 13 AlCl 2 , and the like. Among these organoaluminum compounds, m is preferably a compound having 1 to 2, more preferably (C ₂ H ₅ ) _1.5 AlCl _1.5 .

  The ethylene-α-olefin copolymer (B) used for the layer [II] of the present invention preferably has no long chain branching in the molecular chain from the viewpoint of puncture strength.

  The amorphous or low crystalline α-olefin polymer (C) used in the layer [III] of the present invention is a polymer containing monomer units derived from α-olefin.

  The amorphous or low crystalline α-olefin polymer (C) is preferably selected from the group consisting of α-olefins having 2 to 20 carbon atoms from the viewpoint of the piercing strength of the resulting laminate. Further, it is a copolymer containing two or more kinds of α-olefins, and the α-olefin monomer units in which the total number of carbon atoms of the α-olefin is 6 or more.

  Examples of the α-olefin having 2 to 20 carbon atoms contained in the amorphous or low crystalline α-olefin polymer (C) include ethylene, propylene, 1-butene, 1-pentene, and 1-hexene. 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, Linear olefins such as 1-nonadecene and 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2, Examples include chain olefins such as branched olefins such as 4-trimethyl-1-pentene. Among these, α-olefins having a total number of carbon atoms of 6 or more are selected. Used is. Specific combinations include, for example, ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / 4-methyl-1-pentene, propylene / 1-butene, propylene / 1-hexene, propylene. / 1-octene, ethylene / propylene / 1-butene, ethylene / propylene / 1-hexene, ethylene / 1-butene / 1-hexene, and the like.

  The amorphous or low crystalline α-olefin polymer (C) may contain a monomer unit other than the α-olefin, and as a monomer of the monomer unit, A cyclic olefin, a polyene compound, and a vinyl aromatic compound can be mentioned.

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene. 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1 , 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8- Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5 8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro- 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Phthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene Xene, 4-methyl Examples include cyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene and the like.

  Examples of the polyene compound include so-called conjugated polyene compounds in which one single bond is sandwiched between double bonds, and other non-conjugated polyene compounds. Examples of the conjugated polyene compound include aliphatic conjugated polyene compounds such as linear aliphatic conjugated polyene compounds and branched aliphatic conjugated polyene compounds, and alicyclic conjugated polyene compounds. Examples of the non-conjugated polyene compound include an aliphatic non-conjugated polyene compound, an alicyclic non-conjugated polyene compound, and an aromatic non-conjugated polyene compound. These polyene compounds may contain an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group and the like.

  Here, examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, and 2-isopropyl-1,3-butadiene. 2-hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1 , 3-hexadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2, , 3-dimethyl-1,3-octadiene, 2,3-dimethyl-1,3-decadiene and the like. Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, 2, 3-dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3 -Pentadiene, 2-chloro-1,3-cyclopentadiene, 2-chloro-1,3-cyclohexadiene and the like.

  Here, as the aliphatic non-conjugated polyene compound, for example, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4- Hexadiene, 4-ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3.3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl- 1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-hept Diene, 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 4-methyl-1, 4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1, 5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1, 6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1.6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-e 1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6- Ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7- Methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5- Methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6- Ethyl-1,6-decadiene, 7 -Methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8 -Ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9 -Methyl-1,8-undecadiene, 6,10-dimethyl 1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 4-ethylidene 8-methyl-1,7-nonadiene 13-ethyl-9-methyl-1,9,12-pentadecatriene, 5,9,13-trimethyl-1,4,8,12-tetradecadiene, 8,14,16-trimethyl-1,7 , 14-Hexa Katorien, 4-ethylidene-12-methyl-1,11-penta decadiene, and the like. Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexene, 5-vinyl 2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropenyl-2-norbornene, and cyclohexane. Hexadiene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, 2,3-diisopropylidene-5-norbornene, 2- Ethylidene-3-isopropylidene-5-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5 -Divinylcyclooctane, 1-allyl- -Vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1 -Isopropenyl-3-vinylcyclopentane, methyltetrahydroindene, etc. are mentioned. On the other hand, examples of the aromatic non-conjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, and ethylstyrene. And vinyl naphthalene.

  The content of the monomer unit derived from ethylene of the amorphous or low crystalline α-olefin polymer (C) is 60 mol% or less (provided that the entire polymer is 100 mol%). . Preferably it is 40 mol% or less, More preferably, it is 20 mol% or less, More preferably, it is 10 mol% or less, Most preferably, it is 5 mol% or less. If it exceeds 60 mol%, the puncture strength may deteriorate.

