AU6166290A - Thermoplastic resin composition used for multi-layered molding product - Google Patents
Thermoplastic resin composition used for multi-layered molding productInfo
- Publication number
- AU6166290A AU6166290A AU61662/90A AU6166290A AU6166290A AU 6166290 A AU6166290 A AU 6166290A AU 61662/90 A AU61662/90 A AU 61662/90A AU 6166290 A AU6166290 A AU 6166290A AU 6166290 A AU6166290 A AU 6166290A
- Authority
- AU
- Australia
- Prior art keywords
- polyolefin
- polyamide
- resin
- modified
- polyolefin resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 25
- 239000011342 resin composition Substances 0.000 title claims description 22
- 238000000465 moulding Methods 0.000 title claims description 21
- 229920000098 polyolefin Polymers 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 55
- 229920002647 polyamide Polymers 0.000 claims description 55
- 239000004952 Polyamide Substances 0.000 claims description 54
- -1 polyethylene Polymers 0.000 claims description 32
- 229920005672 polyolefin resin Polymers 0.000 claims description 27
- 239000004698 Polyethylene Substances 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 14
- 229920006122 polyamide resin Polymers 0.000 claims description 14
- 229920001155 polypropylene Polymers 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000002685 polymerization catalyst Substances 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 229920002292 Nylon 6 Polymers 0.000 description 9
- 239000002828 fuel tank Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 238000009863 impact test Methods 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- NIDNOXCRFUCAKQ-RNGGSSJXSA-N (1r,2r,3s,4s)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@@H]2C=C[C@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-RNGGSSJXSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical group CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RRGJXXWAXMTTAM-UHFFFAOYSA-N 2-butylbenzenecarboperoxoic acid Chemical group CCCCC1=CC=CC=C1C(=O)OO RRGJXXWAXMTTAM-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- DTGWMJJKPLJKQD-UHFFFAOYSA-N butyl 2,2-dimethylpropaneperoxoate Chemical group CCCCOOC(=O)C(C)(C)C DTGWMJJKPLJKQD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical group OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
-
- 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
- B32B2377/00—Polyamides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Description
THERMOPLASTIC RESIN COMPOSITION USED FOR
MULTI-LAYERED MOLDING PRODUCT
1. Field of the Invention
The present invention concerns a thermoplastic resin composition used for multi-layered molding products and, more particularly, relates to a thermoplastic resin composition suitable for use as a polyolefin layer in multi-layered highly impact resistant molding products comprising a polyamide layer and a polyolefin layer.
2. Description of the Related Art
Since polyolefin resins are inexpensive and have high strength, they are generally suitable for use in the production of various kinds of
containers. Polyolefin resins, however, suffer the disadvantage that they lack a high resistance to gas
permeability. Consequently, they are not suitable for use as fuel tanks, such as gasoline tanks.
There have been various attempts to blend polyamide resins having excellent gas-barrier
properties, such as nylon, with polyolefin resins to form thermoplastic resin compositions which are excellent both in mechanical strength and gas
barrier properties. See, for instance, Japanese Patent Laid-Open No. 54-123158, 59-232135, 62- 158739, 62-241938 and 62-242941. Further, it has been proposed to produce multi-layered molding products by laminating a polyamide layer to a
polyolefin layer, rather than blending these two components, to obtain enhanced gas barrier
properties. See Japanese Patent Laid-Open No. 54- 113678, 55-91634, 55-121017 and Japanese Patent
Publication No. 60-14695. In these molding
products, since the adhesion between the polyolefin layer and the polyamide layer is generally low, a modified, plastic layer, such as a polyolefin resin modified with an unsaturated carboxylic acid, is placed between the layers to act as an adhesive.
It has also been suggested that one should recover the flash formed upon molding of multilayered molding products and mix these with
polyolefin for reuse. Japanese Patent Laid-Open No. 54-113678 and 55-91634. However, when the flash of the multi-layered molding products is blended with
the polyolefin, one does not always obtain
thermoplastic resin compositions that have
acceptable adhesion strength and impact resistance. It is speculated that this is attributable to the poor compatibility between the polyolefin and the polyamide. Since impact resistance is particularly important in fuel tanks and other impact sensitive applications, a reduction in impact strength greatly impairs the commercial value of a product for such uses. Further, although the impact resistance can be maintained if flash is not used in production, this increases material costs and is therefore undesirable. Accordingly, it is an object of the present invention to provide a thermoplastic resin composition of excellent impact resistance. In particular, it is an objective to provide a
thermoplastic resin composition suitable for use as a polyolefin layer in a multi-layered molding product comprising a polyamide layer and a
polyolefin layer that has excellent impact
resistance.
