CN102712186B - Multilayer blow-molded container, and process for production thereof - Google Patents
Multilayer blow-molded container, and process for production thereof Download PDFInfo
- Publication number
- CN102712186B CN102712186B CN201180006278.4A CN201180006278A CN102712186B CN 102712186 B CN102712186 B CN 102712186B CN 201180006278 A CN201180006278 A CN 201180006278A CN 102712186 B CN102712186 B CN 102712186B
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- China
- Prior art keywords
- alpha
- ethene
- olefin
- olefin copolymer
- copolymer
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- 238000000034 method Methods 0.000 title claims description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 46
- 239000004711 α-olefin Substances 0.000 claims abstract description 209
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 204
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 204
- 239000000203 mixture Substances 0.000 claims abstract description 177
- 229920005989 resin Polymers 0.000 claims abstract description 169
- 239000011347 resin Substances 0.000 claims abstract description 169
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 154
- 229920000098 polyolefin Polymers 0.000 claims abstract description 126
- 238000002844 melting Methods 0.000 claims abstract description 105
- 230000008018 melting Effects 0.000 claims abstract description 105
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229920001577 copolymer Polymers 0.000 claims abstract description 42
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 146
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 claims description 59
- 229920000642 polymer Polymers 0.000 claims description 52
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- -1 aromatic phosphonic acid ester compound Chemical class 0.000 claims description 36
- 238000000071 blow moulding Methods 0.000 claims description 35
- 238000000465 moulding Methods 0.000 claims description 26
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- 229920005789 ACRONAL® acrylic binder Polymers 0.000 claims description 20
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- 238000010103 injection stretch blow moulding Methods 0.000 claims description 9
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- 150000001875 compounds Chemical class 0.000 claims description 7
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- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
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- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 48
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- 239000000463 material Substances 0.000 description 36
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- 239000000155 melt Substances 0.000 description 31
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- 238000012360 testing method Methods 0.000 description 23
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000000996 additive effect Effects 0.000 description 15
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 14
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- 229910019142 PO4 Inorganic materials 0.000 description 10
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 9
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 8
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 229920001684 low density polyethylene Polymers 0.000 description 8
- 239000004702 low-density polyethylene Substances 0.000 description 8
- 229920006132 styrene block copolymer Polymers 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 6
- 241000790917 Dioxys <bee> Species 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 238000005422 blasting Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
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- 239000007788 liquid Substances 0.000 description 4
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- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 4
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- 239000006228 supernatant Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- WEPNJTDVIIKRIK-UHFFFAOYSA-N 2-methylhept-2-ene Chemical compound CCCCC=C(C)C WEPNJTDVIIKRIK-UHFFFAOYSA-N 0.000 description 3
- JTXUVHFRSRTSAT-UHFFFAOYSA-N 3,5,5-trimethylhex-1-ene Chemical compound C=CC(C)CC(C)(C)C JTXUVHFRSRTSAT-UHFFFAOYSA-N 0.000 description 3
- KNIRLWRQSSLZCZ-UHFFFAOYSA-N 3-ethyloct-3-ene Chemical compound CCCCC=C(CC)CC KNIRLWRQSSLZCZ-UHFFFAOYSA-N 0.000 description 3
- BSJOLASGNWRVEH-UHFFFAOYSA-N 7,7-dimethyloct-1-ene Chemical compound CC(C)(C)CCCCC=C BSJOLASGNWRVEH-UHFFFAOYSA-N 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
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- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
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- ICGXPVHBUFIENI-UHFFFAOYSA-M lithium;1,3,7,9-tetratert-butyl-5-methyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Li+].CC1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ICGXPVHBUFIENI-UHFFFAOYSA-M 0.000 description 1
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- YWSUSMUSZKSAAQ-UHFFFAOYSA-M potassium;1,3,7,9-tetratert-butyl-5-methyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [K+].CC1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C YWSUSMUSZKSAAQ-UHFFFAOYSA-M 0.000 description 1
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- XEZJJVRUWKGVIA-UHFFFAOYSA-M sodium;1,3,7,9-tetraethyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].O1P([O-])(=O)OC2=C(CC)C=C(CC)C=C2CC2=CC(CC)=CC(CC)=C21 XEZJJVRUWKGVIA-UHFFFAOYSA-M 0.000 description 1
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- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 1
- IEFYQJPRHOKDLM-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-5-methyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].CC1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C IEFYQJPRHOKDLM-UHFFFAOYSA-M 0.000 description 1
- UXBYXHNQMORKEI-UHFFFAOYSA-M sodium;1,9-ditert-butyl-3,7-diethyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(CC)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(CC)C=C2C(C)(C)C UXBYXHNQMORKEI-UHFFFAOYSA-M 0.000 description 1
- FIAYJSUZUBQZOW-UHFFFAOYSA-M sodium;1,9-ditert-butyl-3,7-dimethyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C)C=C2C(C)(C)C FIAYJSUZUBQZOW-UHFFFAOYSA-M 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Classifications
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- B32—LAYERED PRODUCTS
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- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3032—Preforms or parisons made of several components having components being injected
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/04—Extrusion blow-moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/06—Injection blow-moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/406—Bright, glossy, shiny surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Medicinal Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
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- Containers Having Bodies Formed In One Piece (AREA)
- Laminated Bodies (AREA)
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Abstract
Disclosed is a multilayer blow-molded container having high gloss, excellent surface appearance and excellent impact resistance. The multilayer blow-molded container is characterized in that a resin to be used for the outermost layer comprises an olefin polymer composition (E) comprising a propylene resin (A), an ethylene-alpha-olefin copolymer (B) and a nucleating agent (D), the propylene resin (A) comprises a copolymer of propylene and an alpha-olefin (A-1) and has a crystal melting point of 140 to 155 DEG C (A-2), the ethylene-alpha-olefin copolymer (B) comprises a copolymer of ethylene and at least one alpha-olefin having 4 to 20 carbon atoms (B-1) and has a crystal melting point of not lower than 85 DEG C and lower than 110 DEG C (B-2), and the olefin polymer composition (E) has an MFR value of 5 to 10 g/10 min (E-1).
Description
Technical field
The present invention relates to multilayered blow container and manufacture method thereof.
Background technology
As the raw material of the blow molded articles such as blow-molded container, for example, can use according to purposes the resins such as vinyl chloride resin, polycarbonate resin, vinyl resins, propylene resin.
Among these resins, in the time using the vinyl resins of the such hard of high density polyethylene (HDPE), the problem of glossy variation, in the time using the such soft vinyl resins of low density polyethylene (LDPE), has the problem that rigidity is low.
In addition, in the time using vinyl chloride resin, although excellent on gloss, there is environmental problem, in the time using polycarbonate resin, although very excellent on gloss, there are the problems such as manufacturing cost rising.
On the other hand, in the time using propylene resin, the blow molded article obtaining because manufacturing cost is relatively cheap, than high density polyethylene (HDPE) excellence, therefore extensively uses as the container of liquid lotion, cosmetics, food, medicine etc. in gloss, the transparency.
The gloss of blow molded article is to need the market demands of good appearance and studied physical property all the time in order to tackle, but not yet proposes to meet the blow molded article of sufficient gloss, good mouldability and resistance to impact simultaneously.
As the blow molded article of gloss excellence, a kind of multi-layer blow molding body has been proposed, wherein, using propylene-alpha-olefin copolymers as substrate resin, using crystalline melting point be 110～125 DEG C LLDPE as coordinate resin, using the olefin polymer compositions that contains these resins and nucleator as outermost layer (for example,, with reference to patent documentation 1).But the present inventor studies discovery, even the multi-layer blow molding body of recording in patent documentation 1, gloss and resistance to impact are also still insufficient, also need further improvement.
As the multi-layer bottle of resistance to cold excellence, the sandwich layer of barrier properties for gases resin, the multi-layer bottle (for example,, with reference to patent documentation 2) that outermost layer is formed by polyolefin resin and straight chain shape ultra-low density polyethylene resin are proposed to have.But the present inventor studies discovery, even the multi-layer bottle of recording in patent documentation 2, gloss and mouldability are also still insufficient, also need further improvement.
As thering is excellent gloss, prima facie by the multilayer plastic container with label that in mould, (In-mold) mode is manufactured, propose to use as outermost layer resin used the container (for example,, with reference to patent documentation 3) that comprises the polypropylene random copolymer resin that contains ethene composition, polyvinyl resin, nucleator, ethene-alpha-olefin copolymer resin.But the present inventor studies discovery, the multilayer plastic container of recording in patent documentation 3, resistance to impact is still insufficient, need to further improve.
As the high glaze blow-molded container of the gloss excellence of container outer surface, known outermost layer uses and comprises the polypropylene-based resin that uses metallocene catalyst and obtain and use metallocene catalyst and the composition of the ethene-alpha-olefin copolymer that obtains, by the high glaze blow-molded container (for example,, with reference to patent documentation 4) of multi-layer blow molding method moulding.But the present inventor studies discovery, in patent documentation 4 record high glaze blow-molded container, although compared with existing container gloss excellence, have further room for improvement at the aspect such as heat resistance, gloss.
Prior art document
Patent documentation
Patent documentation 1: No. 3106834 communique of Japan Patent
Patent documentation 2: Japanese kokai publication hei 6-72424 communique
Patent documentation 3: Japanese kokai publication hei 7-304123 communique
Patent documentation 4: TOHKEMY 2003-137928 communique
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide the balanced also excellent multilayered blow container of a kind of high glaze, appearance excellence and resistance to impact excellence and resistance to impact and resistance to being clamminess property.
For solving the method for problem
The present inventor has carried out repeatedly deep research in order to complete above-mentioned problem, found that, the multilayered blow container that outermost layer uses specific olefin polymer compositions to obtain, high glaze, appearance excellence, and resistance to impact excellence, and resistance to impact and resistance to being clamminess property is balanced also excellent, thus complete the present invention.
, multilayered blow container of the present invention is characterised in that, the resin that outermost layer uses comprises olefin polymer compositions (E), this olefin polymer compositions (E) contains propylene resin (A) 80～98 weight portions, ethene-alpha-olefin copolymer (B) 2～20 weight portions (wherein, (A) and (B) add up to 100 weight portions) and nucleator (D) 0.01～0.5 weight portion, aforesaid propylene resinoid (A) meets following condition (A-1) and (A-2), above-mentioned ethene-alpha-olefin copolymer (B) meets following condition (B-1) and (B-2), above-mentioned olefin polymer compositions (E) meets following condition (E-1).
(A-1) be propylene and the copolymer of more than a kind that is selected from the alpha-olefin that ethene and carbon number are 4～20 alkene.
(A-2), according to JIS-K7121, the crystalline melting point recording taking differential scanning calorimetry (DSC) (DSC) is the scope of 140～155 DEG C.
(B-1) be the copolymer of ethene and the a kind of carbon number above alpha-olefin that is 4～20.
(B-2), according to JIS-K7121, the crystalline melting point recording taking DSC is as more than 85 DEG C and be less than the scope of 110 DEG C.
(E-1) according to ASTM D-1238, to measure melt flow rate (MFR) (MFR) that 230 DEG C of temperature, 2.16kg load measuring obtain as the scope of 5～10g/10 minute.
From the viewpoint of the low temperature resistance to impact of multilayered blow container, preferred above-mentioned polymerization of olefines compositions (E) also contains low density ethylene-alpha olefin copolymer (F) 0.1～20 weight portion, above-mentioned low density ethylene-alpha olefin copolymer (F) meets following condition (F-1) and (F-2), the density (d that above-mentioned ethene-alpha-olefin copolymer (B) records with density gradient column method
b[g/cm
3]) and the density (d that records with density gradient column method of low density ethylene-alpha olefin copolymer (F)
f[g/cm
3]) meet following condition (X-1).
(F-1) be the copolymer of ethene and the a kind of carbon number above alpha-olefin that is 3～20.
(F-2) according to JIS-K7121, the crystalline melting point recording taking DSC is as below 89 DEG C, or do not observe the peak based on crystalline melting point.
（X－1）d
B[g/cm
3]＞d
F[g/cm
3]，0.010[g/cm
3]≤（d
B－d
F）[g/cm
3]≤0.050[g/cm
3]。
Preferred above-mentioned ethene-alpha-olefin copolymer (B) also meets following condition (B-4).
(B-4) density recording taking density gradient column method is 0.880～0.910g/cm
3scope.
From the viewpoint of the low temperature resistance to impact of multilayered blow container, preferred above-mentioned ethene-alpha-olefin copolymer (B) also meets following condition (B-4a), and above-mentioned low density ethylene-alpha olefin copolymer (F) also meets following condition (F-3).
(B-4a) density (d recording with density gradient column method
b[g/cm
3]) be 0.890～0.910g/cm
3scope.
(F-3) density (d recording with density gradient column method
f[g/cm
3]) be 0.865～0.900g/cm
3scope.
Preferably aforesaid propylene resinoid (A) also meets following condition (A-4).
(A-4) Mw/Mn recording by GPC is more than 4.0.
Preferably aforesaid propylene resinoid (A) also meets following condition (A-3).
(A-3) according to ASTM D-1238, to measure MFR that 230 DEG C of temperature, 2.16kg load measuring obtain as the scope of 5～10g/10 minute.
Preferred above-mentioned ethene-alpha-olefin copolymer (B) also meets following condition (B-5).
(B-5) Mw/Mn recording by GPC is 1.2～3.0.
Preferred above-mentioned ethene-alpha-olefin copolymer (B) also meets following condition (B-3).
(B-3) according to ASTM D-1238, to measure MFR that 230 DEG C of temperature, 2.16kg load measuring obtain as the scope of 5～10g/10 minute.
Preferred above-mentioned nucleator (D) is for being selected from a kind of above compound in aromatic phosphonic acid ester compound, carboxylic metallic salt nucleator, polymer nucleator, sorbose alcohols nucleator and inorganic compound nucleator.
Preferably aforesaid propylene resinoid (A) is 95.5～98 weight portions, and above-mentioned ethene-alpha-olefin copolymer (B) is 2～4.5 weight portions (wherein, (A) and (B) add up to 100 weight portions).
Multilayered blow container as described in any one in claim 1～10, is characterized in that, above-mentioned multilayered blow container has at least one internal layer, and this internal layer is formed by acronal (G) or polyvinyls (H).
Preferred above-mentioned multilayered blow container obtains by direct blow molding method or the moulding of injection stretch blow molding method.
Multilayered blow container of the present invention is characterised in that, use above-mentioned olefin polymer compositions (E) and olefin polymer compositions (E) thermoplastic resin composition in addition, form outermost layer with above-mentioned olefin polymer compositions (E), above-mentioned olefin polymer compositions (E) thermoplastic resin composition in addition forms the mode of at least one internal layer, by direct blow molding method or the moulding of injection stretch blow molding method.
The effect of invention
According to the present invention, can provide high glaze, appearance excellence and resistance to impact excellence and the resistance to impact balanced also excellent multilayered blow container with resistance to being clamminess property.
Detailed description of the invention
Then, specifically describe the present invention.
[multilayered blow container]
Multilayered blow container of the present invention is characterised in that, the resin that outermost layer uses comprises olefin polymer compositions (E), and this olefin polymer compositions (E) contains propylene resin (A), ethene-alpha-olefin copolymer (B) and nucleator (D).
Multilayered blow container of the present invention, high glaze, appearance excellence, and resistance to impact excellence, also contain in the mode of low density ethylene-alpha olefin copolymer (F) 0.1～20 weight portion at olefin polymer compositions (E), and low temperature resistance to impact is also excellent.
< propylene resin (A) >
The propylene resin (A) using in the present invention meets following condition (A-1) and (A-2), preferably further meets at least one in following condition (A-3), (A-4), more preferably meets following condition (A-3) and (A-4).Propylene resin (A) can use separately one, also can use two or more.
(A-1) be propylene and the copolymer of more than a kind that is selected from the alpha-olefin that ethene and carbon number are 4～20 alkene.Wherein, the alpha-olefin that is 4～20 as carbon number, can enumerate 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-laurylene, 1-hexadecylene, 4-methyl-1-pentene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 3-methyl-1-butene, 3, 3-dimethyl-1-butylene, diethyl-1-butylene, trimethyl-1-butylene, 3-Methyl-1-pentene, ethyl-1-amylene, propyl group-1-amylene, dimethyl-1-amylene, the first and second bases-1-amylene, diethyl-1-hexene, trimethyl-1-amylene, 3-methyl isophthalic acid-hexene, dimethyl-1-hexene, 3, 5, 5-trimethyl-1-hexene, the first and second bases-1-heptene, trimethyl-1-heptene, ethyl-1-octene, methyl isophthalic acid-nonene etc.
As the propylene resin using in the present invention (A), balanced from the viewpoint of physical property, economy, be preferably the copolymer of the propylene alkene above with being selected from the alpha-olefin that ethene and carbon number are 4～10 a kind, more preferably propylene and the copolymer that is selected from ethene and 1-butylene a kind above alpha-olefin, is particularly preferably the copolymer of propylene and ethene.
In addition, the propylene resin (A) using in the present invention is preferably random copolymer.