Specific examples of the amorphous or low crystalline α-olefin polymer (C) include the following copolymers (1) to (15).
(1) Copolymer of ethylene and α-olefin having 4 to 20 carbon atoms such as ethylene-1-butene copolymer (2) Ethylene-1-butene-2-methyl-1,3-butadiene copolymer A copolymer of an ethylene such as ethylene, an α-olefin having 4 to 20 carbon atoms and a polyene compound (3) an ethylene such as an ethylene-1-butene-5-ethylidenenorbornene copolymer and an α- having 4 to 20 carbon atoms Copolymer of olefin and cyclic olefin compound (4) Copolymer of ethylene, α-olefin having 4 to 20 carbon atoms and vinyl aromatic compound such as ethylene-1-butene-styrene copolymer (5) Ethylene A copolymer of ethylene, an α-olefin having 4 to 20 carbon atoms, a polyene compound and a vinyl aromatic compound such as 1-butene-2-methyl-1,3-butadiene-styrene copolymer (6 ) Copolymer of ethylene, propylene and α-olefin having 4 to 20 carbon atoms such as ethylene-propylene-1-butene copolymer (7) Ethylene-propylene-1-butene-2-methyl-1,3- Copolymer of ethylene and propylene of butadiene copolymer v, α-olefin having 4 to 20 carbon atoms and polyene compound (8) Ethylene and propylene such as ethylene-propylene-1-butene-5-ethylidene norbornene copolymer Copolymer of α-olefin having 4 to 20 carbon atoms and cyclic olefin compound (9) Ethylene and propylene such as ethylene-propylene-1-butene-styrene copolymer, and α-olefin having 4 to 20 carbon atoms And vinyl aromatic compound copolymer (10) ethylene-propylene-1-butene-2-methyl-1,3-butadiene-styrene Copolymers of ethylene and propylene such as copolymers, α-olefins having 4 to 20 carbon atoms, polyene compounds and vinyl aromatic compounds (11) Propylene such as propylene-1-butene copolymers and carbon atoms of 4 Copolymer of -20 α-olefin (12) Copolymer of propylene such as propylene-1-butene-2-methyl-1,3-butadiene copolymer, α-olefin having 4 to 20 carbon atoms and polyene compound Polymer (13) Copolymer of propylene such as propylene-1-butene-5-ethylidenenorbornene copolymer, α-olefin having 4 to 20 carbon atoms and cyclic olefin compound (14) Propylene-1-butene-styrene Copolymer of propylene such as copolymer, α-olefin having 4 to 20 carbon atoms and vinyl aromatic compound (15) Propylene-1-butene-2 Copolymer of propylene, α-olefin having 4 to 20 carbon atoms, polyene compound and vinyl aromatic compound such as methyl-1,3-butadiene-styrene copolymer Among these copolymers, a film is obtained. From the viewpoint of the puncture strength, the polymers (1), (6) and (11) are preferred, and the polymer (11) is more preferred.

  The amorphous or low crystalline α-olefin polymer (C) has a molecular weight distribution of 3 or less, preferably 1.5 or more and less than 3. If the molecular weight distribution exceeds 3, the puncture strength may deteriorate. The molecular weight distribution is a ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn), and is measured by gel permeation chromatography (GPC) using standard polystyrene as a molecular weight standard substance.

  The amorphous or low crystalline α-olefin polymer (C) has a heat of crystal fusion of 30 J / g or less obtained by differential scanning calorimetry (DSC) measured in the range of −50 ° C. to 200 ° C. Preferably, it is 20 J / g or less, More preferably, it is 10 J / g or less, More preferably, it is 5 J / g or less. If the heat of crystal fusion exceeds 30 J / g, the deformation recovery property may deteriorate.

  The amorphous or low-crystalline α-olefin polymer (C) has a melting peak with a crystal melting calorie measured by differential scanning calorimetry (DSC) of 1 J / g or more, and a crystallization calorie of 1 J / g. A polymer in which any of the above crystallization peaks is not observed in the range of −100 to 200 ° C. is particularly preferable.

  The intrinsic viscosity [η] of the amorphous or low crystalline α-olefin polymer (C) is not particularly limited, but is preferably 0.1 or more from the viewpoint of uniform stretchability of the obtained film. Preferably it is 0.5 or more, More preferably, it is 1.0 or more, Especially preferably, it is 1.5 or more, Most preferably, it is 2 or more. Moreover, from a viewpoint of extrusion processability, Preferably it is 10 or less, More preferably, it is 7 or less, More preferably, it is 5 or less, Most preferably, it is 4 or less. The intrinsic viscosity [η] is measured using an Ubbelohde viscometer in 135 ° C. tetralin.