Summary of the Invention
The loss of impact strength when polyamide is blended into polyolefin is due to a "peeling
phenomenon" at the polyolefin-polyamide interface. The inventors have found that the peeling phenomenon can be suppressed thereby improving the impact
resistance of the resin composition. This is
accomplished by adding an appropriate amount of a modified polyolefin and a polyamide to the
polyolefin and insuring that the size of the
dispersed particles or grains of polyamide in the resin composition is less than a predetermined size.
The invention thermoplastic resin composition useful for producing multi-layered molding products comprises: (a) about 0.1 to about 5 wt.% of a polyamide based on the weight of the resin
composition, (b) a polyolefin modified with an unsaturated carboxylic acid or its derivative in an amount not less than about 1/5th of the blending amount of the polyamide, and (c) a balance
substantially of a polyolefin resin and optimally additives for specific properties. The polyamide is dispersed in the thermoplastic resin composition, in a granular state, with an average grain size of not greater than about 4 microns.
Brief Description of the Drawing
Fig. 1 is a cross sectional view illustrating one embodiment of the layer structure for a multi- layered molding product prepared by using the resin composition according to the present invention.
Detailed Description of the Preferred Embodiments
The invention highly impact resistant
thermoplastic resin composition comprises a
polyolefin resin having dispersed therein fine particles of a polyamide and including a modified polyolefin as a compatibilizing agent.
The polyamides useful in the present invention include those polyamide resins prepared from
aliphatic, cycloaliphatic or aromatic diamines such as hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4- trimethylenehexamethylene diamine, 1,3- or 1,4- bis(aminomethyl)cyclohexane, bis (p- aminocyclohexylmethane), m- or p-xylene diamine and aliphatic, cycloaliphatic or aromatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, cyclohexane diacarboxylic acid, terephthalic acid or isophthalic acid; polyamide resins prepared from aminocarboxylic acid such as 6-aminocaproic acid, 11-aminoundecanic acid or 12-aminododecanic acid; polyamide resins prepared from lactams such as e-caprolactams or ω-dodecalactam; copolymerized polyamide resins comprising the above-mentioned ingredients or mixtures of such polyamide resins. Specific polyamides include nylon-6, nylon-66, nylon-11, nylon-12 and copolymers thereof.
Furthermore, copolymers comprising more than 50% by
weight of such a nylon resin and resins other than those described above may also be used.
The molecular weight of the polyamide is, preferably, within a range from 3,000 to 200,000 and more preferably within a range from 10,000 to
100,000.
It is further preferred, for improving impact resistance, to incorporate from about 0.5 to 40 wt.% of a plasticizer such as ∊-caprolactam, N- butylbenzene sulfonamide or octyl p-oxybenzoate and the like in the polyamide. More preferably, the plasticizer is present in an amount from about 3-25 wt.%.
The polyolefin used in the present invention may be a homopolymer of α-olefin such as ethylene, propylene, butene-1, hexene-1 or 4-methylpentene-1; a copolymer of ethylene with propylene or another α- olefin, or a copolymer of ethylene with two or more of such α-olefins. Polyethylene, such as low density polyethylene, linear low density
polyethylene, medium density polyethylene or high density polyethylene, as well as polypropylene are preferred. Further, a copolymer of polyethylene or polypropylene with a polymer other than those described above and containing more than 75 wt.% of polyethylene or polypropylene may be used.
The useful polypropylene is not restricted to polypropylene homopolymers but include random or
block copolymers with other α-olefins containing more than 50 mol %, preferably more than 80 mol % polypropylene. Suitable comonomers for propylene include ethylene or like other α-olefins, ethylene being particularly preferred. Accordingly, the term "polypropylene" used in the specification and claims should be construed as including polypropylene copolymers.
When polyethylene is used as the polyolefin, it is preferred that the high load melt-index (HLMI, at 190oC under 21.6 kg of load) be greater than 0.1 g/10 min and the melt-index (MI, at 190°C under 2.16 kg of load) be less than 100 g/10 min. More
preferably, the high load melt-index should be greater than 1 g/10 min and the melt-index less than 50 g/10 min. In the case of polypropylene, the melt flow rate (MFR, at 230°C under 2.16 kg of load) is within a range from 0.01 to 150 g/10 min, preferably from 0.1 to 75 g/10 min.
By using polyethylene or polypropylene having a melt flow property within these ranges, a
composition may readily be kneaded or blended to disperse polyamide particles homogeneously.
The modified polyolefin used in the present invention is a polyolefin modified with an
unsaturated carboxylic acid or its anhydride.