(A-2), according to JIS-K7121, the crystalline melting point recording taking differential scanning calorimetry (DSC) (DSC) is the scope of 140～155 DEG C.If crystalline melting point is in above-mentioned scope, the gloss of multilayered blow container and resistance to impact excellence, manufactures mouldability when multilayered blow container also excellent, so preferably.According to JIS-K7121, with differential scanning calorimetry (DSC) (DSC) if the crystalline melting point recording higher than 155 DEG C, the poor impact resistance of multilayered blow container.In addition, according to JIS-K7121, with differential scanning calorimetry (DSC) (DSC) if the crystalline melting point recording lower than 140 DEG C, the insufficient formability while manufacturing multilayered blow container, produces and is clamminess on the surface of multilayered blow container.
The crystalline melting point of aforesaid propylene resinoid (A) can, by according to JIS-K7121, use differential scanning calorimetry (DSC) (DSC) (for example, the Diamond DSC processed of PerkinElmer company) to measure and try to achieve with following condition determination.Wherein, the summit of endothermic peak when measuring with following condition determination, in the 3rd step is defined as crystalline melting point (Tm).Endothermic peak has when multiple, and the endothermic peak summit of the height maximum at peak is defined as to crystalline melting point (Tm).
(condition determination)
Measure environment: nitrogen atmosphere
Sample size: 5mg
Sample shape: (230 DEG C of moulding, thickness 200～400 μ m) for press mold
The 1st step: be warmed up to 240 DEG C from 30 DEG C with 10 DEG C/min, keep 10min.
The 2nd step: cool to 60 DEG C with 10 DEG C/min.
The 3rd step: be warmed up to 240 DEG C with 10 DEG C/min.
The crystalline melting point that aforesaid propylene resinoid (A) records with differential scanning calorimetry (DSC) (DSC) according to JIS-K7121, for example, can adjust by the importing ratio that is selected from the alpha-olefin that ethene and carbon number are 4～20 a kind alkene above that changes in the manufacture of propylene resin (A) propylene and importing when copolymerization.; by increasing with respect to the import volume import volume of propylene, that be selected from a kind of above alkene in the alpha-olefin that ethene and carbon number are 4～20; can reduce the crystalline melting point recording with differential scanning calorimetry (DSC) (DSC) according to JIS-K7121; by reducing with respect to the import volume import volume of propylene, that be selected from a kind of above alkene in the alpha-olefin that ethene and carbon number are 4～20, can improve the crystalline melting point recording with differential scanning calorimetry (DSC) (DSC) according to JIS-K7121.
(A-3) according to ASTM D-1238, to measure MFR that 230 DEG C of temperature, 2.16kg load measuring obtain as the scope of 5～10g/10 minute.Wherein, MFR refers to the meaning of melt flow rate (MFR).If MFR is in above-mentioned scope, the mobility of the olefin polymer compositions (E) when moulding is the scope that is suitable for moulding of the present invention, the uneven thickness of the olefin polymer compositions (E) of multilayer can be prevented in blow molding, also excellent multilayered blow container of flatness excellence and then gloss can be manufactured.According to ASTM D-1238, if the MFR obtaining with 230 DEG C of temperature of mensuration, 2.16kg load measuring is greater than 10g/10 minute, mouldability while sometimes manufacturing multilayered blow container and the poor impact resistance of multilayered blow container, according to ASTM D-1238, if the MFR obtaining with 230 DEG C of temperature of mensuration, 2.16kg load measuring is less than 5g/10 minute, the glossiness of multilayered blow container is poor sometimes.
The MFR that aforesaid propylene resinoid (A) obtains according to ASTM D-1238, to measure 230 DEG C of temperature, 2.16kg load measuring, for example, can for example, be adjusted by the import volume of the chain-transferring agent (hydrogen) using when the copolymerization in the manufacture of propylene resin (A).; for example, by increasing import volume amount, chain-transferring agent (hydrogen) of the propylene that imports during with respect to the polymerization alkene above with being selected from the alpha-olefin that ethene and carbon number are 4～20 a kind, can improve the MFR that propylene resin (A) obtains to measure 230 DEG C of temperature, 2.16kg load measuring according to ASTM D-1238.In addition, for example, by reducing import volume amount, chain-transferring agent (hydrogen) of the propylene that imports during with respect to the polymerization alkene above with being selected from the alpha-olefin that ethene and carbon number are 4～20 a kind, can reduce the MFR that propylene resin (A) obtains to measure 230 DEG C of temperature, 2.16kg load measuring according to ASTM D-1238.
In addition, under the existence of the radical initiators such as organic peroxide, carry out melting mixing processing by the propylene resin that polymerization is obtained, also can adjust the MFR obtaining with 230 DEG C of temperature of mensuration, 2.16kg load measuring according to ASTM D-1238.For example, under existing at organic peroxide, carry out melting mixing processing, according to ASTM D-1238, increase to measure the MFR that 230 DEG C of temperature, 2.16kg load measuring obtain.In addition, by increasing the addition of organic peroxide, can further improve the MFR obtaining according to ASTM D-1238, to measure 230 DEG C of temperature, 2.16kg load measuring.
(A-4) Mw/Mn recording by GPC is more than 4.0.Wherein, GPC is the meaning of gel permeation chromatography, and Mw is the meaning of weight average molecular weight, and Mn is the meaning of number-average molecular weight, and Mw/Mn is the index of molecular weight distribution.As propylene resin (A), Mw/Mn is preferably more than 1.5, more preferably more than 3.0, if but meet above-mentioned (A-4), that is, if Mw/Mn is more than 4.0, can obtain the blow molded article of gloss excellence owing to not being subject to the surface roughness affect of blow mold, so particularly preferably.Although its reason is still not clear, the present inventor considers as follows.,, if Mw/Mn is more than 4.0,, compared with being less than the situation of this scope, there is more part and the more low-molecular-weight part of HMW.Can think resin flows distortion when the existence of the part of HMW more reduces blow molding, the existence of more low-molecular-weight part is accelerated to solidify.Therefore, the present inventor infers, if use the composition of the scope of above-mentioned Mw/Mn as (A) composition, no matter use the mould that surface roughness is large still to use the mould that surface roughness is little, the multilayered blow container obtaining can roller mould surface roughness, and form good gloss.In addition, be not particularly limited as the upper limit of Mw/Mn, but be generally 50.0 from the viewpoint of productivity ratio, be preferably 30.0, more preferably 20.0, be more preferably 16.0, be particularly preferably 12.0, most preferably be 8.0.Wherein, measuring Mw/Mn by GPC can carry out with the method for recording in embodiment.
The Mw/Mn that aforesaid propylene resinoid (A) records by GPC, for example, the kind of the catalyst of using when manufacture that can be by propylene resin (A) is adjusted.For example, can, by using Ziegler-Natta catalyst, preferably use solid titanium catalyst as catalyst, be met the propylene resin (A) of above-mentioned condition (A-4).In addition, as other the example of method of adjusting Mw/Mn, there is the method for the propylene resin of more than two kinds that combined molecular weight is different.Particularly, from forming the viewpoint of part of above-mentioned more HMW, solid titanium catalyst is favourable.
In addition, as propylene resin (A), will be by
13that C-NMR calculates, from the construction unit of propylene be that the total of the construction unit of the above alkene of in 4～20 alpha-olefin a kind is while being made as 100 % by weight from being selected from ethene and carbon number, be generally the scope of 80～99 % by weight from the weight of the construction unit of propylene, be preferably the scope of 90～99 % by weight.In addition, be the scope that the weight of the construction unit of a kind of above alkene in 4～20 alpha-olefin is generally 1～20 % by weight from being selected from ethene and carbon number, be preferably the scope of 1～10 % by weight.In above-mentioned scope time, manufacture physical property balanced good of the being clamminess property etc. of mouldability when multilayered blow container and multilayered blow container, so preferred.
Will be by
13c-NMR calculate from the construction unit of propylene be the total of the construction unit of the above alkene of in 4～20 alpha-olefin a kind while being made as 100 % by weight from being selected from ethene and carbon number, measure, calculate with following condition from the weight of the construction unit of propylene.
(
13c-NMR condition determination)
Determinator: NEC's LA400 type processed nuclear magnetic resonance device
Mode determination: BCM(Bilevel Complete decoupling)
Observing frequency: 100.4MHz
Observation scope: 17006.8Hz
Pulse width: 45 ° of C cores (7.8 μ second)
Pulse-recurrence time: 5 seconds
Coupon:
Coupon rotating speed: 12Hz
The tired number of times of calculating: 20000 times
Measure temperature: 125 DEG C
Solvent: 1,2,4-trichloro-benzenes: 0.35ml/ heavy benzol: 0.2ml
Sample size: about 40mg
(from the calculating of the weight of the construction unit of propylene)
While being selected from ethene and carbon number and being a kind of above alkene (being comonomer) in 4～20 alpha-olefin for ethene, according to following document (1), by from obtained
13c-NMR spectrogram is determined the distribute ratio of (two unit groups (2 cellular chain) distribution) of monomer chain, can calculate in propylene resin (A) mole fraction (mol%) (being designated as below E(mol%) from the construction unit of ethene) and from the mole fraction (mol%) (being designated as below P(mol%) of the construction unit of propylene).From obtained E(mol%) and P(mol%) be scaled % by weight, can calculate in propylene resin (A) from the % by weight of the construction unit of propylene with from the % by weight of the construction unit of ethene.
Document (1): Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T., Macromolecules 1982,15, (4), 1150-1152
In the time that to be selected from ethene and carbon number be more than a kind alkene (being comonomer) in 4～20 alpha-olefin for the carbon number alpha-olefin that is 4～20, according to following document (2), by from obtained
13c-NMR spectrogram is determined the distribute ratio of (two unit groups (2 cellular chain) distribution) of monomer chain, thereby can calculate the mole fraction (mol%) (being designated as below A(mol%) of the construction unit of the alpha-olefin that is 4～20 from carbon number in propylene resin (A)) and from the mole fraction (mol%) (being designated as below P(mol%) of the construction unit of propylene).From the A(mol% trying to achieve) and P(mol%) be scaled % by weight, can calculate the % by weight of the construction unit from propylene in propylene resin (A) and the % by weight of the construction unit of the alpha-olefin that is 4～20 from carbon number.
Document (2): James C.Randall, Macromolecules, 1978,11,592-597
Adjustment from the weight of the construction unit of propylene can be made as amount arbitrarily by adjusting described later creating conditions.More specifically, by reducing in the manufacture of propylene resin (A) when the copolymerization with respect to the import volume import volume of propylene, that be selected from the more than a kind alkene in the alpha-olefin that ethene and carbon number are 4～20, can increase the weight from the construction unit of propylene.In addition, by increasing the import volume with respect to a kind of above alkene in the alpha-olefin import volume of propylene, that to be selected from from ethene and carbon number be 4～20, can reduce the weight from the construction unit of propylene.
In addition, preferably aforesaid propylene resinoid (A) is propylene and the random copolymer of more than a kind that is selected from the alpha-olefin that ethene and carbon number are 4～20 alkene.Aforesaid propylene resinoid (A) can be by under existing at Ziegler-Natta catalyst or metallocene catalyst, and the alkene that propylene is above with being selected from the alpha-olefin that ethene and carbon number are 4～20 a kind carries out copolymerization, preferably carry out random copolymerization obtains.As the catalyst using when the polymerization aforesaid propylene resinoid (A), if use Ziegler-Natta catalyst, preferably use solid titanium catalyst, can meet above-mentioned condition (A-4).In addition, by the different propylene resin of more than two kinds (A) of combined molecular weight, also can be adjusted into satisfy condition (A-4).In addition, in the time of polymerization, also can import the chain-transferring agent taking hydrogen as representative.And, also the propylene resin being obtained by polymerization can be carried out to melting mixing processing under the radical initiator such as organic peroxide exists and obtain propylene resin (A).
As above-mentioned organic peroxide, although be not particularly limited, can illustrate benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide acetic acid butyl ester, tert-butylperoxy isopropyl carbonate, 2,5-dimethyl-2,5-bis-(benzoyl peroxide) hexane, 2,5-dimethyl-2,5-bis-(benzoyl peroxide) hexin-3, the diperoxy adipic acid tert-butyl ester, peroxidating-3,5, the 5-tri-methyl hexanoic acid tert-butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, cumyl peroxide, 2,5-dimethyl-2,5-bis-(tert-butyl peroxide) hexane, 2,5 ,-dimethyl-2,5-bis-(tert-butyl peroxide) hexin-3, two (tert-butyl peroxide isopropyl) benzene of 1,3-, tert-butyl hydroperoxide diisopropylbenzene (DIPB), two (tert-butyl peroxide)-3,3 of 1,1-, 5-trimethyl-cyclohexane, two (tert-butyl peroxide) cyclohexanes of 1,1-, two (tert-butyl peroxide) butane of 2,2-, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, hydrogen phosphide cumene, TBHP, p-Cymene hydroperoxide, 1,1,3,3-tetramethyl butyl hydroperoxide or 2,5-dimethyl-2, the organic peroxide of 5-bis-(hydrogen peroxide) hexane etc.In addition, among them, more preferably 2,5-dimethyl-2,5-bis-(benzoyl peroxide) hexane, 1, two (tert-butyl peroxide isopropyl) benzene of 3-.While using organic peroxide, wish to use below 0.1 weight portion with respect to propylene resin 100 weight portions that obtained by polymerization.Melting mixing processing can be listed below method: in propylene resin, add after above-mentioned organic peroxide, drop in the mixers such as Henschel mixer, Banbury, rotary drum mixer and mix, then, the mixture obtaining, by extruder moulding such as single screw extrusion machine, double screw extruders, is obtained to the line material of propylene resin (A).Wherein, above-mentioned line material is conventionally carrying out before blow molding, uses comminutor etc. to make pellet shape.
< ethene-alpha-olefin copolymer (B) >
The ethene-alpha-olefin copolymer (B) using in the present invention meets following condition (B-1) and (B-2), preferably also meets at least one in following condition (B-3), (B-4), more preferably meets following condition (B-3) and (B-4).In addition, also preferably meet following condition (B-5).Ethene-alpha-olefin copolymer (B) can use separately one, also can use two or more.
(B-1) be the copolymer of ethene and the a kind of carbon number above alpha-olefin that is 4～20.Wherein, the alpha-olefin that is 4～20 as carbon number, can enumerate 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-laurylene, 1-hexadecylene, 4-methyl-1-pentene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 3-methyl-1-butene, 3, 3-dimethyl-1-butylene, diethyl-1-butylene, trimethyl-1-butylene, 3-Methyl-1-pentene, ethyl-1-amylene, propyl group-1-amylene, dimethyl-1-amylene, the first and second bases-1-amylene, diethyl-1-hexene, trimethyl-1-amylene, 3-methyl isophthalic acid-hexene, dimethyl-1-hexene, 3, 5, 5-trimethyl-1-hexene, the first and second bases-1-heptene, trimethyl-1-heptene, ethyl-1-octene, methyl isophthalic acid-nonene etc.
As the ethene-alpha-olefin copolymer using in the present invention (B), from the balanced viewpoint of physical property and economy, be preferably ethene and be selected from the copolymer that carbon number is the above alkene of in 4～10 alpha-olefin a kind, more preferably ethene and the copolymer that is selected from 1-butylene, 1-hexene and 1-octene a kind above alpha-olefin, is particularly preferably the copolymer of ethene and 1-hexene.
(B-2) crystalline melting point recording taking DSC according to JIS-K7121 is as more than 85 DEG C and lower than the scope of 110 DEG C.If crystalline melting point is in above-mentioned scope, the resistance to impact of multilayered blow container, outermost layer and other layers is excellent in adhesion, so preferably.The crystalline melting point that ethene-alpha-olefin copolymer (B) records taking DSC according to JIS-K7121 is when more than 110 DEG C, cementability and poor impact resistance, the crystalline melting point recording with DSC according to JIS-K7121 is during lower than 85 DEG C, and cementability is poor, and produce be clamminess, so not preferred.In addition, from the balanced viewpoint of resistance to impact, cementability and being clamminess property, crystalline melting point is preferably below 109 DEG C, more preferably, below 108 DEG C, is particularly preferably below 105 DEG C.
The crystalline melting point that the ethene-alpha-olefin copolymer (B) using in the present invention records with DSC according to JIS-K7121 can be made as amount arbitrarily by adjusting creating conditions of ethene-alpha-olefin copolymer.
More specifically, in the polymerization of ethene-alpha-olefin copolymer (B), the ratio of feeding quantity that can be by changing ethene when polymerizing ethylene-alpha olefin copolymer and alpha-olefin is adjusted.Particularly, the feeding quantity by increase with respect to the alpha-olefin of the feeding quantity of ethene, can reduce the crystalline melting point recording with DSC according to JIS-K7121.In addition, the feeding quantity by minimizing with respect to the alpha-olefin of the feeding quantity of ethene, can improve the crystalline melting point recording with DSC according to JIS-K7121.
The crystalline melting point of above-mentioned ethene-alpha-olefin copolymer (B) can use differential scanning calorimetry (DSC) (DSC) to measure according to JIS-K7121.Particularly, can be measured by the method same with the crystalline melting point of above-mentioned propylene resin (A).
(B-3) according to ASTM D-1238, to measure MFR that 230 DEG C of temperature, 2.16kg load measuring obtain as the scope of 5～10g/10 minute.If MFR in above-mentioned scope, the favorable dispersibility of ethene-alpha-olefin copolymer (B) to propylene resin (A), the glossiness of multilayered blow container, resistance to impact excellence, outermost layer and other layers excellent in adhesion, so preferably.