The amorphous or low crystalline α-olefin polymer (C) can be produced using a known Ziegler-Natta type catalyst or a known single site catalyst (metallocene, etc.). From the standpoint of further improving the properties, known single site catalysts (metallocene, etc.) are preferred. Examples of such single site catalysts include Japanese Patent Application Laid-Open Nos. 58-19309, 60-35005, and JP-A-60-35006, JP-A-60-35007, JP-A-60-35008, JP-A-61-130314, JP-A-3-16388, JP-A-4-268307, Kaihei 9-12790, JP-A-9-87313, JP-A-10-508055, JP-A-11-80233, JP No. 0-508055, etc., JP-A-10-316710, JP-A-11-1000039, JP-A-11-80228, JP-A-11-80227, JP-A-10- Non-metallocene complex catalysts described in JP-A-513489, JP-A-10-338706, JP-A-11-71420 and the like can be mentioned. Among these, metallocene catalysts are preferable from the viewpoint of availability, and among them, suitable metallocene catalysts include, for example, an element periodic table having at least one cyclopentadiene type anion skeleton and a C ₁ symmetric structure. A transition metal complex of Group 12 to Group 12 is preferred. Further, as an example of the production method using a metallocene catalyst, there can be mentioned the method of European Patent Application No. 12111287.

  Examples of the crystalline propylene polymer (D) used in the layer [III] of the present invention include a polymer having a content of monomer units derived from propylene of 50% by weight or more. The propylene homopolymer, propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-1-butene copolymer A polymer, a propylene-ethylene-1-hexene copolymer, etc. can be mentioned. Moreover, as these polymers, those having a wide structure such as a random type and a block type can be used.

  The number average molecular weight of the crystalline propylene polymer (D) used for the layer [III] of the present invention is not particularly limited, but a polymer of 10,000 to 1,000,000 is preferably used.

  As a method for producing the crystalline propylene polymer (D) used in the layer [III] of the present invention, a known polymerization method using a known olefin polymerization catalyst is used. For example, a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like using a complex catalyst such as a Ziegler-Natta catalyst, a metallocene complex, or a nonmetallocene complex may be used. It is also possible to use commercially available products.

  As the content of the amorphous or low crystalline α-olefin polymer (C) and the content of the crystalline propylene polymer (D) in the layer [III] of the present invention, uniform stretching of the resulting laminate is performed. From the viewpoint of safety, when the total of the polymer (C) and the polymer (D) is 100% by weight, the content of the polymer (C) is 10 to 45% by weight, and the content of the polymer (D) is 90 to 55% by weight, preferably 15 to 40% by weight of polymer (C) and 85 to 60% by weight of polymer (D), more preferably polymer (C) The content of C) is 20 to 35% by weight, and the content of the polymer (D) is 80 to 65% by weight.

In the layer [I], layer [II], and layer [III] of the present invention, petroleum resins may be blended if necessary within a range not impairing the object of the present invention. Examples of petroleum resins include rosin resins, terpene resins, thermoplastic resins obtained by polymerizing and solidifying a cracked oil fraction produced by thermal decomposition of petroleum, coumarone-indene resins, alkyl-phenol resins, and the like. Examples of the rosin resin include gum rosin, wood rosin, hydrogenated rosin, esterified rosin esterified with alcohol, and rosin phenolic resin obtained by reacting phenol and rosin. Examples of the terpene resins include α-pinene and β-pinene polymerized terpene resins, terpene phenol resins obtained by reacting phenol and terpene, aromatic modified terpene resins imparted with polarity by styrene, hydrogenated terpene resins, and the like. It is done. The cracked oil fraction of polymerized thermoplastic resin is solidified to produce by pyrolysis of petroleum, aromatic petroleum that aliphatic petroleum resin obtained by the C ₅ fraction as a raw material, the C ₉ fraction as a raw material Examples thereof include resins, alicyclic petroleum resins made from dicyclopentadiene, copolymerized petroleum resins in which two or more of these are copolymerized, and hydrogenated petroleum resins obtained by hydrogenating these. Specifically, for example, “Highlets”, “Petrogin” manufactured by Mitsui Chemicals, Inc., “Arcon” manufactured by Arakawa Chemical Industries, Ltd., “Clearon” manufactured by Yashara Chemical Co., Ltd., etc. should be used. Can do.

  Among the petroleum resins, hydrogenated derivatives such as hydrogenated rosin, hydrogenated terpene resin, and hydrogenated petroleum resin are preferable in terms of hue and odor.