In addition, ethene-alpha-olefin copolymer (B) is according to ASTM D-1238, to measure the adjustment of the MFR that 230 DEG C of temperature, 2.16kg load measuring obtain, can be made as value arbitrarily by adjusting creating conditions of ethene-alpha-olefin copolymer (B).
More specifically, in the polymerization of ethene-alpha-olefin copolymer described later (B), the feeding quantity of hydrogen of feeding quantity that can be by adjusting ethene during with respect to polymerization and/or alpha-olefin is controlled.By increasing the feeding quantity of hydrogen of feeding quantity of the ethylene gas during with respect to polymerization, or in the time adding ethene and alpha-olefin, increase the feeding quantity with respect to the hydrogen of the feeding quantity of ethene and alpha-olefin, can improve the MFR obtaining according to ASTM D-1238, to measure 230 DEG C of temperature, 2.16kg load measuring.Feeding quantity by minimizing with respect to the hydrogen of the feeding quantity of ethylene gas, or in the time adding ethene and alpha-olefin, reduce the feeding quantity with respect to the hydrogen of the feeding quantity of ethene and alpha-olefin, can reduce the MFR obtaining according to ASTM D-1238, to measure 230 DEG C of temperature, 2.16kg load measuring.
(B-4) density recording taking density gradient column method is 0.880～0.910g/cm
3scope.If density is in above-mentioned scope, the gloss of multilayered blow container and resistance to impact, outermost layer and other layers is excellent in adhesion, so preferably.
In addition, in the time that multilayered blow container of the present invention is used for needing the purposes of low temperature resistance to impact, preferably use low density ethylene-alpha olefin copolymer described later (F), and ethene-alpha-olefin copolymer (B) meets following condition (B-4a).
(B-4a) density (d recording with density gradient column method
b[g/cm
3]) be 0.890～0.910g/cm
3scope.If density is in above-mentioned scope, the gloss of multilayered blow container, resistance to impact, low temperature resistance to impact, outermost layer and other layers is excellent in adhesion, and being clamminess property is low, and the shock-resistant characteristic such as resistance to impact, low temperature resistance to impact and patience is balanced good, so preferably.
The density that the ethene-alpha-olefin copolymer (B) using in the present invention records with density gradient column method can be made as amount arbitrarily by adjusting creating conditions of ethene-alpha-olefin copolymer (B).
More specifically, in the polymerization of ethene-alpha-olefin copolymer described later (B), the ratio of feeding quantity that can be by changing ethene when polymerizing ethylene-alpha olefin copolymer and alpha-olefin is adjusted.Particularly, the feeding quantity by increase with respect to the alpha-olefin of the feeding quantity of ethene, can reduce the density recording with density gradient column method.In addition, the feeding quantity by minimizing with respect to the alpha-olefin of the feeding quantity of ethene, can improve the density recording with density gradient column method.
Wherein, the density that the ethene-alpha-olefin copolymer (B) using in the present invention records with density gradient column method is that the line material of the ethene-alpha-olefin copolymer (B) that obtains during by the mensuration of above-mentioned MFR was 120 DEG C of heat treatments 1 hour, with 1 hour linearly Slow cooling after room temperature, the measured value recording with density gradient column.
(B-5) Mw/Mn recording by GPC is 1.2～3.0.Wherein, as ethene-alpha-olefin copolymer (B), more preferably Mw/Mn is 1.5～3.0.If Mw/Mn is in above-mentioned scope, the gloss excellence of multilayered blow container of the present invention, so preferably.
The Mw/Mn that above-mentioned ethene-alpha-olefin copolymer (B) records by GPC, for example can be by ethene-alpha-olefin copolymer (B) manufacture time the catalyst that uses kind adjust.For example, as catalyst, by using metallocene catalyst, can be met the ethene-alpha-olefin copolymer (B) of above-mentioned condition (B-5).
In addition, above-mentioned ethene-alpha-olefin copolymer (B) can be by ethene, alpha-olefin copolymer are obtained, but ethene-alpha-olefin copolymer is preferably the copolymer that uses metallocene catalyst polymerisation to obtain.In addition, in the time of polymerization, also can import the chain-transferring agent taking hydrogen as representative.
If the ethene-alpha-olefin copolymer of the ethene-alpha-olefin copolymer using in the present invention (B) for using metallocene catalyst polymerisation to obtain, compared with the ethene-alpha-olefin copolymer obtaining with the so-called Ziegler-Natta catalyst polymerization of existing use, composition is evenly distributed, therefore with respect to the favorable dispersibility of propylene resin (A), can obtain the olefin polymer compositions that gloss is better (E).In addition, if the ethene-alpha-olefin copolymer that uses metallocene catalyst polymerisation to obtain,, compared with the ethene-alpha-olefin copolymer that uses Ziegler-Natta catalyst polymerization to obtain, molecular weight distribution also narrows, and reduces as the low molecular weight compositions of the main cause that resistance to impact is worsened.And, if the ethene-alpha-olefin copolymer that uses metallocene catalyst polymerisation to obtain,, compared with the ethene-alpha-olefin copolymer that uses Ziegler-Natta catalyst polymerization to obtain, the composition of copolymer distributes and also becomes evenly, also tails off as the amorphous component of the reason being clamminess.In addition, the bonding inequality between outermost layer and other layers also tails off, also can expect suppress through time outward appearance worsen.
From foregoing, the ethene-alpha-olefin copolymer (B) that uses metallocene catalyst to carry out polymerization to obtain by utilization, can obtain gloss excellence, and resistance to impact excellence, the olefin polymer compositions (E) that being clamminess property is low.
< low density ethylene-alpha olefin copolymer (F) >
In the time that multilayered blow container of the present invention needs low temperature resistance to impact, as olefin polymer compositions (E), preferably use the composition that also contains in addition low density ethylene-alpha olefin copolymer (F) at propylene resin (A), ethene-alpha-olefin copolymer (B) and nucleator (D) as mentioned above.
Above-mentioned low density ethylene-alpha olefin copolymer (F) meets following condition (F-1) and (F-2), preferably also meets following condition (F-3).Low density ethylene-alpha olefin copolymer (F) can use separately one, also can use two or more.
(F-1) be the copolymer of ethene and the a kind of carbon number above alpha-olefin that is 3～20.Wherein, the alpha-olefin that is 3～20 as carbon number, can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-laurylene, 1-hexadecylene, 4-methyl-1-pentene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 3-methyl-1-butene, 3, 3-dimethyl-1-butylene, diethyl-1-butylene, trimethyl-1-butylene, 3-Methyl-1-pentene, ethyl-1-amylene, propyl group-1-amylene, dimethyl-1-amylene, the first and second bases-1-amylene, diethyl-1-hexene, trimethyl-1-amylene, 3-methyl isophthalic acid-hexene, dimethyl-1-hexene, 3, 5, 5-trimethyl-1-hexene, the first and second bases-1-heptene, trimethyl-1-heptene, ethyl-1-octene, methyl isophthalic acid-nonene etc.
As above-mentioned low density ethylene-alpha olefin copolymer (F), from the balanced viewpoint of physical property and economy, be preferably ethene and be selected from the copolymer that carbon number is the above alkene of in 3～10 alpha-olefin a kind, more preferably the copolymer of the ethene alpha-olefin above with being selected from propylene, 1-butylene, 1-hexene and 1-octene a kind.As above-mentioned low density ethylene-alpha olefin copolymer (F), wherein, be preferably the copolymer of copolymer, ethene and the 1-octene of copolymer, ethene and the 1-butylene of ethene and propylene, the more preferably copolymer of the copolymer of ethene and 1-butylene, ethene and 1-octene, is particularly preferably the copolymer of ethene and 1-butylene.
(F-2) according to JIS-K7121, the crystalline melting point recording taking DSC is as below 89 DEG C, or do not observe the peak based on crystalline melting point.In the time thering is crystalline melting point, be preferably below 75 DEG C.If crystalline melting point is in above-mentioned scope, multilayered blow container is excellent in low temperature resistance to impact, so preferably.
The crystalline melting point of above-mentioned low density ethylene-alpha olefin copolymer (F) can use differential scanning calorimetry (DSC) (DSC) to measure according to JIS-K7121.Particularly, can measure with the method that embodiment described later was recorded.
(F-3) density (d recording with density gradient column method
f[g/cm
3]) be 0.865～0.900g/cm
3scope.More preferably 0.870～0.900g/cm of above-mentioned density
3scope.If density in above-mentioned scope, the gloss excellence of multilayered blow container, low temperature resistance to impact is excellent especially, so preferably.
In addition, the density (d that above-mentioned ethene-alpha-olefin copolymer (B) records with density gradient column method
b[g/cm
3]) and the density (d that records with density gradient column method of low density ethylene-alpha olefin copolymer (F)
f[g/cm
3]) meet following condition (X-1).
（X-1）d
B[g/cm
3]＞d
F[g/cm
3]，0.010[g/cm
3]≤（d
B-d
F）[g/cm
3]≤0.050[g/cm
3]。That is, the density of low density ethylene-alpha olefin copolymer (F) is less than the density of above-mentioned ethene-alpha-olefin copolymer (B), the density contrast (d of ethene-alpha-olefin copolymer (B) and low density ethylene-alpha olefin copolymer (F)
b-d
f) be 0.010～0.050[g/cm
3].In addition density contrast (d,
b-d
f) be preferably 0.010～0.040[g/cm
3].
If density contrast (d
b-d
f) in above-mentioned scope, the gloss excellence of multilayered blow container, and low temperature resistance to impact excellence, so preferably.
In addition, as low density ethylene-alpha olefin copolymer (F), preferably according to ASTM D-1238, to measure MFR that 230 DEG C of temperature, 2.16kg load measuring obtain as the scope of 0.1～50g/10 minute, the more preferably scope of 0.5～30g/10 minute, is particularly preferably the scope of 5～10g/10 minute.If MFR in above-mentioned scope, the favorable dispersibility of low density ethylene-alpha olefin copolymer (F), gloss, low-temperature impact improve.
In addition, above-mentioned low density ethylene-alpha olefin copolymer (F) can be by obtaining ethene and alpha-olefin copolymer, but ethene-alpha-olefin copolymer can be both the polymer that uses Ziegler-Natta catalyst polymerization to obtain, it can be also the polymer that uses metallocene catalyst polymerisation to obtain.
< nucleator (D) >
In the present invention, use nucleator (D).As nucleator (D), can enumerate the a kind of above compound being selected from aromatic phosphonic acid ester compound, carboxylic metallic salt nucleator, polymer nucleator, sorbose alcohols nucleator and inorganic compound nucleator.Nucleator (D) does not preferably make the foul smell of multilayered blow container worsen.Nucleator (D) can be used, or two or more may be used separately.
As above-mentioned aromatic phosphonic acid ester compound, be preferably with the compound shown in following formula [III] and/or [IV].
In above-mentioned formula [III], [IV], R
1that carbon number is 1～10 divalent alkyl, R
2and R
3be respectively that hydrogen atom or carbon number are 1～10 alkyl independently, M is the metallic atom of 1～3 valency, the integer that n is 1～3, and m is 1 or 2.
As the concrete example of the aromatic phosphonic acid ester compound shown in general formula [III], can enumerate 2,2'-methylene-bis-(4,6-di-tert-butyl-phenyl) phosphate sodium, 2,2'-ethylidene-bis-(4,6-di-tert-butyl-phenyl) phosphate sodium, 2,2'-methylene-bis-(4,6-di-tert-butyl-phenyl) phosphate lithium, 2,2'-ethylidene-bis-(4,6-di-tert-butyl-phenyl) phosphate lithium, 2,2'-ethylidene-bis-(4-isopropyl-6-tert-butyl-phenyl) phosphate sodium, 2,2'-methylene-bis-(4-methyl-6-tert butyl phenyl) phosphate lithium, 2,2'-methylene-bis-(4-ethyl-6-tert-butyl-phenyl) phosphate lithium, 2,2'-butylidene-bis-(4,6-3,5-dimethylphenyl) phosphate sodium, 2,2'-butylidene-bis-(4,6-di-tert-butyl-phenyl) phosphate sodium, the tertiary octyl group methylene of 2,2'--bis-(4,6-3,5-dimethylphenyl) phosphate sodium, the tertiary octyl group methylene of 2,2'--bis-(4,6-di-tert-butyl-phenyl) phosphate sodium, two (2,2'-methylene-bis-(4,6-di-tert-butyl-phenyl) phosphate) calcium, two [2,2'-methylene-bis-(4,6-di-tert-butyl-phenyl) phosphate] magnesium, two [2,2'-methylene-bis-(4,6-di-tert-butyl-phenyl) phosphate] barium, 2,2'-methylene-bis-(4-methyl-6-tert butyl phenyl) phosphate sodium, 2,2'-methylene-bis-(4-ethyl-6-tert-butyl-phenyl) phosphate sodium, 2,2'-ethylidene-bis-(butyl-6-tert-butyl-phenyl between 4-) phosphate sodium, 2,2'-methylene-bis-(4,6-3,5-dimethylphenyl) phosphate sodium, 2,2'-methylene-bis-(4,6-diethyl phenyl) phosphate sodium, 2,2'-ethylidene-bis-(4,6-di-tert-butyl-phenyl) phosphate potassium, two [2,2'-ethylidene-bis-(4,6-di-tert-butyl-phenyl) phosphate] calcium, two [2,2'-ethylidene-bis-(4,6-di-tert-butyl-phenyl) phosphate] magnesium, two [2,2'-ethylidene-bis-(4,6-di-tert-butyl-phenyl) phosphate] barium, three [2,2'-methylene-bis-(4,6-di-tert-butyl-phenyl) phosphate] aluminium, three [2,2'-ethylidene-bis-(4,6-di-tert-butyl-phenyl) phosphate] aluminium, with two or more mixture in them etc.
As aromatic phosphonic acid ester compound, also can use the hydroxy Al phosphate compound shown in general formula [IV], particularly preferably R
2and R
3be the compound shown in the general formula [V] of the tert-butyl group.
In formula [V], R
1be that carbon number is 1～10 divalent alkyl, m is 1 or 2.Particularly preferred aromatic phosphonic acid ester compound is the compound shown in general formula [VI].
In formula [VI], R
1methylene or ethylidene.As the compound shown in general formula [VI], particularly, be two [2,2-methylene-bis-(4,6-di-t-butyl) phosphate] hydroxy Al (another name: two (2,4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] encircle-6-of dioxy phospha eight oxide) aluminium hydroxide salt) or two [2,2-ethylidene-bis-(4,6-di-t-butyl) phosphate] hydroxy Al.
As carboxylic metallic salt nucleator, for example, can use p-tert-butyl benzoic acid aluminium salt, adipic acid aluminium, Sodium Benzoate.
Preferably use a chain alpha-olefine polymers as polymer nucleator.As the example of a chain alpha-olefine polymers, can enumerate 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, the homopolymers of 3-ethyl-1-hexene or the copolymer between them, can also enumerate the copolymer of the alpha-olefin of they and other.
These polymer nucleators can either directly coordinate in the time manufacturing polymerization of olefines compositions (E), also can be in the time that propylene resin (A) be manufactured, before the polymerization of propylene resin (A) or carry out afterwards the polymerization of above-mentioned chain alpha-olefin, by use the propylene resin (A) that contains a chain alpha-olefine polymers to coordinate (be denoted as polymer nucleator and coordinate propylene resin (A')) as nucleator (D) block.When raw material using polymer nucleator cooperation propylene resin (A') as polymerization of olefines compositions (E) uses, it is the use level of the nucleator (D) in polymerization of olefines compositions (E) that polymer nucleator coordinates the amount of polymer nucleator contained in propylene resin (A').In addition, will coordinate the part of the amount that has deducted polymer nucleator propylene resin (A') as the propylene resin (A) in polymerization of olefines compositions (E) from polymer nucleator.
In addition, prepolymerization when above-mentioned polymer nucleator can either use known method by manufacture polymer (A), polymer (B), polymer (F) forms, and also can in the time manufacturing polymer (B), polymer (F), form by segment copolymerization method.
In addition, now, also can be used together the propylene resin (A) that polymer nucleator coordinates propylene resin (A') and do not contain polymer nucleator.In addition, also can be used together polymer nucleator and coordinate propylene resin (A') and other nucleator (D).
These polymer nucleators, in the time that polymerization of olefines compositions (E) contains other resinaes described later, also can be by coordinating with the masterbatch that contains other resinaes and polymer nucleator in the time manufacturing polymerization of olefines compositions (E).When raw material using this masterbatch as polymerization of olefines compositions (E) uses, the use level of the nucleator (D) using the amount of polymer nucleator contained in masterbatch in polymerization of olefines compositions (E).In addition, also can be used together masterbatch and other nucleators (D), manufacture polymerization of olefines compositions.
As polymer nucleator, the viewpoint of good from the characteristic of the transparency, low temperature resistance to impact, rigidity in economy, the particularly preferably polymer of 3-methyl-1-butene.
As sorbose alcohols nucleator, can preferably utilize 1,2,3-, tri-deoxidation-4,6 ︰ 5,7-pair-O-[(4-propyl phenyl) methylene]-nonyl alcohol.
As inorganic compound nucleator, for example, can use talcum, mica, calcium carbonate.