  The layers [I], [II], and [III] of the present invention may be recycled by blending, for example, a resin generated from trimming loss or the like within a range that does not impair the object of the present invention.

  In the layers [I], [II], and [III] of the present invention, various additives and fillers, for example, antioxidants, nucleating agents, and ultraviolet absorbers, as necessary, within a range that does not impair the purpose of the present invention. An agent, a lubricant, an antiblocking agent, an antistatic agent, an antifogging agent and the like can be blended.

  The layer structure of the laminate of the present invention and the stretched film or stretched sheet may be, for example, layer [I] / layer [II] / layer [III], layer [I] / layer [III] / layer [II], Layer [II] / Layer [I] / Layer [III], Layer [I] / Layer [II] / Layer [III] / Layer [I], Layer [I] / Layer [II] / Layer [III] / Layer [II], Layer [I] / Layer [III] / Layer [I] / Layer [II], Layer [II] / Layer [I] / Layer [III] / Layer [II], Layer [I] / Layer [II] / Layer [III] / Layer [II] / Layer [I], Layer [I] / Layer [II] / Layer [III] / Layer [I] / Layer [II], Layer [II] / Examples thereof include layer [I] / layer [III] / layer [I] / layer [II].

  In the layer structure of the laminate of the present invention and the stretched film or stretched sheet, at least one surface layer is preferably layer [I] from the viewpoint of heat sealability.

  From the viewpoint of heat sealability, the layer structure of the laminate of the present invention, and the stretched film or stretched sheet are adjacent to the layer [I], the layer [II], and the layer [III], and the layer [I]. The layers are preferably laminated in the order of / layer [II] / layer [III].

  The laminate of the present invention, and the stretched film or stretched sheet have at least one layer [I], [II] and [III], respectively, and are a laminate composed of at least three layers. A multilayer film having a layer [IV] other than the layer [I], the layer [II] and the layer [III] may be used. The layer [III] includes a layer containing an olefin resin, a layer containing a polyamide resin, a layer containing a polyvinyl alcohol resin, a layer containing a polyester resin, a layer containing an adhesive resin, and a recycled resin. A layer etc. can be mentioned.

  Examples of the layer configuration order of the layer [I], the layer [II], the layer [III], and the layer [IV] include layer [I] / layer [II] / layer [III] / layer [IV], layer [I] / layer [II] / layer [IV] / layer [III], layer [I] / layer [IV] / layer [II] / layer [III], layer [IV] / layer [I] / layer [II] / layer [III], layer [I] / layer [II] / layer [III] / layer [IV] / layer [I], layer [I] / layer [II] / layer [IV] / layer [III] / layer [I], layer [I] / layer [IV] / layer [II] / layer [III] / layer [I], layer [IV] / layer [I] / layer [II] / layer [III] / Layer [I], Layer [I] / Layer [II] / Layer [III] / Layer [IV] / Layer [III] / Layer [II] / Layer [I], Layer [I] / Layer [III] / Layer [II] / Layer [IV] / Layer [II] / Layer [III] / [I], layer [II] / layer [I] / layer [III] / layer [IV] / layer [III] / layer [I] / layer [II], layer [II] / layer [III] / layer [I] / layer [IV] / layer [I] / layer [III] / layer [II] and the like.

  Although the total thickness of the laminated body of this invention is not specifically limited, Although it can select arbitrarily, Preferably it is 30 micrometers-10 mm, More preferably, they are 60 micrometers-5 mm, More preferably, they are 100 micrometers-1 mm.

  The total thickness of the stretched film of the present invention is not particularly limited and can be arbitrarily selected, but is preferably 1 to 500 μm, more preferably 3 to 300 μm, still more preferably 5 to 100 μm, Especially preferably, it is 10-50 micrometers.

  The total thickness of the stretched sheet of the present invention is not particularly limited and can be arbitrarily selected, but is preferably 500 μm to 5 mm, more preferably 1 mm to 3 mm.

  The thickness ratio of the layer [I] to the total thickness of the laminate of the present invention and the stretched film or stretched sheet is not particularly limited and can be arbitrarily selected. Usually, the thickness ratio of the layer [I] is 1 to 99% with respect to the total thickness, preferably 5 to 90%, more preferably 10 to 80%, and still more preferably 20 to 70%.

  The thickness ratio of the layer [II] to the total thickness of the laminate of the present invention and the stretched film or stretched sheet is not particularly limited, and can be arbitrarily selected. Usually, the thickness ratio of the layer [II] is 1 to 99% with respect to the total thickness, preferably 5 to 90%, more preferably 10 to 80%, and still more preferably 20 to 70%.