Among these nucleators (D), from the viewpoint of the transparency, low temperature resistance to impact, rigidity and low foul smell, preferably use and be selected from 1,2,3-tri-deoxidation-4,6 ︰ 5,7-pair-O-[(4-propyl phenyl) methylene]-nonyl alcohol and two (2,4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] encircle-6-of dioxy phospha eight oxide) at least a kind of nucleator in aluminium hydroxide salt.Among them, more preferably use two (2,4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] encircle-6-of dioxy phospha eight oxide) aluminium hydroxide salt.
As the nucleator using in the present invention (D), can use commercially available product, for example, ADKSTAB NA-21(ADEKA company system) as containing two (2,4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] encircle-6-of dioxy phospha eight oxide) aluminium hydroxide salt is principal component nucleator is commercially available, 1,2,3-, tri-deoxidation-4,6 ︰ 5,7-is two-O-[(4-propyl phenyl) methylene]-nonyl alcohol is with MIRADE NX8000(Miriken company system) trade name commercially available.
< olefin polymer compositions (E) >
The resin that the outermost layer that the olefin polymer compositions (E) using in the present invention is multilayered blow container of the present invention uses, it is the composition that contains above-mentioned propylene resin (A) 80～98 weight portions, ethene-alpha-olefin copolymer (B) 2～20 weight portions (wherein, (A) and (B) add up to 100 weight portions) and nucleator (D) 0.01～0.5 weight portion.
In addition, in the time that multilayered blow container of the present invention needs low temperature resistance to impact, as mentioned above, as olefin polymer compositions (E), preferably use the composition that also contains in addition low density ethylene-alpha olefin copolymer (F) 0.1～20 weight portion at propylene resin (A), ethene-alpha-olefin copolymer (B) and nucleator (D).
In addition, in the time that multilayered blow container does not need low temperature resistance to impact, also preferred olefin polymers composition (E) is the composition that does not contain low density ethylene-alpha olefin copolymer (F).
The use amount of propylene resin (A) and ethene-alpha-olefin copolymer (B), from the viewpoint of the good viewpoint of being clamminess property and economy and productivity ratio, preferably aforesaid propylene resinoid (A) is 95.5～98 weight portions, above-mentioned ethene-alpha-olefin copolymer (B) is 2～4.5 weight portions (wherein, (A) and (B) add up to 100 weight portions).
The aforesaid propylene resinoid (A) using in order to obtain olefin polymer compositions (E) is more than 98 weight portions, when above-mentioned ethene-alpha-olefin copolymer (B) is less than 2 weight portion, the resistance to impact of multilayered blow container, poor with the cementability of other layers, the aforesaid propylene resinoid (A) coordinating in olefin polymer compositions (E) is less than 80 weight portions, above-mentioned ethene-alpha-olefin copolymer (B) is during more than 20 weight portion, generation is clamminess, so not preferred.
In addition, in the time that multilayered blow container needs low temperature resistance to impact, from being clamminess and the viewpoint of economy, the above-mentioned low density ethylene-alpha olefin copolymer (F) coordinating in preferred olefin polymers composition (E) is 3～15 weight portions.
By total amount 100 weight portions with respect to propylene resin (A) and ethene-alpha-olefin copolymer (B), use the nucleator (D) of 0.01～0.5 weight portion, the effect of the glossiness of the multilayered blow container that can be improved.If the addition of nucleator (D) is less than 0.01 weight portion, the effect that improves glossiness is little.Even if add the addition of nucleator (D) more than 0.5 weight portion, not only effect does not change, and also unfavorable economically, so not preferred.
Above-mentioned olefin polymer compositions (E) meets following condition (E-1).
(E-1) according to ASTM D-1238, to measure melt flow rate (MFR) (MFR) that 230 DEG C of temperature, 2.16kg load measuring obtain as the scope of 5～10g/10 minute.If MFR in above-mentioned scope, the fine melt fracture (MF) that mobility of the olefin polymer compositions (E) when moulding occurs in the time being suitable for the scope of moulding, can suppressing moulding.In addition, the uneven thickness of the olefin polymer compositions (E) of blow molding can be prevented, the multilayered blow container of flatness excellence can be obtained.
According to ASTM D-1238, to measure melt flow rate (MFR) (MFR) that 230 DEG C of temperature, 2.16kg load measuring obtain if higher than 10g/10 minute, insufficient formability, if lower than 5g/10 minute, glossiness is poor.
The condition (E-1) relevant to olefin polymer compositions (E), according to ASTM D-1238, the melt flow rate (MFR) (MFR) obtaining with 230 DEG C of temperature of mensuration, 2.16kg load measuring, can adjust by the propylene resin of suitable choice for use (A), ethene-alpha-olefin copolymer (B) and the low density ethylene-alpha olefin copolymer (F) using as required.
The propylene resin (A) and the ethene-alpha-olefin copolymer (B) that use, according to ASTMD-1238, when measuring melt flow rate (MFR) (MFR) that 230 DEG C of temperature, 2.16kg load measuring obtain all as the scope of 5～10g/10 minute, can carry out by low density ethylene-alpha olefin copolymer (F) of suitably selecting propylene resin (A), ethene-alpha-olefin copolymer (B) and use as required the condition of satisfied (E-1).
In addition, in addition in the situation that, for example, as propylene resin (A), using according to ASTM D-1238, to measure 230 DEG C of temperature, the melt flow rate (MFR) (MFR) that 2.16kg load measuring obtains is for to be less than about 5g/10 minute, in the situation of the propylene resin that MFR is lower, by propylene resin (A), ethene-alpha-olefin copolymer (B) and nucleator (D), and the low density ethylene-alpha olefin copolymer (F) using as required forms olefin polymer compositions when (E), can under existing at organic peroxide, carry out melting mixing, and carry out propylene resin (A), ethene-alpha-olefin copolymer (B), or the modification of the low density ethylene-alpha olefin copolymer (F) using as required, the MFR of olefin polymer compositions (E) is adjusted in above-mentioned scope.Wherein, as organic peroxide, can enumerate the identical material of recording with the project of above-mentioned < propylene resin (A) >.
In addition, as other examples, when use MFR to exceed the higher propylene resin of the MFR of 10g/10 minute as propylene resin (A), low density ethylene-the alpha olefin copolymer (F) that can use as the ethene-alpha-olefin copolymer (B) of combination, as required by the low copolymer of use MFR, is adjusted at the MFR of olefin polymer compositions (E) in above-mentioned scope.
The crystalline melting point that above-mentioned olefin polymer compositions (E) preferably records taking DSC according to JIS-K7121 is the scope of 140～155 DEG C.In the time that crystalline melting point is in above-mentioned scope, can obtain the multilayered blow container that gloss is good, resistance to impact is good.
The crystalline melting point of above-mentioned olefin polymer compositions (E) can use differential scanning calorimetry (DSC) (DSC) to measure according to JIS-K7121.Particularly, can measure with the method same with the crystalline melting point of aforesaid propylene resinoid (A).
In addition, preferably flexible chain (t of above-mentioned olefin polymer compositions (E)
1/2) be the scope of 50～1000 seconds, the more preferably scope of 100～500 seconds.In above-mentioned scope, in the time of blow molding mould transfer printing good, can obtain the multilayered blow container that gloss is good.
Wherein, flexible chain (t
1/2), can, as make olefin polymer compositions (E) crystallization under 125 DEG C of isothermys, measure the now thermal discharge of accompanying crystallization, from heat release, (crystallization starts) is till thermal discharge reaches the time of the value of total thermal discharge half measures.
Flexible chain (the t of above-mentioned olefin polymer compositions (E)
1/2) can adjust by the amount of the contained nucleator (D) of olefin polymer compositions (E).Can accelerate flexible chain (t by the amount that increases the contained nucleator (D) of olefin polymer compositions (E)
1/2), otherwise, can postpone flexible chain (t by the amount that reduces nucleator (D)
1/2).
In olefin polymer compositions of the present invention (E), also can contain aforesaid propylene resinoid (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F) and nucleator (D) composition in addition.
As above-mentioned (A), (B), (F) and (D) composition in addition, can enumerate other resinae, various additives etc.
As other resinae, can enumerate for example propylene resin (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F) and nucleator (D) polyolefin resin in addition.As polyolefin resin, can illustrate propylene resin (A) propylene resin (P) in addition.As propylene resin (P), can enumerate the homopolymers (comprising syndiotactic propylene homopolymers etc.) of the propylene different from propylene resin (A) etc.Conventionally the Tm that, propylene resin (P) records taking differential scanning calorimetry (DSC) (DSC) according to JISK7121 is 140～155 DEG C.In addition, the MFR obtaining with 230 DEG C of temperature of mensuration, 2.16kg load measuring according to ASTM D-1238 as propylene resin (P), is preferably 0.01～20g/10 minute, is particularly preferably 0.1～5g/10 minute.
In addition, as other resins, for example, also can illustrate phenylethylene elastomer or its hydride (S).In addition,, in the time that hope reduces gloss to the dependence of die surface roughness, preferred mode is not add phenylethylene elastomer or its hydride (S).
As phenylethylene elastomer or its hydride (S), can enumerate styrene-content 10～70 % by weight, preferably 10～65 % by weight, more preferably 10～40 % by weight, and conjugated diene content 30～90 % by weight, preferably 35～90 % by weight, more preferably phenylethylene elastomer or its hydride (S) of 60～90 % by weight.
As above-mentioned phenylethylene elastomer or its hydride (S), can enumerate and contain styrenic polymer block composition (below, sometimes also referred to as styrene block) and SBC, styrene butadiene random copolymer, styrene-isoprene random copolymer, styrene-chlorobutadiene random copolymer and their hydride etc. of conjugated diolefine polymer block composition (following, sometimes also referred to as diene block).Optimization styrene based block copolymer among them.
The styrenic polymer block composition that forms above-mentioned SBC is made up of styrene or derivatives thereof, as the concrete material of monomer, can enumerate styrene, AMS, p-methylstyrene, chlorostyrene, vinyl naphthalene etc.Optimization styrene among them.These monomers can use separately one, or are used in combination two or more.
As the concrete material of monomer that forms above-mentioned conjugated diolefine polymer block, can enumerate butadiene, isoprene, chlorobutadiene etc.Preferred butadiene, isoprene among them.These monomers can use separately one, or are used in combination two or more.
Styrene block in SBC and the combination of diene block are not particularly limited, but optimization styrene block-diene block or styrene block-[diene block-styrene block]
nthe mode of (wherein, n is 1～5).
The content of wishing the styrenic polymer block composition in SBC is 10～70 % by weight, be preferably 10～65 % by weight, more preferably 10～40 % by weight, the content of wishing conjugated diolefine polymer block composition is 30～90 % by weight, be preferably 35～90 % by weight, more preferably 60～90 % by weight.
Wish SBC according to ASTM D-1238, taking 230 DEG C, the melt flow rate (MFR) (MFR) that records of load 2160g more than 0.1g/10min, be preferably 0.3～20g/10min, be particularly preferably 5～10g/10min.
As the object lesson of SBC, can enumerate styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), SBS (SBS), SIS (SIS) and styrene-ethylene-propylene-based block copolymer (SEP) etc.
In the time that olefin polymer compositions (E) contains other resinaes, with respect to above-mentioned (A) and 100 weight portions of total (B), the upper limit is generally below 20 weight portions, more preferably below 10 weight portions, be more preferably below 5 weight portions, lower limit is generally 0.1 weight portion.
As other resins, while using aforesaid propylene resinoid (P), aforesaid propylene resinoid (P) is with respect to above-mentioned (A) and 100 weight portions of total (B), the upper limit is generally below 20 weight portions, more preferably below 10 weight portions, be more preferably below 5 weight portions, lower limit is generally 0.1 weight portion.
As other resins, while using above-mentioned phenylethylene elastomer or its hydride (S), above-mentioned phenylethylene elastomer or its hydride (S), with respect to above-mentioned (A) and 100 weight portions of total (B), the upper limit is generally below 20 weight portions, more preferably, below 10 weight portions, be more preferably below 5 weight portions, lower limit is generally 0.1 weight portion.
As other resins, while using at least one in aforesaid propylene resinoid (P) and above-mentioned phenylethylene elastomer or its hydride (S), the total of aforesaid propylene resinoid (P) and above-mentioned phenylethylene elastomer or its hydride (S), with respect to above-mentioned (A) and 100 weight portions of total (B), the upper limit is generally below 20 weight portions, more preferably, below 10 weight portions, be more preferably below 5 weight portions, lower limit is generally 0.1 weight portion.
In addition, in the case of wishing that gloss is little to the dependence of die surface roughness, the mode of do not add the mode of aforesaid propylene resinoid (P), not adding above-mentioned phenylethylene elastomer or its hydride (S) is the mode of more wishing, the mode of not adding aforesaid propylene resinoid (P) and above-mentioned phenylethylene elastomer or its hydride (S) is the mode of more wishing.
In addition, while stating in the use phenylethylene elastomer or its hydride (S), from the viewpoint being clamminess, it is one of preferred mode that above-mentioned low density ethylene-alpha olefin copolymer (F) exists on a small quantity or not.
In the time not using above-mentioned low density ethylene-alpha olefin copolymer (F), use by aforesaid propylene resinoid (A) 80～98 weight portions, ethene-alpha-olefin copolymer (B) 2～20 weight portions (wherein, (A) and (B) add up to 100 weight portions), with the polymerization of olefines compositions (E) that to be selected from as the Tm of any composition be at least one polymer 0～20 weight portion (for the amount with respect to (A) and 100 weight portions of total (the B)) formation in fact in propylene resin (P) and phenylethylene elastomer or its hydride (S) of 140～155 DEG C be also one of optimal way of the present invention.Wherein also comprise that Tm is that the propylene resin (P) of 140～155 DEG C and the total of phenylethylene elastomer or its hydride (S) are the situation of 0 weight portion with respect to (A) and 100 weight portions of total (B).Wherein, it is to represent polymerization of olefines compositions (E) that what is called forms in fact, as other compositions, also can contain additive in the scope of not damaging effect of the present invention, but does not comprise the composition beyond it.
As additive, can enumerate fluidity amendment, the weld strength modifying agent etc. of antioxidant, hydrochloric acid absorbent, heat-resisting stabilizing agent, light stabilizer, ultra-violet absorber, lubricant, antistatic additive, fire retardant, pigment, dyestuff, dispersant, copper evil preventing agent, nertralizer, blowing agent, plasticizer, bubble preventing agent, crosslinking agent, peroxide etc.As these additives, be not particularly limited, for example can use commercially available product.
In the time that olefin polymer compositions (E) contains additive, as the amount of additive, as long as be the amount that can obtain the scope of effect of the present invention, be not particularly limited, but with respect to above-mentioned (A) and 100 weight portions of total (B), be generally 0.01～1.00 weight portion.
The olefin polymer compositions (E) using in the present invention, because MFR is specific scope, therefore it is difficult only carrying out blow molding with olefin polymer compositions (E), but the top layer that can serve as multi-layer blow molding body is used, by using as top layer, show excellent gloss, there is excellent physical property.
Preparation method as olefin polymer compositions (E) is not particularly limited, for example can be listed below method: by propylene resin (A), ethene-alpha-olefin copolymer (B) and nucleator (D), can arbitrarily used low density ethylene-alpha olefin copolymer (F), other resinaes and additive drop into Henschel mixer, Banbury, in the mixers such as rotary drum mixer, mix, then, obtained mixture is passed through to single screw extrusion machine, the extruder moulding such as double screw extruder, obtain the line material of olefin polymer compositions (E).In addition, above-mentioned line material is conventionally carrying out before blow molding, uses comminutor etc. to be shaped to pellet.
In addition, in the time using the additive of the peroxide such as organic peroxide, crosslinking agent isoreactivity as above-mentioned additive, while utilizing above-mentioned mixer to mix, also can follow propylene resin (A), ethene-alpha-olefin copolymer (B), the modification of low density ethylene-alpha olefin copolymer (F) of using as required.
In addition, the multilayered blow container that uses olefin polymer compositions (E) to form as the outermost resin of formation shows that the reason of good physical property is still not clear, but can think and there is the ethene-alpha-olefin copolymer (B) of the crystalline melting point of particular range by use, ethene-alpha-olefin copolymer (B) carries out differential to propylene resin (A) and falls apart, therefore, the gloss of the multilayered blow container obtaining, appearance excellence, resistance to impact improves, and can take into account resistance to impact and low being clamminess property.In addition, can think at the polymer as forming the internal layer joining with outermost layer, while using acronal described later (G) or polyvinyls (H), due to loose with ethene-alpha-olefin copolymer (B) differential of outermost adhesive spots as this layer, therefore the number of adhesive spots increases, also excellent with the cementability of internal layer.In addition, can think, in the time using low density ethylene-alpha olefin copolymer (F), Jie of ethene-alpha-olefin copolymer (B) under, low density ethylene-alpha olefin copolymer (F) differential in propylene resin (A) is loose, therefore gloss, appearance excellence, and resistance to impact and low temperature resistance to impact improve, and can think that being therefore clamminess property also can suppress very lowly because differential is loose.
< multilayered blow container >
Multilayered blow container of the present invention, the resin that outermost layer uses comprises above-mentioned olefin polymer compositions (E).Multilayered blow container of the present invention, as the layer beyond outermost layer, has at least one internal layer.
Be not particularly limited as other layers (internal layer) that form multilayered blow container, conventionally formed by olefin polymer compositions (E) thermoplastic resin in addition.
As olefin polymer compositions (E) thermoplastic resin in addition, can enumerate acronal (G), polyvinyls (H), styrenic polymer, pet resin, polyamide, ABS resin, ethene-vinyl acetate copolymer, polyvinyl alcohol resin or Corvic, Corvic and modified polyolefin resin etc., also can use the mixture of above-mentioned resin of more than two kinds.Wherein, preferred acronal (G), polyvinyls (H).
Wherein, acronal (G) refers to the acronal with 51 % by mole of above construction units from propylene, and polyvinyls (H) refers to the polyvinyls with 51 % by mole of above construction units from ethene.
Multilayered blow container have as other layers (internal layer) is formed by styrenic polymer or pet resin, polyamide, ABS resin, ethene-vinyl acetate copolymer, polyvinyl alcohol resin, Corvic isopolarity resin layer time, from the viewpoint of the adhesive strength of interlayer, between the layer preferably forming at outermost layer and by styrenic polymer or polar resin, there is the layer being formed by modified polyolefin resin (I).
The outermost layer of multilayered blow container of the present invention, the layer being formed by olefin polymer compositions (E) is high glaze.In addition, the resistance to impact of multilayered blow container is also excellent.
The outermost layer of multilayered blow container of the present invention, the layer being formed by olefin polymer compositions (E), the MFR as the liquidity scale of olefin polymer compositions (E) is specific scope.Therefore, can infer in blow molding, the surface that is about to the heating and melting resin before contacting with mould easily becomes smoothly, also easily becomes level and smooth in blow molding rear surface, can think, can obtain thus the multilayered blow container of lustrous surface excellence.In addition, because the MFR as the liquidity scale of olefin polymer compositions (E) is specific scope, therefore appearance is also good.
In addition, olefin polymer compositions (E), can use ethene-alpha-olefin copolymer (B) as the raw material of said composition.Because above-mentioned ethene-alpha-olefin copolymer (B) has the crystalline melting point of particular range, therefore the formed body that obtained is except showing the excellent specific properties such as above-mentioned adhesiveness between layers excellence, being clamminess property be low, in the case of ethene-alpha-olefin copolymer (B) is few with respect to the use amount of propylene resin (A), also can improve efficiently resistance to impact.Its reason is not yet definite, but can infer, has the ethene-alpha-olefin copolymer (B) of the fusing point of particular range by selection, has appropriate layer thickness, and articulamentum is also optimum with the amount of the tie molecule (tiemolecular) of layer.
In addition, olefin polymer compositions (E), as the raw material of said composition, can use low density ethylene-alpha olefin copolymer (F) as required.In the case of above-mentioned low density ethylene-alpha olefin copolymer (F) is few with respect to the use amount of propylene resin (A), also can improve efficiently low temperature resistance to impact.
According to above content, the present inventor infers that multilayered blow container of the present invention is high glaze, resistance to impact excellence simultaneously, and while stating in the use low density ethylene-alpha olefin copolymer (F), low temperature resistance to impact is also excellent.
Multilayered blow container of the present invention, resistance to impact excellence, therefore can suppress by breaking of causing from outside impact etc., and outermost layer is high glaze, and therefore container has the glossiness that has transparent feel.In addition, multilayered blow container of the present invention is due to low temperature resistance to impact excellence, therefore in multilayered blow container, is filled with content and under cryogenic conditions, transports, in the situation such as storage, also can suppress by breaking of causing from outside impact etc.
As the layer structure of multilayered blow container of the present invention, as long as outermost layer is for comprising the layer of olefin polymer compositions (E), be not particularly limited, for example can enumerate the outermost layer that comprises olefin polymer compositions (E), with the two-layer structure of innermost layer (with the layer structure of the arranged in order of outermost layer/innermost layer), the outermost layer that comprises olefin polymer compositions (E), the intermediate layer adjacent with this outermost layer, with with the three-decker of the adjacent innermost layer in this intermediate layer (with the layer structure of the arranged in order of outermost layer/intermediate layer/innermost layer), the outermost layer that comprises olefin polymer compositions (E), the intermediate layer (1) adjacent with this outermost layer, the intermediate layer (2) adjacent with this intermediate layer (1), with with four-layer structure of this intermediate layer (2) adjacent innermost layer (with the layer structure of the arranged in order of outermost layer/intermediate layer (1)/intermediate layer (2)/innermost layer) etc.
Wherein, in the present invention, the layer that is positioned at outermost layer inner side is defined as to internal layer.That is, in the present invention, above-mentioned innermost layer, intermediate layer are equivalent to internal layer, and multilayered blow container of the present invention at least has one deck internal layer, also can have more than two layers internal layer.
Have in the multilayered blow container of the present invention of olefin polymer compositions (E) at outermost layer, with the adjacent layer of outermost layer while being formed by acronal (G) or polyvinyls (H), even if do not use so-called adhering resin also to show firmly cementability.From with the viewpoint of the outermost cementability that comprises olefin polymer compositions (E) of multilayered blow container of the present invention, be preferably acronal (G) or polyvinyls (H) with the adjacent layer of the outermost layer that comprises olefin polymer compositions (E).
In addition, with the adjacent layer of olefin polymer compositions (E) be aforesaid propylene base polymer (G) and polyvinyls (H) in addition layer time, from the viewpoint with the outermost cementability that comprises olefin polymer compositions (E), preferably, across adhesive resin layer, form the outermost layer and other layers that comprise olefin polymer compositions (E).
Multilayered blow container of the present invention, its arbitrarily layer can be colored.
As aforesaid propylene base polymer (G), be not particularly limited, can enumerate homo-polypropylene, propylene-alpha-olefin random copolymer, propylene-alpha-olefin block copolymer etc.As the MFR obtaining according to ASTM D-1238, to measure 230 DEG C of temperature, 2.16kg load measuring of acronal (G), be preferably the scope of 0.1～20.0g/10 minute, be particularly preferably 0.1～5g/10 minute.The crystalline melting point preferably recording taking differential scanning calorimetry (DSC) (DSC) according to JIS-K7121 is in addition the scope of 100～168 DEG C.
As above-mentioned polyvinyls (H), be not particularly limited, can enumerate so-called high density polyethylene (HDPE), straight chain shape low density polyethylene (LDPE), low density polyethylene (LDPE).The density that polyvinyls (H) records with density gradient column method is preferably 0.860～0.980g/cm
3, as the MFR obtaining with 230 DEG C of temperature of mensuration, 2.16kg load measuring according to ASTM D-1238, preferably 0.01～20g/10 minute, is particularly preferably 0.1～5g/10 minute in addition.
As above-mentioned modified polyolefin resin (I), be not particularly limited, generally can use acid modified polyolefin.The acid that acid is used in modification, for example, can enumerate vinyl unsaturated carboxylic acid or its acid anhydrides of maleic anhydride, acrylic acid, methacrylic acid, itaconic anhydride and so on.In addition, as the vistanex using in modification, optimal ethylene-alpha olefin copolymer, Noblen, propylene-alpha-olefin copolymers.
In addition, in multilayered blow container, with the adjacent layer of outermost layer beyond internal layer be preferably by acronal (G), polyvinyls (H), styrenic polymer or be selected from that the resin of at least a kind in pet resin, polyamide, ABS resin, ethene-vinyl acetate copolymer, polyvinyl alcohol resin or Corvic forms layer.
In addition, in the layer beyond outermost layer, also can contain other resinaes, various additive.
As the method for forming of multilayered blow container of the present invention, as long as blow molding, can be any method.As the method for forming, can enumerate direct blow molding method (hollow molding method), injection stretch blow molding method (injection hollow molding method), extrude stretch blow-molded method, sheet material blow molding method etc.As multilayered blow container, the viewpoint of the productivity ratio when producing in a large number, the container preferably obtaining by direct blow molding method or the moulding of injection stretch blow molding method.
In the time being shaped to multilayered blow container by direct blow molding method, for example, use multilayer blow moulding mould, by olefin polymer compositions (E) and other resins so that olefin polymer compositions (E) is outermost mode, with tubular extruded,, clamp with blow mold also during molten condition at obtained parison, in parison, be blown into fluid and be shaped to regulation shape.Because the layer being formed by olefin polymer compositions (E) is outermost layer, therefore can obtain the multilayered blow container of high glaze.
And, (E) in view of its MFR, separately time, there is the situation (for example sometimes slightly having any problem in big blow molding) being restricted in blow molding, if but use the application's technology, by the layer beyond suitable selection outermost layer (for example, by suitably selecting (G) or (H)), also can realize gloss etc. simultaneously and maximize etc.
Although condition of molding also depends on the proterties of resin, the temperature of the resin while being preferably blown into fluid, forming temperature is 120～260 DEG C, the pressure that is blown into of preferably fluid is 2～10kg/cm
2, consider from the viewpoint of mouldability, preferably blowing ratio is 1.2～5.0.
Here said blowing is than the value that obtains divided by the external diameter of the tubular molten parison of being extruded by extruder die portion of external diameter of bottle that refers to moulding.
In the time being shaped to multilayered blow container by injection stretch blow molding method, for example, by by olefin polymer compositions (E) and other resins, so that olefin polymer compositions (E) is outermost mode, be shaped to young base by injection moulding.Then, under the situation of this young bird base in molten condition or soft state, or after heating again after temporarily making young base solidify, use stretching rods etc. are by this young bird base longitudinal stretching forcibly, then for again at cross directional stretch, in young base, be pressed into pressure fluid, can obtain thus multilayered blow container.By injection moulding during by young base moulding, the injection temperature of olefin polymer compositions (E) is generally the scope of 160～260 DEG C.The young base temperature that is about to carry out before above-mentioned longitudinal stretching is preferably 110～150 DEG C, and longitudinal stretching multiplying power is preferably 1.5～4.0 times, and cross directional stretch multiplying power is preferably 1.5～3.0 times.
Thickness, the size of multilayered blow container of the present invention can suitably determine according to the purposes of multilayered blow container etc., but thickness is 0.3～10.0mm conventionally, are of a size of diameter 10～300mm, height 10～300mm.
The outermost thickness of multilayered blow container of the present invention is the Thickness Ratio (skin/internal layer) preferably 50/50～5/95 of the outer internal layer with other preferably, and more preferably 30/70～10/90.In above-mentioned scope, outer field high glaze is easy to performance most, and mouldability is also good, so preferably.
Multilayered blow container of the present invention, when the layer beyond outermost layer also uses transparent resin, the transparency is excellent.Particularly, preferably according to JIS-K7105, the mist value (turbidity) that uses nephelometer to record is below 30, more preferably below 20.In above-mentioned scope time, can obtain the visibility of content very good, bottle that surcharge is high.
Multilayered blow container gloss excellence of the present invention, particularly, the 60 degree glossiness that preferably outermost layer records taking gloss meter according to JIS-K7105 are as more than 70, more preferably more than 75.In the time of above-mentioned scope, can obtain showing excellent glossy appearance, the bottle that surcharge is high.
Multilayered blow container of the present invention can use in various uses, for example be suitable as the container of food such as filling sauce, baste, fruit juice, fruit, dessert, poach vegetables, be suitable as the container of the amenities such as container, filling liquid lotion of Toiletries such as filling cosmetics, shampoo.
[manufacture method of multilayered blow container]
The manufacture method of multilayered blow container of the present invention, preferably use above-mentioned olefin polymer compositions (E) and olefin polymer compositions (E) thermoplastic resin composition in addition, form outermost layer with above-mentioned olefin polymer compositions (E), above-mentioned olefin polymer compositions (E) thermoplastic resin composition in addition forms the mode of at least one internal layer, carries out moulding by direct blow molding method or injection stretch blow molding method.
As the propylene resin using in manufacture method of the present invention (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F), nucleator (D), olefin polymer compositions (E) and olefin polymer compositions (E) thermoplastic resin in addition, can use the material illustrating in the project of above-mentioned [multilayered blow container], also can use other resinaes that illustrate, various additive in the project of [multilayered blow container].
In manufacture method of the present invention, by direct blow molding method or injection stretch blow molding method, the multilayered blow container moulding that outermost layer is formed by olefin polymer compositions (E).Therefore, the multilayered blow container obtaining, owing to containing ethene-alpha-olefin copolymer (B) at the outermost layer of this multilayered blow container, is therefore high glaze.In addition, multilayered blow container is also excellent in resistance to impact.
The multilayered blow container obtaining by manufacture method of the present invention, due to resistance to impact excellence, so suppressed by breaking of causing from outside impact etc., because outermost layer is high glaze, container has the glossiness that has transparent feel.
Embodiment
Then, represent embodiment, illustrate in greater detail the present invention, but the present invention is not limited by these embodiment.
[manufacture of propylene resin (A-1)]
(1) preparation of solid catalyst component
Anhydrous magnesium chloride 95.2g, decane 442ml and 2-Ethylhexyl Alcohol 390.6g are carried out adding for 2 hours thermal response at 130 DEG C to be made after homogeneous solution, in this solution, add phthalic anhydride 21.3g, carry out being uniformly mixed for 1 hour at 130 DEG C again, phthalic anhydride is dissolved.
By after the homogeneous solution cool to room temperature that operation obtains like this, this homogeneous solution 75ml was added dropwise in the titanium tetrachloride 200ml that is held in-20 DEG C with 1 hour.Add after end, the temperature of this mixed liquor was warmed up to 110 DEG C with 4 hours, in the time reaching 110 DEG C, add diisobutyl phthalate (DIBP) 5.22g, stir and keep 2 hours in this temperature thus.
After the reaction of 2 hours finishes, collect solid part by heat filtering, after making this solid part be suspended in again in the titanium tetrachloride of 275ml, then 110 DEG C of heating 2 hours.After reaction finishes, then collects solid part by heat filtering, fully cleans with the decane of 110 DEG C and hexane, until in solution detection do not go on a tour from titanium compound.Solid part after cleaning is as solid titanium catalyst component (A).Solid titanium catalyst component (A) is preserved as decane slurry, but the object forming for Study of Catalyst is dry by a part wherein.Above-mentioned solid titanium catalyst component (A) consist of titanium 2.3 % by weight, chlorine 61 % by weight, magnesium 19 % by weight, DIBP12.5 % by weight.
Wherein, the detection of above-mentioned free titanium compound is carried out with following method.In Schlenk reactor at the 100ml of the displacement of nitrogen in advance with branch, add the supernatant 10ml of above-mentioned solid catalyst component with syringe collecting.Then, by nitrogen fluidized drying solvent hexane, then vacuum drying 30 minutes.Add therein deionized water 40ml, 50 capacity % sulfuric acid 10ml, stir 30 minutes.This aqueous solution, by filter paper, is transferred in 100ml volumetric flask, then, added conc.H as the screening agent of iron (II) ion
3pO
41ml, and add 3%H as the colour reagent of titanium
2o
2aqueous solution 5ml, then volume is adjusted into 100ml by deionized water.Vibration mixes this volumetric flask, uses the absorbance of UV observation 420nm, the detection of the titanium that dissociates after 20 minutes.The cleaning of the titanium that dissociates is removed and the detection of the titanium that dissociates, until do not observe this absorption.
(2) preparation of pre-polymerized catalyst composition
The there-necked flask with mixer of internal volume 500ml, with after nitrogen replacement, is added to heptane 400ml, triethyl aluminum 19.2mmol, dicyclopentyl dimethoxyl silane 3.8mmol, above-mentioned solid titanium catalyst component (A) 4g through processed.Internal temperature is remained on to 20 DEG C, import continuously propylene gas with the speed of 8g/hr while stirring.After 1 hour, stop stirring result has obtained every 1g solid titanium catalyst component (A) polymerization pre-polymerized catalyst composition (B) of 2g propylene.
(3) polymerization
After fully dry the stainless steel autoclave with mixer of internal volume 10L, nitrogen are replaced, add heptane 6L, triethyl aluminum 12.5mmol, dicyclopentyl dimethoxyl silane 0.6mmol through processed.After the nitrogen in propylene displacement system, add hydrogen 0.30MPa-G, then import while stirring propylene and ethene.In addition, adjust import volume, make the ethylene concentration of the gas phase portion in polymerization tank reach 1.5mol%.
In system, be stabilized in after 80 DEG C of internal temperatures, stagnation pressure 0.8MPa-G, add in the Ti atom heptane slurry 20.8ml that contains above-mentioned pre-polymerized catalyst composition (B) 0.10mmol that converts, supply with continuously propylene and ethene with the mode limit that keeps stagnation pressure and ethylene concentration, polymerization in 3 hours is carried out at 80 DEG C in limit.
Stop reaction at the methyl alcohol that adds 50ml after the stipulated time, lower the temperature, take off and press.Content is all transferred to the lautertuns with filter, is warming up to 60 DEG C and carries out Separation of Solid and Liquid.Clean 2 solid part with the heptane 6L of 60 DEG C again.By propylene/ethylene copolymer (propylene resin (the A-1)) vacuum drying that operation obtains like this.
The melt flow rate (MFR) (MFR) of the propylene resin (A-1) obtaining (ASTM D-1238, measure 230 DEG C of temperature, load 2.16kg) is 7.0g/10 minute, will be by
13the weight of the construction unit from ethene that C-NMR calculates, while being made as 100 % by weight from the construction unit of propylene with from the total of the construction unit of ethene is 3.2 % by weight, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording taking DSC) be 145 DEG C, Mw/Mn(molecular weight distribution) be 5.3.