  The thickness ratio of the layer [III] to the total thickness of the laminate of the present invention and the stretched film or stretched sheet is not particularly limited and can be arbitrarily selected. Usually, the thickness ratio of the layer [III] is 1 to 99% with respect to the total thickness, preferably 5 to 90%, more preferably 10 to 80%, and still more preferably 20 to 70%.

  The thickness ratio of the layer [I] and the layer [II] of the laminate of the present invention and the stretched film or stretched sheet is not particularly limited and can be arbitrarily selected. Usually, layer [I] / layer [II] = 1% / 99% to 99% / 1%, preferably 5% / 95% to 95% / 5%, more preferably 10% / 90% It is -90% / 10%, More preferably, it is 20% / 80% -80% -20%, Most preferably, it is 30% / 70% -70% / 30%.

  The ratio of the total thickness of the layer [I] and the layer [II] of the laminate of the present invention and the stretched film or stretched sheet and the thickness of the layer [III] is not particularly limited and may be arbitrarily selected. Can do. Usually, the ratio of the total thickness of layer [I] and layer [II] to the thickness of layer [III] is 1% / 99% to 99% / 1%, preferably 5% / 95% to 95%. / 5%, more preferably 10% / 90% to 90% / 10%, still more preferably 20% / 80% to 80% to 20%, particularly preferably 30% / 70% to 70%. % / 30%.

  The method for producing the laminate of the present invention is not particularly limited, and a method for thermally bonding another layer to a layer formed by a known method, for example, an inflation method, a T-die method, a calendar method, or the like, Examples of the method include coextrusion of each layer and film formation by an inflation method, a T-die method, or the like.

  The stretched film or stretched sheet of the present invention is obtained by stretching the laminate in at least a uniaxial direction. The stretching direction may be uniaxial or biaxial. In the case of uniaxial stretching, for example, a commonly used roll stretching method is preferred. In the case of biaxial stretching, a tubular stretching method, a tenter stretching method, or the like may be used, for example, a sequential stretching method in which stretching is performed in one direction and then stretching in the other direction, or a method of simultaneously stretching in two directions. But you can.

  The stretching conditions of the stretched film or stretched sheet of the present invention are not particularly limited, but from the viewpoint of deformation recovery, the stretching temperature is preferably from room temperature to the melting point of the crystalline propylene polymer (D). More preferably, it is 40-150 degreeC, More preferably, it is 60-130 degreeC, Most preferably, it is 80 degreeC-110 degreeC. Moreover, from the viewpoint of the balance between deformation recovery and puncture strength, the stretching ratio is 2 to 10 times, preferably 2.5 to 8 times, more preferably 3 to 6 times in both the vertical and horizontal directions. is there. About the draw ratio of a length direction and a horizontal direction, it may be the same or may differ, and it can select arbitrarily according to a use. Moreover, you may heat set after extending | stretching.

  The stretched film or stretched sheet of the present invention has heat shrinkability. The heat shrinkage rate is preferably at least a uniaxial value of 5% or more, more preferably 10%, as measured in the measurement of immersing the stretched film or stretched sheet in silicone oil at 110 ° C. for 5 seconds. % Or more, and particularly preferably 15% or more.

  The laminate of the present invention, and the stretched film or stretched sheet are used for various applications, and among them, it is preferably used for stretch films, and the film is used for packaging food, pallet cargo, grass, books, toys and the like. Among them, among these, foods such as fruits and vegetables, fresh fish, fresh meat, and side dishes, books, stationery, miscellaneous goods, and the like are preferably used for food packaging that is packaged directly on a plastic tray or the like.

Hereinafter, the present invention will be described in detail based on examples. The physical properties were evaluated by the following methods.
(1) Monomer content of amorphous or low crystalline α-olefin polymer (C) Using a nuclear magnetic resonance apparatus (trade name AC-250, manufactured by Bruker), ¹ H-NMR spectrum, ¹³ It calculated based on the measurement result of the C-NMR spectrum. Specifically, in the ¹³ C-NMR spectrum, from the ratio of the spectral intensity of methyl carbon derived from the propylene monomer unit to the spectral intensity of methyl carbon derived from the 1-butene monomer unit, the propylene monomer unit and 1 -The composition ratio of the butene monomer unit was calculated, and then in the ¹ H-NMR spectrum, the ethylene unit amount was determined from the ratio between the spectral intensity of hydrogen derived from the methine unit and the methylene unit and the spectral intensity of hydrogen derived from the methyl unit. The composition ratio of the body unit, the propylene monomer unit and the 1-butene monomer unit was calculated.
(2) Molecular weight distribution measurement The gel permeation chromatograph (GPC) method was used and the measurement was performed under the following conditions.
Equipment: 150C ALC / GPC manufactured by Waters
Column: Shodex Packed Column A-80M manufactured by Showa Denko KK Temperature: 140 ° C
Solvent: o-dichlorobenzene elution solvent flow rate: 1.0 ml / min Sample concentration: 1 mg / ml
Measurement injection volume: 400 μl
Molecular weight standard: Standard polystyrene Detector: Differential refraction (3) Differential scanning calorimetry (DSC)
It measured on condition of the following using the differential scanning calorimeter (Seiko Electronics Co., Ltd. DSC220C: input compensation DSC). Indium was used as a standard material for measurement.
(I) About 5 mg of the sample was heated from room temperature to 200 ° C. at a rate of temperature increase of 30 ° C./min, and held for 5 minutes after completion of the temperature increase.
(Ii) Next, the temperature was decreased from 200 ° C. to −100 ° C. at a rate of temperature decrease of 10 ° C./min, and held for 5 minutes after the temperature decrease was completed.
(Iii) Next, the temperature was increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min.
(4) Intrinsic viscosity [η]
The measurement was performed at 135 ° C. using an Ubbelohde viscometer. Amorphous or low-crystalline α-olefin-based weight in which the concentration c of amorphous or low-crystalline α-olefin-based polymer per unit volume of tetralin is 0.6, 1.0, 1.5 mg / ml A combined tetralin solution was prepared and the intrinsic viscosity at 135 ° C. was measured. The measurement was repeated three times at each concentration, and the average value of the three values obtained was taken as the specific viscosity (η _sp ) at that concentration, and the value obtained by extrapolating c of η _sp / c to zero was used as the intrinsic viscosity [η ].
(5) Melt flow rate (MFR)
The crystalline propylene polymer (D) was measured according to JIS K7210 under conditions of a load of 21.18 N and a temperature of 230 ° C.

(6) Composition distribution coefficient of variation (Cx)
It measured using the Tosoh Corporation temperature rising elution fractionation apparatus (TREF). An ethylene-α-olefin copolymer was dissolved in an orthodichlorobenzene (ODCB) solvent heated to 145 ° C., and the concentration was adjusted to about 0.01 g / ml to prepare a measurement sample. 10 ml of a measurement sample was injected into a column (150 mm long, 21 mm inner diameter, filled with 50-80 mesh sea sand) installed in a column oven heated to 145 ° C. The oven temperature was lowered to 105 ° C. at a rate of 40 ° C./45 minutes, further lowered from 105 ° C. to −15 ° C. over 8 hours, and held at −15 ° C. for 4 hours. Subsequently, while flowing ODCB through the column at a rate of 2.5 ml / min, the temperature was raised at a rate of 10 ° C./60 minutes and raised to 125 ° C., while the relative concentration of the measurement sample eluted from the column was determined. FT-IR connected to The FT-IR measurement was performed every 2 ° C. from a temperature of −14 ° C. to 110 ° C., and the absorption peak area of 2985 to 2780 cm ⁻¹ was used for the measurement. The short chain branching degree (SCB) per 1000 carbon atoms of the ethylene-α-olefin copolymer eluted at each temperature was determined by the following (formula 2). However, no elution was observed at a temperature at which SCB was negative in the calculation.
SCB = −0.7322 × elution temperature (° C.) + 70.68 (Formula 2)
A composition distribution curve (x-axis: short-chain branch, y-axis: relative concentration) is obtained from the obtained short-chain branching degree and its relative concentration, and the average short-chain branching degree per 1000 carbon atoms (SCB _ave ) from this curve. And a standard deviation (σ) of the composition distribution was obtained, and a composition distribution variation coefficient Cx representing the breadth of the distribution was calculated from the following (formula 1).
Cx = σ / SCB _ave (Formula 1)
Average short chain branching degree (SCB _ave ) = ΣN (i) · W (i)
N (i): degree of short chain branching at the i-th data sampling point W (i): relative concentration at the i-th data sampling point, ie, ΣW (i) = 1
Standard deviation of composition distribution (σ) = {Σ (N (i) −SCB _ave ) ² · W (i)} ^0.5
(7) Puncture strength A circular sample film 1 having a diameter of 44.45 mm is fixed to the film fixing jig 2, and a hemispherical pin 3 having a radius of 6.35 mm at the center of the film is attached to the center of the film at 100 mm / min. The film was pushed in until the film was broken, and the maximum value of the stress in the stress-strain curve recorded on the chart paper was defined as the puncture strength. FIG. 1 is a side view of an apparatus for measuring puncture strength.