[manufacture of propylene resin (A-2)]
In the manufacture of acronal (A-1), the ethylene concentration that is adjusted into the gas phase portion in polymerization tank is 2.2mol%, in addition, carries out polymerization with the same operation of manufacture of acronal (A-1).
The melt flow rate (MFR) (MFR) of the propylene resin (A-2) obtaining (ASTM D-1238, measure 230 DEG C of temperature, load 2.16kg) is 7.0g/10 minute, will be by
13the weight of the construction unit from ethene that C-NMR calculates, while being made as 100 % by weight from the construction unit of propylene with from the total of the construction unit of ethene is 4.8 % by weight, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording taking DSC) be 136 DEG C, Mw/Mn(molecular weight distribution) be 5.5.
[manufacture of propylene resin (A-3)]
In the manufacture of acronal (A-1), the ethylene concentration that is adjusted into the gas phase portion in polymerization tank is 0.8mol%, in addition, carries out polymerization with the same operation of manufacture of acronal (A-1).
The melt flow rate (MFR) (MFR) of the propylene resin (A-3) obtaining (ASTM D-1238, measure 230 DEG C of temperature, load 2.16kg) is 7.0g/10 minute, will be by
13the weight of the construction unit from ethene that C-NMR calculates, while being made as 100 % by weight from the construction unit of propylene with from the total of the construction unit of ethene is 1.0 % by weight, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording taking DSC) be 156 DEG C, Mw/Mn(molecular weight distribution) be 5.0.
[manufacture of propylene resin (A-4)]
In the manufacture of acronal (A-1), after the nitrogen in propylene displacement system, pack hydrogen 0.15MPa-G into, in addition, carry out polymerization with the same operation of manufacture of acronal (A-1).
The melt flow rate (MFR) (MFR) of the propylene resin (A-4) obtaining (ASTM D-1238, measure 230 DEG C of temperature, load 2.16kg) is 3.0g/10 minute, will be by
13the weight of the construction unit from ethene that C-NMR calculates, while being made as 100 % by weight from the construction unit of propylene with from the total of the construction unit of ethene is 3.2 % by weight, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording taking DSC) be 145 DEG C, Mw/Mn(molecular weight distribution) be 5.3.
[manufacture of propylene resin (A-5)]
In the manufacture of acronal (A-1), after the nitrogen in propylene displacement system, add hydrogen 0.45MPa-G, in addition, carry out polymerization with the same operation of manufacture of acronal (A-1).
The melt flow rate (MFR) (MFR) of the propylene resin (A-5) obtaining (ASTM D-1238, measure 230 DEG C of temperature, load 2.16kg) is 15.0g/10 minute, will be by
13the weight of the construction unit from ethene that C-NMR calculates, while being made as 100 % by weight from the construction unit of propylene with from the total of the construction unit of ethene is 3.2 % by weight, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording taking DSC) be 145 DEG C, Mw/Mn(molecular weight distribution) be 5.3.
[manufacture of ethene-alpha-olefin copolymer (B-1)]
(1) preparation of catalyst
In the reactor of 300 liters of fully nitrogen displacement, be added in 600 DEG C and be dried 154 liters of the silica 1 0.0kg of 10 hours and toluene, make and be suspended shape, be cooled to 0 DEG C.Then, in this suspension, with 23.4 liters of toluene solutions (Al=3.02 mol/L) that drip MAO for 1 hour.Now, the temperature in system is remained on to the scope of 0～5 DEG C.
Then make its reaction 30 minutes at 0 DEG C, be then warming up to 95 DEG C with 1.5 hours, make its reaction 4 hours in this temperature.Then be cooled to 60 DEG C, remove supernatant by decantation.The solid constituent that operation obtains is like this cleaned after 2 times with toluene, be suspended with 100 liters of toluene again, making total amount is 160 liters.
In the suspension that like this operation obtains, with 20.0 liters of toluene solutions (Zr=25.6 mM/l) that drip two (1,3-normal-butyl methyl cyclopentadienyl) zirconium dichlorides for 30 minutes, then make its reaction 2 hours at 35 DEG C at 35 DEG C.Then, remove supernatant, by cleaning 2 times with hexane, obtain the solid catalyst component (1) that every 1g solid catalyst component contains 3.2mg zirconium.
(2) preparation of pre-polymerized catalyst composition
In the reactor of 350 liters of fully nitrogen displacement, pack the above-mentioned solid catalyst component making (1) 7.0kg and hexane into, making total measurement (volume) is 285 liters.To in system, be cooled to after 10 DEG C, by ethene with 8Nm
3the flow of/hr is blown into 5 minutes in hexane.Therebetween, the temperature in system remains on 10～15 DEG C.Then, stop ethene and supply with, pack 2.4 moles of diisobutyl aluminium hydrides (DIBALH) and 1-hexene 1.2kg into.Make in system as after enclosed system, with 8Nm
3the flow of/hr starts the supply of ethene again.After 15 minutes, the flow of ethene is dropped to 2Nm
3/ hr, making the pressure in system is 0.08MPaG.Therebetween, the temperature rise to 35 DEG C in system.Then, the temperature in system is adjusted to 32～35 DEG C by limit, and limit is with 4Nm
3the flow of/hr is supplied with 3.5 hours ethene.Therebetween, the pressure in system remains on 0.07～0.08MPaG.Then, after replacing by nitrogen in system, remove supernatant, clean 2 times with hexane.Operation like this, the pre-polymerized catalyst (2) of 3g polymer that obtained the prepolymerization of every 1g solid catalyst component.
(3) polymerization
Use continous way thermopnore gas phase polymerization apparatus, carry out the copolymerization of ethene and 1-hexene second with stagnation pressure 2.0MPaG, 70 DEG C of polymerization temperatures, linear gas velocity 0.7m/.
Limit is taking the pre-polymerized catalyst (2) of above-mentioned preparation as 4.1g/hr, supply with continuously as the ratio of 5 mMs/hr taking TIBA, and limit starts polymerization.In order to maintain certain gas composition between polymerization period, supply with continuously ethene, 1-hexene, hydrogen, nitrogen (gas composition (mol ratio); 1-hexene/ethene=0.04, hydrogen/ethene=4.0 × 10
-4, ethylene concentration=71%).
The receipts amount of the ethene-1-hexene copolymer obtaining is 6.0kg/hr, and DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 98 DEG C, and the density recording taking density gradient column method is 0.903g/cm
3, MFR(ASTM-1238,230 DEG C of temperature of mensuration, load 2.16kg) and be 7.0g/10 minute, Mw/Mn(molecular weight distribution) be 2.6.
Wherein, also obtained ethene-1-hexene copolymer is designated as to ethene-alpha-olefin copolymer (B-1).
[manufacture of ethene-alpha-olefin copolymer (B-2)]
In the manufacture of ethene-alpha-olefin copolymer (B-1), polymerization temperature is changed to 80 DEG C, gas composition (mol ratio) is changed to 1-hexene/ethene=0.03, hydrogen/ethene=4.2 × 10
-4, ethylene concentration=71%, in addition, the same operation of manufacture with ethene-alpha-olefin copolymer (B-1), obtains ethene-1-hexene copolymer.
The receipts amount of the ethene-1-hexene copolymer obtaining is 6.0kg/hr, and DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 113 DEG C, and the density recording taking density gradient column method is 0.913g/cm
3, MFR(ASTM-1238,230 DEG C of temperature of mensuration, load 2.16kg) and be 7.0g/10 minute, Mw/Mn(molecular weight distribution) be 2.6.
Wherein, also obtained ethene-1-hexene copolymer is designated as to ethene-alpha-olefin copolymer (B-2).
[manufacture of ethene-alpha-olefin copolymer (B-3)]
In the manufacture of ethene-alpha-olefin copolymer (B-1), polymerization temperature is changed to 80 DEG C, gas composition (mol ratio) is changed to 1-hexene/ethene=0.02, hydrogen/ethene=4.6 × 10
-4, ethylene concentration=70%, in addition, the same operation of manufacture with ethene-alpha-olefin copolymer (B-1), obtains ethene-1-hexene copolymer.
The receipts amount of the ethene-1-hexene copolymer obtaining is 5.8kg/hr, and DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 120 DEG C, and the density recording taking density gradient column method is 0.924g/cm
3, MFR(ASTM-1238,230 DEG C of temperature of mensuration, load 2.16kg) and be 7.0g/10 minute, Mw/Mn(molecular weight distribution) be 2.6.
Wherein, also obtained ethene-1-hexene copolymer is designated as to ethene-alpha-olefin copolymer (B-3).
[embodiment A 1]
By propylene resin (A-1) 97 weight portions and ethene-alpha-olefin copolymer (B-1) 3 weight portions, also has the ADK STAB NA-21(ADEKA company system as nucleator (D): contain two (2, 4, 8, 10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1, 3, 2] encircle-6-of dioxy phospha eight oxide) aluminium hydroxide salt is as the aromatic phosphonic acid ester compound class nucleator of main component) 0.15 weight portion, with the phenol antioxidant [pentaerythrite four [3-(3 as additive, 5-di-tert-butyl-hydroxy phenyl) propionic ester]] 0.10 weight portion, Phosphorus antioxidant [three (2, 4-di-tert-butyl-phenyl) phosphite ester] 0.10 weight portion, as calcium stearate 0.09 weight portion of nertralizer, glyceryl monostearate 0.10 weight portion as antistatic additive is uniformly mixed with Henschel mixer, use the double screw extruder (NR-36) of the Nakatani of Co., Ltd. machine made to carry out under the following conditions melting mixing in this mixture, obtain line material.
(double screw extruder condition)
Model: NR-36
Screw speed 250rpm
200 DEG C of resin temperatures
By after obtained line material water cooling, cut off with comminutor, obtain thus the pellet of olefin polymer compositions (E-1).
The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of olefin polymer compositions (E-1) is 7.0g/10 minute, and DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
The measurement result of result and flexible chain, foul smell is together illustrated in table.
Then, use this pellet to implement blow molding.
Use 3 kind of 3 direct blow molding machine of layer multi-layer (LACO of P Co., Ltd. system, 3B504040 blow molding machine), as condition of molding, barrel temperature is set as 200 DEG C, and the pressure setting that is blown into of fluid is 5.0kg/cm
2the molten parison that the crosshead mold forming that utilizes mold hole dimension 14.0mm, core size 12.5mm is external diameter 20.0mm tubular, the cylindric multilayered blow container of 2 layers of structure of manufacture weight 34g, inner capacities 780ml, oral area major diameter of thread 27.0mm, body week external diameter 72mm, body week average wall thickness 0.5mmt.
Particularly, do not use the extruder of internal layer, and use barrel temperature to be set as intermediate layer and the outer field extruder of 200 DEG C, to be used for the propylene random copolymers B251VT(Puriman Polymer Co., Ltd system of base material (internal layer), melt flow rate (MFR) (MFR) (ASTM D-1238, measure 230 DEG C of temperature, load 2.16kg) be 1.2g/10 minute, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording taking DSC) be 146 DEG C) with the extruder in intermediate layer, by olefin polymer compositions (E-1) with outer field extruder, so that the mode melting that outer wall thickness rate example is 15%, after the molten parison that is tubular by crosshead mold forming, temperature is adjusted into by water-flow circuit to the blow mold clamping of 25 DEG C, make its stretching be attached to mould and cooling curing with compressed air, obtain multilayered blow container.Wherein, as blow mold, be used as surface treatment to carry out the mould and these the two kinds of moulds of mould that carried out blasting treatment #200 of blasting treatment #400, use each mould to obtain multilayered blow container.
Use the multilayered blow container obtaining as bottle for test, measure turbidity, gloss (gloss), mouldability, cementability, resistance to impact (full water falls impact strength), being clamminess property by the evaluation method of following record.In addition, for whether the surface treatment of studying mould has impact to the gloss of the multilayered blow container obtaining, use two kinds of Mold Making multilayered blow containers, evaluate respectively its gloss.In table, represent these results.
[embodiment A 2]
Except changing to the ratio of propylene resin (A-1) 95.5 weight portions and ethene-alpha-olefin copolymer (B-1) 4.5 weight portions, carry out same with embodiment A 1.The melt flow rate (MFR) (MFR) (ASTMD-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-2) obtaining in embodiment A 2 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
[embodiment A 3]
When multi-layer blow molding, replace the propylene random copolymers B251VT(Puriman Polymer Co., Ltd system for base material (internal layer)), using propylene random block copolymer B 511QA(Puriman Polymer Co., Ltd system, melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) in intermediate layer is 1.2g/10 minute, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording taking DSC) be 158 DEG C), in addition, carry out same with embodiment A 2.
In table, represent result.
[embodiment A 4]
When multi-layer blow molding, replace the propylene random copolymers B251VT(Puriman Polymer Co., Ltd system for base material (internal layer)), use PE resinoid HDPE, HZ-6008B(Puriman Polymer Co., Ltd system in intermediate layer, melt flow rate (MFR) (MFR) (ASTMD-1238,230 DEG C of temperature of mensuration, load 2.16kg) is 0.7g/10 minute, and the density recording taking density gradient column method is 0.958g/cm
3), in addition, carry out same with embodiment A 2.
In table, represent result.
[embodiment A 5]
Except changing to the ratio of propylene resin (A-1) 80.0 weight portions and ethene-alpha-olefin copolymer (B-1) 20.0 weight portions, carry out same with embodiment A 1.The melt flow rate (MFR) (MFR) (ASTMD-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-3) obtaining in embodiment A 5 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 148 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
[embodiment A 6]
As nucleator (D), replace ADK STAB NA-21(ADEKA company system) 0.15 weight portion, change to Gel All MD(New Japan Chem Co., Ltd goods name, chemical name=1,3,2,4-bis-(to methyl benzal) D-sorbite, in table, be recited as G-MD) 0.30 weight portion, in addition, carry out same with embodiment A 2.The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-7) obtaining in embodiment A 6 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 149 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
[embodiment A 7]
Propylene resin (A-1) is replaced with to propylene resin (A-4), while being uniformly mixed with Henschel mixer, add [2 as organic peroxide, 5-dimethyl-2,5-bis-(benzoyl peroxide) hexane] 0.006 weight portion, in addition, carry out same with embodiment A 2.
The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-20) obtaining in embodiment A 7 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
[Comparative examples A 1]
Except changing to the ratio of propylene resin (A-1) 100 weight portions and ethene-alpha-olefin copolymer (B-1) 0 weight portion, carry out same with embodiment A 1.The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-4) obtaining in Comparative examples A 1 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 1, owing to not coordinating ethene-alpha-olefin copolymer (B), so the condition of discontented unabridged version claim.Owing to not coordinating ethene-alpha-olefin copolymer (B), therefore cementability and resistance to impact (full water falls impact strength) are poor.
[Comparative examples A 2]
Except changing to the ratio of propylene resin (A-1) 70.0 weight portions and ethene-alpha-olefin copolymer (B-1) 30.0 weight portions, carry out same with embodiment A 1.The melt flow rate (MFR) (MFR) (ASTMD-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-5) obtaining in Comparative examples A 2 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 2, the use level of ethene-alpha-olefin copolymer (B) is higher than the scope specifying in claim.Therefore being clamminess property is poor.
[Comparative examples A 3]
Except not adding the ADK STAB NA-21(ADEKA company system as nucleator (D)), carry out same with embodiment A 2.The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-6) obtaining in Comparative examples A 3 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 145 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 3, owing to not coordinating nucleator (D), so the condition of discontented unabridged version claim 1.Therefore gloss (gloss) is poor.
[Comparative examples A 4]
Change to propylene resin (A-2) carry out same with embodiment A 2 except replacing propylene resin (A-1).The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-8) obtaining in Comparative examples A 4 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 138 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 4, the DSC fusing point of propylene resin (A) (according to JIS-K7121, the crystalline melting point recording with DSC) is lower than the scope of claim defined.Therefore mouldability and being clamminess property are poor.
[Comparative examples A 5]
Change to propylene resin (A-3) carry out same with embodiment A 2 except replacing propylene resin (A-1).The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-9) obtaining in Comparative examples A 5 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 158 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 5, the DSC fusing point of propylene resin (A) (according to JIS-K7121, the crystalline melting point recording with DSC) is higher than the scope of claim defined.Therefore resistance to impact (full water falls impact strength) is poor.
[Comparative examples A 6]
Change to propylene resin (A-4) carry out same with embodiment A 2 except replacing propylene resin (A-1).The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-10) obtaining in Comparative examples A 6 is 3.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 6, the melt flow rate (MFR) (MFR) of olefin polymer compositions (E) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) is lower than the scope of claim defined.Therefore gloss (gloss) is poor.
[Comparative examples A 7]
Change to propylene resin (A-5) carry out same with embodiment A 2 except replacing propylene resin (A-1).The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-11) obtaining in Comparative examples A 7 is 15.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 7, the melt flow rate (MFR) (MFR) of olefin polymer compositions (E) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) is higher than the scope of claim defined.Therefore mouldability and resistance to impact (full water falls impact strength) are poor.