(8) Deformability recovery Using the same measuring device as the puncture strength, push in to a predetermined indentation depth of 5 at a speed of 100 mm / min. It was measured whether it disappeared. The maximum indentation depth 5 at which the imprint marks disappear completely was defined as deformation recovery. The greater the maximum indentation depth, the better the deformation recovery.

<Example 1>
[1] Manufacture and Evaluation of Amorphous α-Olefin Polymer In a 100 L SUS polymerizer equipped with a stirrer, propylene and 1-butene were used as molecular weight regulators, and hydrogen was continuously used as follows. To obtain a propylene-1-butene copolymer.
From the lower part of the polymerization vessel, hexane as a polymerization solvent was continuously fed at a feed rate of 100 L / hour, propylene was fed at a feed rate of 24.00 kg / hour, and 1-butene was fed at a feed rate of 1.81 kg / hour. Supplied.
The reaction mixture is continuously withdrawn from the upper part of the polymerization vessel so that the reaction mixture in the polymerization vessel maintains an amount of 100 L. From the lower part of the polymerization vessel, dimethylsilylene (tetramethylcyclopentadiene) is used as a component of the polymerization catalyst. Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride at a feed rate of 0.005 g / hr and triphenylmethyltetrakis (pentafluorophenyl) borate at a feed rate of 0.298 g / hr Triisobutylaluminum was continuously fed at a feed rate of 2.315 g / hr.
The copolymerization reaction was carried out at 45 ° C. by circulating cooling water through a jacket attached to the outside of the polymerization vessel.
A small amount of ethanol is added to the reaction mixture continuously withdrawn from the top of the polymerization vessel to stop the polymerization reaction, followed by demonomerization and water washing, and then the solvent is removed by steam in a large amount of water. Thus, a propylene-1-butene copolymer was obtained, and this was dried under reduced pressure at 80 ° C. for 1 day. The production rate of the copolymer was 7.10 kg / hour. Table 1 shows the physical property evaluation results of the polymer (hereinafter referred to as polymer (C-1)).

[2] Production and Evaluation of Film (1) Preparation of Resin Composition (E-1) Crystalline propylene-ethylene random copolymer (Sumitomo Chemical Co., Ltd. “Nobrene”) which is a crystalline propylene polymer (A) FS2011DG2 ”, MFR (temperature 230 ° C., load 21.18 N) = 2.5 g / 10 minutes, melting main peak temperature = 158 ° C.) 80% by weight, amorphous or low crystalline α-olefin polymer (C The polymer composition (C-1) (20% by weight) was melt-extruded at 220 ° C. with a twin-screw kneading extruder and granulated using a pelletizer to prepare a resin composition (D-1).

(2) Production of film Ethylene-vinyl acetate copolymer (“Evertate H2021F” manufactured by Sumitomo Chemical Co., Ltd.) as the resin composition for the layer [I], content of monomer units derived from ethylene = 85% by weight, MFR (190 ° C., load 21.18 N) = 2 g / 10 min, durometer A hardness = 92), and ethylene-α-olefin copolymer (Sumitomo Chemical Co., Ltd.) as the resin composition for layer [II] Resin as a resin composition for layer [III] using “Excellen FX CX2001”, MFR (190 ° C.) = 2 g / 10 min, density = 898 kg / m ³ , Cx = 0.25, no long chain branching) One layer [I] extruder and one layer [II] each equipped with a 5-layer sheet processing machine manufactured by Tanabe Plastics Machine Co., Ltd., using the composition (E-1) Extruder, and one layer [ III] is supplied to an extruder and processed at an extruder cylinder temperature of 230 ° C. and a die temperature of 230 ° C., so that the layer composition order is layer [I] / layer [II] / layer [III] / layer [II]. / Layer [I], and the thickness composition ratio is 9% / 16% / 50% / 16% / layer [I] / layer [II] / layer [III] / layer [II] / layer [I] in this order. A laminate having a thickness of 9% and a total thickness of 160 μm was produced. From this laminate, a test piece of laminate take-up direction (vertical) × laminate width direction (horizontal) = 92 mm × 92 mm was sampled and stretched under the stretching conditions shown below to obtain a biaxially stretched film having a total thickness of 16 μm. Obtained.
<Extension conditions>
Stretching machine: Desktop biaxial stretching machine manufactured by Toyo Seiki Co., Ltd. Preheating temperature: 90 ° C
Stretching temperature: 90 ° C
Preheating time: 3 minutes Stretch ratio: Vertical × Horizontal = 3.3 times × 3.3 times Stretching speed: 5 m / min Various characteristic values of the obtained film are shown in Table 2.

<Example 2>
Ratio of crystalline propylene-ethylene random copolymer (“Nobrene FS2011DG2” manufactured by Sumitomo Chemical Co., Ltd.) and amorphous or low crystalline α-olefin polymer (C) as the resin composition for layer [III] Was carried out in the same manner as in Example 1 except that the content was changed to 50% by weight and 50% by weight. Various characteristic values of the obtained film are shown in Table 2.

<Comparative Example 1>
Both layer [I] and layer [II] were performed in the same manner as in Example 1 except that an ethylene-vinyl acetate copolymer (“Ebate H2021F” manufactured by Sumitomo Chemical Co., Ltd.) was used as the resin composition. Various characteristic values of the obtained film are shown in Table 2.

<Comparative example 2>
As the resin composition for the layer [III], 80% by weight of a crystalline propylene-ethylene random copolymer (“Nobrene FS2011DG2” manufactured by Sumitomo Chemical Co., Ltd.) and an amorphous or low crystalline α-olefin polymer ( C) “Ubetak UT2780” manufactured by Ube Lexen Co., Ltd., content of monomer unit derived from ethylene = 0 mol%, molecular weight distribution = 6.1, heat of crystal melting measured by DSC is 8.6 J / g ) Except for using 20% by weight of a resin composition (E-2) prepared by melting and kneading at 220 ° C. with a Banbury kneader, passing through a pressure roll to form a sheet, and further granulating using a pelletizer. The same operation as in Example 1 was performed. Various characteristic values of the obtained film are shown in Table 2.

It is a side view of the apparatus which measures the puncture strength of a film.

Explanation of symbols

1 Circular Sample Film 2 Film Fixing Jig 3 Pin 4 Load Cell 5 Indentation Depth

Claims (8)

A laminate comprising at least one of the following layers [I], [II] and [III], and comprising at least three layers.
Layer [I]: Copolymer of ethylene and ethylenically unsaturated ester, copolymer of ethylene and unsaturated carboxylic acid, copolymer of ethylene and unsaturated carboxylic anhydride, ethylene and unsaturated carboxylic acid At least one ethylene copolymer (A) selected from the group consisting of metal salts of copolymers with anhydrides
Layer [II]: ethylene-α-olefin copolymer (B)
Layer [III]: 1 to 99% by weight of an amorphous or low crystalline α-olefin polymer (C) satisfying the following requirements (c1), (c2) and (c3), and a crystalline propylene polymer ( D) Resin composition (E) containing 99 to 1% by weight (provided that the whole resin composition (E) is 100% by weight)
(C1) The content of monomer units derived from ethylene is 60 mol% or less (provided that the entire polymer is 100 mol%).
(C2) The molecular weight distribution is 3 or less.
(C3) The crystal melting heat quantity obtained by measuring in the range of −50 ° C. to 200 ° C. by differential scanning calorimetry (DSC) is 30 J / g or less. The laminate according to claim 1, wherein the ethylene-α-olefin copolymer (B) satisfies the following requirements (b1) and (b2).
(B1) The melt flow rate is 0.5 to 30 g / 10 minutes.
(B2) The density is 870 to 910 kg / m ³ .   The melting peak having a crystal heat of fusion measured by differential scanning calorimetry (DSC) of the amorphous or low-crystalline α-olefin polymer (C) according to claim 1, and a heat of crystallization. The laminate according to claim 1 or 2, which is a polymer in which no crystallization peak of 1 J / g or more is observed in the range of -100 to 200 ° C.   The laminated body according to any one of claims 1 to 3, wherein the amorphous or low-crystalline α-olefin polymer (C) according to claim 1 has an intrinsic viscosity of 0.1 to 10 dl / g.   The layer [I], the layer [II] and the layer [III] according to claim 1 are adjacent to each other and are laminated in the order of layer [I] / layer [II] / layer [III]. The laminated body in any one of 1-4.   The stretched film or stretched sheet formed by extending | stretching the laminated body in any one of Claims 1-5.   The stretched film or stretched sheet according to claim 6 having heat shrinkability. It is an object for food packaging, The laminated body in any one of Claims 1-5, and the stretched film or stretched sheet of Claim 6 or 7.

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