[Comparative examples A 8]
Change to ethene-alpha-olefin copolymer (B-2) carry out same with embodiment A 2 except replacing ethene-alpha-olefin copolymer (B-1).The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-12) obtaining in Comparative examples A 8 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
The ethene-alpha-olefin copolymer (B-2) that Comparative examples A 8 is used, the DSC fusing point (according to JIS-K7121, the crystalline melting point recording with DSC) of ethene-alpha-olefin copolymer (B) is higher than the scope of claim defined.Therefore cementability and resistance to impact (full water falls impact strength) are poor.And resistance to impact and the characteristic that is clamminess is balanced bad.
[Comparative examples A 9]
Except changing to the ratio of propylene resin (A-1) 90.0 weight portions and ethene-alpha-olefin copolymer (B-2) 10.0 weight portions, carry out same with Comparative examples A 8.The melt flow rate (MFR) (MFR) (ASTMD-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-13) obtaining in Comparative examples A 9 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
The ethene-alpha-olefin copolymer (B-2) using in Comparative examples A 9, the DSC fusing point (according to JIS-K7121, the crystalline melting point recording with DSC) of ethene-alpha-olefin copolymer (B) is higher than the scope of claim defined.Therefore cementability and resistance to impact (full water falls impact strength) are poor.And resistance to impact and the characteristic that is clamminess is balanced bad.
[Comparative examples A 10]
Except changing to the ratio of propylene resin (A-1) 80.0 weight portions and ethene-alpha-olefin copolymer (B-2) 20.0 weight portions, carry out same with Comparative examples A 8.The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-14) obtaining in Comparative examples A 10 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
The ethene-alpha-olefin copolymer (B-2) using in Comparative examples A 10, the DSC fusing point (according to JIS-K7121, the crystalline melting point recording with DSC) of ethene-alpha-olefin copolymer (B) is higher than the scope of claim defined.Therefore cementability and resistance to impact (full water falls impact strength) are poor.And the equilibrium of resistance to impact and the characteristic that is clamminess is bad.
[Comparative examples A 11]
Change to ethene-alpha-olefin copolymer (B-3) carry out same with embodiment A 2 except replacing ethene-alpha-olefin copolymer (B-1).The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-15) obtaining in Comparative examples A 11 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
The ethene-alpha-olefin copolymer (B-3) using in Comparative examples A 11, the DSC fusing point (according to JIS-K7121, the crystalline melting point recording with DSC) of ethene-alpha-olefin copolymer (B) is higher than the scope of claim defined.Therefore gloss (gloss), cementability and resistance to impact (full water falls impact strength) are poor.And resistance to impact and the characteristic that is clamminess is balanced bad.
[Comparative examples A 12]
Replace ethene-alpha-olefin copolymer (B-1), change to not with metallocene catalyst with the PE resinoid L-LDPE(straight chain shape low density polyethylene (LDPE) of Ziegler-Natta catalyst manufacturing), ULT-ZEX 1030L(Puriman Polymer Co., Ltd system, density 0.909g/cm
3melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) is 7.0g/10min, and DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 115 DEG C), in addition, carry out same with embodiment A 2.
The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-16) obtaining in Comparative examples A 12 is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 12, replace ethene-alpha-olefin copolymer (B), use ULT-ZEX1030L.The DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) of ULT-ZEX 1030L is 115 DEG C, higher than the scope of the DSC fusing point of the ethene-alpha-olefin copolymer (B) of claim defined.And ULT-ZEX 1030L not with metallocene catalyst with Ziegler-Natta catalyst polymerization, cementability, being clamminess property and the resistance to impact (full water falls impact strength) of the multilayered blow container therefore being formed by olefin polymer compositions (E-16) are poor.And resistance to impact and the characteristic that is clamminess is balanced bad.
[Comparative examples A 13]
Replace ethene-alpha-olefin copolymer (B-1), change to PE resinoid HDPE(high density polyethylene (HDPE)), HZ-2100J(Puriman Polymer Co., Ltd system, density 0.956g/cm
3melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) is 11.0g/10 minute, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording taking DSC) be 131 DEG C, Mw/Mn(molecular weight distribution) be 7.0), change to propylene resin (A-1) 90.0 weight portions and PE resinoid HDPE, HZ-2100J(Puriman Polymer Co., Ltd system) ratio of 10.0 weight portions, in addition, carry out same with embodiment A 1.
The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-17) obtaining in Comparative examples A 13 is 8.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 13, use HZ-2100J to replace ethene-alpha-olefin copolymer (B).The DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) of HZ-2100J is 131 DEG C, higher than the scope of the DSC fusing point of the ethene-alpha-olefin copolymer (B) of claim defined.And the density that HZ-2100J records taking density gradient column method is 0.956g/cm
3.The cementability of the multilayered blow container therefore being formed by olefin polymer compositions (E-17) and resistance to impact (full water falls impact strength) are poor.And resistance to impact and the characteristic that is clamminess is balanced bad.
[Comparative examples A 14]
Replace ethene-alpha-olefin copolymer (B-1), as ethene-alpha-olefin copolymer (B), change to TAFMER P-0680(polyethylene rubber (EPR), Mitsui Chemicals, Inc's system, density 0.870g/cm
3, melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) is 1.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording with DSC) can't detect.), change to propylene resin (A-1) 90.0 weight portions and the TAFMER P-0680(Mitsui Chemicals, Inc system as ethene-alpha-olefin copolymer (B)) ratio of 10.0 weight portions, in addition, carry out same with embodiment A 1.
The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-18) obtaining in Comparative examples A 14 is 6.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 14, use TAFMER P-0680(Mitsui Chemicals, Inc system) replacement ethene-alpha-olefin copolymer (B).TAFMER P-0680 can't detect DSC fusing point (according to JIS-K7121, the crystalline melting point recording with DSC), unsuitable with ethene-alpha-olefin copolymer (B).In addition, melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) is 1.0g/10 minute, and the density recording taking density gradient column method is also 0.870g/cm
3.
Glossiness (gloss), cementability and the being clamminess property of the multilayered blow container therefore, being formed by olefin polymer compositions (E-18) are poor.
[Comparative examples A 15]
Replace ethene-alpha-olefin copolymer (B-1), change to TAFMER P-0180(polyethylene rubber (EPR), Mitsui Chemicals, Inc's system, density 0.870g/cm as ethene-alpha-olefin copolymer (B)
3, melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) is 8.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording with DSC) can't detect.), change to propylene resin (A-1) 90.0 weight portions and the TAFMER P-0180(Mitsui Chemicals, Inc system as ethene-alpha-olefin copolymer (B)) ratio of 10.0 weight portions, in addition, carry out same with embodiment A 1.
The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of the olefin polymer compositions (E-19) that Comparative examples A 15 obtains is 7.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
Measurement result and the multilayered blow container result of the test of result and flexible chain, foul smell are together illustrated in table.
In Comparative examples A 15, replace ethene-alpha-olefin copolymer (B), use TAFMERP-0180(Mitsui Chemicals, Inc system).TAFMER P-0180 can't detect DSC fusing point (according to JIS-K7121, the crystalline melting point recording with DSC), unsuitable with ethene-alpha-olefin copolymer (B).In addition, density is 0.870g/cm
3.The cementability of the multilayered blow container therefore, being formed by olefin polymer compositions (E-19) and being clamminess property are poor.
[Embodiment B 1]
By propylene resin (A-1) 97 weight portions and ethene-alpha-olefin copolymer (B-1) 3 weight portions, also has the ADK STAB NA-21(ADEKA company system as nucleator (D): contain two (2, 4, 8, 10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1, 3, 2] encircle-6-of dioxy phospha eight oxide) the aluminium hydroxide salt aromatic phosphonic acid ester compound class nucleator that is main component) 0.15 weight portion, as the TAFMER P-0280(ethylene-propylene copolymer of the Mitsui Chemicals society system of low density ethylene-alpha olefin copolymer (F), the density recording with density gradient column method: 0.870g/cm
3, Ziegler-Natta catalyst, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording with DSC): do not observe, MFR(ASTM-1238, measure 230 DEG C of temperature, load 2.16kg): 5.4g/10 minute) 15 weight portions, with the phenol antioxidant [pentaerythrite four [3-(3 as additive, 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.10 weight portion, Phosphorus antioxidant [three (2, 4-di-tert-butyl-phenyl) phosphite ester]] 0.10 weight portion, as calcium stearate 0.09 weight portion of nertralizer, be uniformly mixed with Henschel mixer, the double screw extruder (NR-36) that this mixture is used to the Nakatani of Co., Ltd. machine made under the following conditions melting mixing obtains line material.
(double screw extruder condition)
Model: NR-36
Screw speed 250rpm
200 DEG C of resin temperatures
By after obtained line material water cooling, cut off with comminutor, obtain thus the pellet of olefin polymer compositions (E-21).
The melt flow rate (MFR) (MFR) (ASTM D-1238,230 DEG C of temperature of mensuration, load 2.16kg) of Propenes resin composition (E-21) is 7.0g/10 minute, and DSC fusing point (according to JIS-K7121, the crystalline melting point recording taking DSC) is 147 DEG C.
The measurement result of result and flexible chain, foul smell is together illustrated in table.
Then, use this pellet to implement blow molding.
Use 3 kind of 3 direct blow molding machine of layer multi-layer (LACO of P Co., Ltd. system, 3B504040 blow molding machine), as condition of molding, barrel temperature is set as 200 DEG C, and the pressure setting that is blown into of fluid is 5.0kg/cm
2crosshead mold forming by mold hole dimension 14.0mm, core size 12.5mm is the molten parison of external diameter 20.0mm tubular, manufactures the cylindric multilayered blow container of 2 layers of structure of weight 34g, inner capacities 780ml, oral area major diameter of thread 27.0mm, body week external diameter 72mm, body week average wall thickness 0.5mmt.
Particularly, do not use the extruder of internal layer, and use, barrel temperature is set as to intermediate layer and the outer field extruder of 200 DEG C, to be used for the propylene random copolymers B251VT(Puriman Polymer Co., Ltd system of base material (internal layer), melt flow rate (MFR) (MFR) (ASTM D-1238, measure 230 DEG C of temperature, load 2.16kg) be 1.2g/10 minute, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording taking DSC) be 146 DEG C) with the extruder in intermediate layer, by olefin polymer compositions (E-21) with outer field extruder, so that the mode melting that outer wall thickness rate example is 15%, utilize after the molten parison that crosshead mold forming is tubular, temperature is adjusted into by water-flow circuit to the blow mold clamping of 25 DEG C, make its stretching be attached to mould and cooling curing with compressed air, obtain multilayered blow container.Wherein, as blow mold, be used as surface treatment to carry out the mould and these the two kinds of moulds of mould that carried out blasting treatment #200 of blasting treatment #400, use each mould to obtain multilayered blow container.
Use the multilayered blow container that obtains as bottle for test, by the evaluation method of following record measure turbidity, gloss (gloss), mouldability, cementability, be clamminess, resistance to impact (full water falls impact strength) and low temperature resistance to impact (full water falls impact strength).In addition, for whether the surface treatment of studying mould has impact to the gloss of the multilayered blow container obtaining, use two kinds of Mold Making multilayered blow containers, evaluate respectively its gloss.In table, represent these results.
[Embodiment B 2]
Low density ethylene-alpha olefin copolymer (F) is changed to the TAFMER A-4085S(ethylene-butene copolymer of Mitsui Chemicals society system from the TAFMER P-0280 of Mitsui Chemicals society system, the density recording with density gradient column method: 0.885g/cm
3, DSC fusing point is (according to JIS-K7121, the crystalline melting point recording with DSC): 70 DEG C, MFR(ASTM-1238,230 DEG C of mensuration temperature, load 2.16kg): 6.7g/10 minute), its use level is changed to 7 weight portions from 15 weight portions, use glyceryl monostearate 0.1 weight portion as antistatic additive, in addition, carry out same with Embodiment B 1, obtains line material.
Except using this line material, carry out same with Embodiment B 1, obtains multilayered blow container.
In table, represent result.
[Embodiment B 3]
Propylene resin (A-1) is changed to 90 weight portions, ethene-alpha-olefin copolymer (B-1) is changed to 10 weight portions, low density ethylene-alpha olefin copolymer (F) is changed to the TAFMERA-4085S of Mitsui Chemicals society system from the TAFMER P-0280 of Mitsui Chemicals society system, its use level is changed to 5 weight portions from 15 weight portions, in addition, carry out same with Embodiment B 1, obtains line material.
Except using this line material, carry out same with Embodiment B 1, obtains multilayered blow container.
In table, represent result.
[Embodiment B 4]
Except low density ethylene-alpha olefin copolymer (F) is changed to from the TAFMER P-0280 of Mitsui Chemicals society system the TAFMER A-4085S of Mitsui Chemicals society system, carry out same with Embodiment B 1, obtains line material.
Except using this line material, carry out same with Embodiment B 1, obtains multilayered blow container.
In table, represent result.
[Embodiment B 5]
Except not using low density ethylene-alpha olefin copolymer (F), carry out same with Embodiment B 1, obtains line material.
Except using this line material, carry out same with Embodiment B 1, obtains multilayered blow container.
In table, represent result.
[Embodiment B 6]
Propylene resin (A-1) is changed to 95.5 weight portions, ethene-alpha-olefin copolymer (B-1) is changed to 4.5 weight portions, do not use low density ethylene-alpha olefin copolymer (F), use glyceryl monostearate 0.1 weight portion as antistatic additive, in addition, carry out same with Embodiment B 1, obtains line material.
Except using this line material, carry out same with Embodiment B 1, obtains multilayered blow container.
In table, represent result.
[Embodiment B 7]
Propylene resin (A-1) is changed to 90 weight portions, ethene-alpha-olefin copolymer (B-1) is changed to 10 weight portions, do not use low density ethylene-alpha olefin copolymer (F), in addition, carry out same with Embodiment B 1, obtains line material.
Except using this line material, carry out same with Embodiment B 1, obtains multilayered blow container.
In table, represent result.
[reference example B1]
Propylene resin (A-1) is changed to 95.5 weight portions, ethene-alpha-olefin copolymer (B-1) is changed to 4.5 weight portions, low density ethylene-alpha olefin copolymer (F) is changed to 25 weight portions from 15 weight portions, in addition, carry out same with Embodiment B 1, obtains line material.
Except using this line material, carry out same with Embodiment B 1, obtains multilayered blow container.
In table, represent result.
[comparative example B1]
Ethene-alpha-olefin copolymer (B-1) is changed to ethene-alpha-olefin copolymer (B-2), propylene resin (A-1) is changed to 95.5 weight portions, use ethene-alpha-olefin copolymer (B-2) 4.5 weight portions, low density ethylene-alpha olefin copolymer (F) is changed to the TAFMER P-0275(ethylene-propylene copolymer of Mitsui Chemicals society system from the TAFMER P-0280 of Mitsui Chemicals society system, the density recording with density gradient column method: 0.860g/cm
3, DSC fusing point (according to JIS-K7121, the crystalline melting point recording with DSC): do not observe, MFR(ASTM-1238, measure 230 DEG C of temperature, load 2.16kg): 5.4g/10 minute), in addition, carry out same with Embodiment B 1, obtains line material.
Except using this line material, carry out same with Embodiment B 1, obtains multilayered blow container.
In table, represent result.
[evaluation method]
According to the method for following record, measure the physical property of acronal (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F) or olefin polymer compositions (E).In table, represent result.
[MFR(melt flow rate (MFR))]
The MFR of aforesaid propylene resinoid (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F) and olefin polymer compositions (E) is according to ASTM D-1238, to measure 230 DEG C of temperature, load 2.16kg mensuration.
The line material obtaining while collecting according to ASTM D-1238 instrumentation MFR uses in the mensuration of following density.
[fusing point (Tm)]
The crystalline melting point of aforesaid propylene resinoid (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F) and olefin polymer compositions (E) is according to JIS-K7121, use differential scanning calorimetry (DSC) (DSC, PerkinElmer company system (Diamond DSC)) to measure.Wherein the summit of the endothermic peak in the 3rd step of measuring is defined as to crystalline melting point (Tm).Endothermic peak has when multiple, and the endothermic peak summit of peak height maximum is defined as to crystalline melting point (Tm).
(condition determination)
Measure environment: nitrogen atmosphere
Sample size: 5mg
Sample shape: (230 DEG C of moulding, thickness 200～400 μ m) for press mold
The 1st step: be warming up to 240 DEG C from 30 DEG C with 10 DEG C/min, keep 10min.
The 2nd step: be cooled to 60 DEG C with 10 DEG C/min.
The 3rd step: be warming up to 240 DEG C with 10 DEG C/min.
[flexible chain (T
1/2)]
Flexible chain (the T of olefin polymer compositions (E)
1/2) use differential scanning calorimetry (DSC) (DSC, PerkinElmer company system (DSC7)) to measure.Under 125 DEG C of isothermys, make olefin polymer compositions (E) crystallization, measure the now thermal discharge of accompanying crystallization, measure from heat release (crystallization starts) till thermal discharge reaches the time (second) of the value of the half of total thermal discharge as flexible chain (t
1/2).Flexible chain (t
1/2) value littlely mean that crystallization speed is larger.
(condition determination)
Measure environment: nitrogen atmosphere
Sample size: 5mg
Sample shape: (230 DEG C of moulding, thickness 200～400 μ m) for press mold
The 1st step: be warming up to 220 DEG C from 30 DEG C with 10 DEG C/min, keep 3min.
The 2nd step: be cooled to 125 DEG C with 60 DEG C/min.
[density]
For the density of ethene-alpha-olefin copolymer (B) and low density ethylene-alpha olefin copolymer (F), the ethene-alpha-olefin copolymer (B) obtaining during by the mensuration of above-mentioned MFR and the line material of low density ethylene-alpha olefin copolymer (F) are respectively 120 DEG C of heat treatments 1 hour, slowly cool to after room temperature through 1 hour, measure with density gradient column.
[Mw/Mn(molecular weight distribution)]
The Mw/Mn of aforesaid propylene resinoid (A) and ethene-alpha-olefin copolymer (B) tries to achieve by the weight average molecular weight (Mw) and the number-average molecular weight (Mn) that record with following determination method.
Mw and Mn use the following time-and-motion study of the GPC-150C Plus processed of Waters company.
Splitter uses TSKgel GMH6-HT and TSKgel GMH6-HTL, column dimension is respectively internal diameter 7.5mm, length 600mm, column temperature is made as 140 DEG C, mobile phase uses o-dichlorohenzene (with the pure pharmaceutical worker's industry of light (strain)) and BHT(and the pure pharmaceutical worker's industry of light (strain) as antioxidant) 0.025 % by weight, flowed with 1.0ml/ minute, sample solution concentration is made as 0.1 % by weight, and sample size is made as 500 microlitres, uses differential refractometer as detector.
For polystyrene standard, molecular weight is at Mw < 1000 and Mw > 4 × 10
6time use the polystyrene standard of eastern Cao (strain) system, molecular weight is in 1000≤Mw≤4 × 10
6time use the polystyrene standard of Pressure Chemical company system.
[turbidity]
For the turbidity of multilayered blow container, cut and measure position from container main part, taking JIS-K7105 as benchmark, use nephelometer (NIPPON DENSHOKU(NDH2000)) mensuration turbidity (mist value).The value of turbidity is less, can say that the transparency is more excellent.
[gloss]
The evaluation of glossiness is evaluated by the mensuration of following gloss (gloss).For the gloss (gloss) of multilayered blow container, from container main part cut measure position, taking JIS-K7105 as benchmark, use gloss meter (NIPPON DENSHOKU(VG2000)) measure outer field 60 degree glossiness.The value of gloss (gloss) is larger, can say and more have excellent glossiness.
[mouldability]
For the mouldability of multilayered blow container, observe the container appearances obtaining, the fold causing with the molten parison rough surface in the time that container body part has or not blowing is evaluated.
AA: there is no fold or not obvious completely, good forming ability
BB: can observe fold or obvious, insufficient formability
[cementability]
At the interlayer of the outermost layer being formed by the application's olefin polymer compositions (E) of multilayered blow container and adjacent layer, evaluate burr cut portion container top and container bottom pinch off portion occur in the time of container formation layer and peel off having or not of the rope form that can observe that causes or banded bad order.
AA: without bad order, cementability is good
BB: carefully see and can observe bad order, cementability is slightly poor
CC: have obvious bad order, cementability is poor
[foul smell]
For the foul smell of olefin polymer compositions (E), the pellet of 10g said composition is added in 100ml conical flask, cover gag sealing, after 1 hour, take out with baking oven heating at 100 DEG C, then open immediately gag, the quality of foul smell occurs as judged with sensory test.
AA---is without foul smell
BB---has foul smell slightly
CC---has foul smell
[resistance to impact]
The evaluation of resistance to impact has or not to evaluate by the surface checking that utilizes following full water dropping impact strength determination method to record.The filling containers that fills water in multilayered blow container (inner capacities 780ml) is cooled to 5 DEG C (evaluations of resistance to impact), respectively 10 containers that are respectively cooled to this temperature are vertically fallen from the high position of concrete surface 1m from the bottom surface of container, fall standard evaluation according to following.Having or not that the judgement of breaking occurs with top layer be full of cracks judges.
AA: all do not chap on surface
BB: more than halfly do not chap on surface, but at least 1 is chapped on surface
CC: plurality chaps on surface
It is better that full water falls the evaluation of impact strength determination method, can say that resistance to impact is better.
[low temperature resistance to impact]
The evaluation of low temperature resistance to impact has or not to evaluate by the surface checking that utilizes following full water dropping impact strength determination method to record.To in multilayered blow container (inner capacities 780ml), fill the volume/volume by glycol/water=5/5() filling containers of liquid that forms is cooled to-5 DEG C (evaluations of low temperature resistance to impact), respectively 10 containers that are respectively cooled to this temperature are vertically fallen from the high position of the 1m of concrete surface from the bottom surface of container, fall standard evaluation according to following.Having or not that the judgement of breaking occurs with top layer be full of cracks judges.
AA: all do not chap on surface
BB: more than halfly do not chap on surface, but at least 1 is chapped on surface
CC: plurality chaps on surface
It is better that full water falls the evaluation of impact strength determination method, can say that low temperature resistance to impact is better.
[being clamminess property]
About the surperficial sense of touch of multilayered blow container, to the surface of 48～72 hours bottles after 23 DEG C of states are adjusted after moulding, have or not the quality of the sense of touch being clamminess as judged with sensory test.
AA: do not feel to be clamminess completely
BB: feel to be hardly clamminess
CC: how much feel to be clamminess
DD: feel to be clamminess
In the application's multilayered blow container, the container not preferably being clamminess, is evaluated as by the container being clamminess being clamminess property poor.
[by
13in the propylene resin that C-NMR calculates from the weight of the construction unit of alpha-olefin]
Will be by
13that C-NMR calculates, from the construction unit of propylene be that the total of the construction unit of a kind of above alkene in 4～20 alpha-olefin is while being made as 100 % by weight from being selected from ethene and carbon number, from being selected from the weight that ethene and carbon number are the construction unit of a kind of above alkene in 4～20 alpha-olefin, according to
13described in being determined as follows of C-NMR, measuring, calculate and determine.
13c-NMR condition determination
Determinator: NEC's LA400 type processed nuclear magnetic resonance device
Mode determination: BCM(Bilevel Complete decoupling)
Observing frequency: 100.4MHz
Observation scope: 17006.8Hz
Pulse width: 45 ° of C cores (7.8 μ second)
Pulse-recurrence time: 5 seconds
Coupon:
Coupon rotating speed: 12Hz
The tired number of times of calculating: 20000 times
Measure temperature: 125 DEG C
Solvent: 1,2,4-trichloro-benzenes: 0.35ml/ heavy benzol: 0.2ml
Sample size: about 40mg
When comonomer is ethene, according to following document (1), by obtained
13c-NMR spectrum is determined the distribute ratio of (two unit groups (2 cellular chain) distribution) of monomer chain, calculates in propylene resin (A) mole fraction (mol%) (being designated as below E(mol%) from the construction unit of ethene) and from the mole fraction (mol%) (being designated as below P(mol%) of the construction unit of propylene).From tried to achieve E(mol%) and P(mol%) be scaled % by weight, calculate the % by weight of the construction unit from propylene in propylene resin (A) and the % by weight from the construction unit of ethene.
Document (1): Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T., Macromolecules 1982,15, (4), 1150-1152
Wherein, in the evaluation of the physical property about multilayered blow container, for turbidity, mouldability, cementability, resistance to impact, low temperature resistance to impact and being clamminess property, the multilayered blow container that uses the Mold Making of having carried out blasting treatment #400 is measured.
[table 1]
[table 2]
[table 3]
[table 4]
Claims (13)
1. a multilayered blow container, is characterized in that:
The resin that outermost layer uses comprises olefin polymer compositions (E), this olefin polymer compositions (E) contains propylene resin (A) 80～98 weight portions, ethene-alpha-olefin copolymer (B) 2～20 weight portions and nucleator (D) 0.01～0.5 weight portion, wherein, (A) and (B) add up to 100 weight portions
Described propylene resin (A) meets following condition (A-1) and (A-2),
Described ethene-alpha-olefin copolymer (B) meets following condition (B-1) and (B-2),
Described olefin polymer compositions (E) meets following condition (E-1),
(A-1) be propylene and the copolymer of more than a kind that is selected from the alpha-olefin that ethene and carbon number are 4～20 alkene;
(A-2), according to JIS-K7121, the crystalline melting point recording taking differential scanning calorimetry (DSC) (DSC) is the scope of 140～155 DEG C;
(B-1) be the copolymer of ethene and the a kind of carbon number above alpha-olefin that is 4～20;
(B-2), according to JIS-K7121, the crystalline melting point recording taking DSC is as more than 85 DEG C and be less than the scope of 110 DEG C;
(E-1) according to ASTM D-1238, to measure melt flow rate (MFR) (MFR) that 230 DEG C of temperature, 2.16kg load measuring obtain as the scope of 5～10g/10 minute.
2. multilayered blow container as claimed in claim 1, is characterized in that:
Described olefin polymer compositions (E) also contains low density ethylene-alpha olefin copolymer (F) 0.1～20 weight portion,
Described low density ethylene-alpha olefin copolymer (F) meets following condition (F-1) and (F-2),
Density (the d that described ethene-alpha-olefin copolymer (B) records with density gradient column method
b[g/cm
3]) and the density (d that records with density gradient column method of low density ethylene-alpha olefin copolymer (F)
f[g/cm
3]) meet following condition (X-1),
(F-1) be the copolymer of ethene and the a kind of carbon number above alpha-olefin that is 3～20;
(F-2) according to JIS-K7121, the crystalline melting point recording taking DSC is as below 89 DEG C, or do not observe the peak based on crystalline melting point;
（X－1）d
B[g/cm
3]＞d
F[g/cm
3]，0.010[g/cm
3]≤（d
B－d
F）[g/cm
3]≤0.050[g/cm
3]。
3. multilayered blow container as claimed in claim 1, is characterized in that:
Described ethene-alpha-olefin copolymer (B) also meets following condition (B-4),
(B-4) density recording taking density gradient column method is 0.880～0.910g/cm
3scope.
4. multilayered blow container as claimed in claim 2, is characterized in that:
Described ethene-alpha-olefin copolymer (B) also meets following condition (B-4a), and described low density ethylene-alpha olefin copolymer (F) also meets following condition (F-3),
(B-4a) density (d recording with density gradient column method
b[g/cm
3]) be 0.890～0.910g/cm
3scope;
(F-3) density (d recording with density gradient column method
f[g/cm
3]) be 0.865～0.900g/cm
3scope.
5. multilayered blow container as claimed in claim 1, is characterized in that:
Described propylene resin (A) also meets following condition (A-4),
(A-4) Mw/Mn recording by GPC is more than 4.0.
6. multilayered blow container as claimed in claim 1, is characterized in that:
Described propylene resin (A) also meets following condition (A-3),
(A-3) according to ASTM D-1238, to measure MFR that 230 DEG C of temperature, 2.16kg load measuring obtain as the scope of 5～10g/10 minute.
7. multilayered blow container as claimed in claim 1, is characterized in that:
Described ethene-alpha-olefin copolymer (B) also meets following condition (B-5),
(B-5) Mw/Mn recording by GPC is 1.2～3.0.
8. multilayered blow container as claimed in claim 1, is characterized in that:
Described ethene-alpha-olefin copolymer (B) also meets following condition (B-3),
(B-3) according to ASTM D-1238, to measure MFR that 230 DEG C of temperature, 2.16kg load measuring obtain as the scope of 5～10g/10 minute.
9. multilayered blow container as claimed in claim 1, is characterized in that:
Described nucleator (D) is for being selected from a kind of above compound in aromatic phosphonic acid ester compound, carboxylic metallic salt nucleator, polymer nucleator, sorbose alcohols nucleator and inorganic compound nucleator.
10. multilayered blow container as claimed in claim 1, is characterized in that:
Described propylene resin (A) is 95.5～98 weight portions, and described ethene-alpha-olefin copolymer (B) is 2～4.5 weight portions, wherein, (A) and (B) add up to 100 weight portions.
11. multilayered blow containers as claimed in claim 1, is characterized in that: described multilayered blow container has at least one internal layer, and this internal layer is formed by acronal (G) or polyvinyls (H).
12. multilayered blow containers as claimed in claim 1, is characterized in that: described multilayered blow container obtains by direct blow molding method or the moulding of injection stretch blow molding method.
The manufacture method of 13. 1 kinds of multilayered blow containers, is characterized in that:
Right to use requires olefin polymer compositions (E) and olefin polymer compositions (E) thermoplastic resin composition in addition described in 1,
Form outermost layer with described olefin polymer compositions (E), described olefin polymer compositions (E) thermoplastic resin composition in addition forms the mode of at least one internal layer, by direct blow molding method or the moulding of injection stretch blow molding method.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-012354 | 2010-01-22 | ||
| JP2010012354 | 2010-01-22 | ||
| JP2010-031430 | 2010-02-16 | ||
| JP2010031430 | 2010-02-16 | ||
| PCT/JP2011/050939 WO2011090101A1 (en) | 2010-01-22 | 2011-01-20 | Multilayer blow-molded container, and process for production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102712186A CN102712186A (en) | 2012-10-03 |
| CN102712186B true CN102712186B (en) | 2014-07-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180006278.4A Active CN102712186B (en) | 2010-01-22 | 2011-01-20 | Multilayer blow-molded container, and process for production thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5379247B2 (en) |
| KR (1) | KR101333450B1 (en) |
| CN (1) | CN102712186B (en) |
| WO (1) | WO2011090101A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104077956B (en) * | 2013-03-28 | 2017-05-17 | 优泊公司 | Label for intramode molding and labeled plastic container utilizing label for intramode molding |
| WO2015137268A1 (en) * | 2014-03-10 | 2015-09-17 | 株式会社プライムポリマー | Propylene resin composition and stretched container made from same |
| MY181341A (en) * | 2015-01-16 | 2020-12-21 | Prime Polymer Co Ltd | Laminate, container and manufacturing method thereof, and sheet for use as raw material of laminate |
| US10173813B2 (en) * | 2016-09-29 | 2019-01-08 | Dow Global Technologies Llc | Flexible container with pop-up spout |
| JP7055598B2 (en) * | 2017-05-31 | 2022-04-18 | 株式会社プライムポリマー | Sterilization container |
| JP6980452B2 (en) * | 2017-08-09 | 2021-12-15 | 住友化学株式会社 | Hollow container and its manufacturing method, and polypropylene resin composition for blow fill seal |
| JP6935748B2 (en) * | 2018-01-09 | 2021-09-15 | 日本ポリプロ株式会社 | Propylene resin composition and its molded product |
| JP6995184B2 (en) * | 2018-03-20 | 2022-01-14 | 株式会社プライムポリマー | Laminates and liquid packaging bags |
| EP3856837A1 (en) * | 2018-09-26 | 2021-08-04 | Borealis AG | Propylene copolymer composition with excellent optical and mechanical properties |
| KR102157673B1 (en) * | 2020-04-28 | 2020-09-21 | 라니홀딩스(주) | Container for food packaging |
| EP4172259A1 (en) | 2020-06-30 | 2023-05-03 | Fina Technology, Inc. | Clear polypropylene composition for thermoforming |
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|---|---|---|---|---|
| CN1263899A (en) * | 1999-02-04 | 2000-08-23 | 株式会社宏大化纤 | Polypropylene block copolymer resin and preparation method thereof |
| CN101384627A (en) * | 2006-02-15 | 2009-03-11 | 三井化学株式会社 | Ethylene resin and blow-molded article comprising the same |
| CN101511930A (en) * | 2006-09-12 | 2009-08-19 | 三井化学株式会社 | Polypropylene resin and blown container |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0631796A (en) * | 1992-07-14 | 1994-02-08 | Chisso Corp | Polyolefin resin-made hollow container |
| JPH09166476A (en) * | 1995-12-13 | 1997-06-24 | Kyoto Puratetsuku:Kk | Liquid-level sensor |
| JPH09165476A (en) * | 1995-12-15 | 1997-06-24 | Chisso Corp | Multilayer hollow vessel |
| JP2009013333A (en) * | 2007-07-06 | 2009-01-22 | Sumitomo Chemical Co Ltd | Polypropylene-based resin composition |
-
2011
- 2011-01-20 WO PCT/JP2011/050939 patent/WO2011090101A1/en active Application Filing
- 2011-01-20 CN CN201180006278.4A patent/CN102712186B/en active Active
- 2011-01-20 JP JP2011550944A patent/JP5379247B2/en active Active
- 2011-01-20 KR KR1020127021432A patent/KR101333450B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263899A (en) * | 1999-02-04 | 2000-08-23 | 株式会社宏大化纤 | Polypropylene block copolymer resin and preparation method thereof |
| CN101384627A (en) * | 2006-02-15 | 2009-03-11 | 三井化学株式会社 | Ethylene resin and blow-molded article comprising the same |
| CN101511930A (en) * | 2006-09-12 | 2009-08-19 | 三井化学株式会社 | Polypropylene resin and blown container |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011090101A1 (en) | 2013-05-23 |
| KR101333450B1 (en) | 2013-11-26 |
| KR20120104436A (en) | 2012-09-20 |
| JP5379247B2 (en) | 2013-12-25 |
| WO2011090101A1 (en) | 2011-07-28 |
| CN102712186A (en) | 2012-10-03 |
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