Examples of the unsaturated carboxylic acid or its anhydride, include for example monocarboxylic acids
such as acrylic acid or methacrylic acid,
dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid, dicarboxylic acid anhydrides such as maleic acid anhydride, itaconic acid anhydride or himic acid anhydride. Dicarboxylic acids and their derivatives are particularly preferred.
Specifically, a modified polyolefin with maleic acid anhydride or himic acid anhydride are particularly preferred.
The unsaturated carboxylic acids or their derivatives in the modified polyolefin are
preferably present in the invention composition in the range from 0.005 - 5 wt.%. When maleic acid anhydride is used, its preferred range is from
0.01 - 3 wt.%, more preferably, 0.1 - 1 wt.%. When himic acid anhydride is used the preferred range is from 0.015 - 4 wt.%, more preferably, from 0.15 to 1.5 wt.%. If the degree of modification with maleic acid anhydride or himic acid anhydride is less than the above-specified lower limits, then there is not a significant or effective improvement in
compatibility between the polyamide and the
polyolefin. On the other hand, if the amount exceeds the above-mentioned upper limits,
compatibility is reduced. It is preferred that the molar ratio of the terminal amines of the polyamide to the carboxylic acid groups in the modified
polyolefin be greater than 0.1, for improved impact resistance.
The modified polyolefin can be prepared by either a solution method or a melt-kneading method. In the case of the melt-kneading or melt-blending method, a polyolefin, a modifying unsaturated
carboxylic acid (or acid anhydride) and a catalyst are charged to an extruder, double-screw kneader, etc. and melt blended while heating at a temperature of about 150 - 250°C. In the case of the solution method, the starting materials are dissolved in an organic solvent, such as xylene, and preparation is conducted while stirring at a temperature from about 80 to about 140°C. In either of these cases, a radical polymerization catalyst may be used, for example peroxides, such as benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide, acetyl
peroxide, tertiary butyl peroxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, or 2,5-dimethyl-2,5 ditertiary butyl peroxy hexine; or diazo compounds such as azobisisobutyronitrile are preferred. The catalyst is added in amounts from about 1 to about 100 parts by weight, based upon 100 parts by weight of the modifying unsaturated carboxylic acid or its anhydride. As the size of the polyamide
particles dispersed in the resin composition is reduced, the impact resistance is further improved.
The more preferred grain size of the dispersed polyamide is less than two microns on average.
In the invention thermoplastic resin
composition, the content of the polyamide is from 0.1 to 5 wt.%, preferably from 0.1 to 3 wt.% based upon the resin content. The content of the modified polyolefin is not less than 0.2 times, preferably 1 - 4 times the polyamide content. The balance substantially comprises a polyolefin and optional additives and fillers.
The average grain size of the dispersed
polyamide particles in the resin composition may be reduced to less than 4 microns by blending or kneading the composition for a sufficient length of time under melt conditions.
If the polyamide is less than 0.1 wt.%, the composition is ineffective for modifying the polyolefin and improving the impact resistance. On the other hand, if the polyamide content exceeds 5% by weight, the composition develops brittleness and no improvement in impact resistance is obtained. Further, if the content of the modified polyolefin is not more than 0.2 times the polyamide content, the compatibility between the polyolefin and the polyamide is not improved. Thus, the peeling phenomenon between the polyolefin and the polyamide is not suppressed.
The invention thermoplastic resin composition may also include inorganic fillers such as carbon, etc. in order to improve mechanical strength, heat resistance, etc. When such fillers are added, it is preferred that the blending ratio of the
thermoplastic resin composition be more than 50 volume percent at 23°C. If additives such as organic fillers or carbon black comprise more than 50 percent by volume, not only is the moldability of the composition reduced thereby making it difficult to prepare a molding product, but the mechanical strength is also reduced.
Other additives may also be included in the invention composition, for example, heat
stabilizers, light stabilizers, flame retardants, plasticizers, antistatic agents, releasing agents, foaming agents and nucleating agents.
The invention composition may be produced by kneading or blending in a molten state while heating by using an extruder, such as a single or double screw extruder. Further, each of the above
ingredients may be premixed in a Henschel mixer, or the like, and the mixture may then be melt-kneaded in an extruder. Further, upon melt kneading of the composition, if there is a great difference in the melt viscosity between the polyolefin and the modified polyolefin, and the polyamide, the
dispersion may be improved by pre-kneading the
polyamide and the modified polyolefin under melt conditions and thereafter kneading them together under melt conditions with the polyolefin.
A multi-layered molding product having a layer structure as shown in Fig. 1 can be prepared using the invention composition. The multi-layered
molding product comprises resin layers 1,1 composed of a composition according to the present invention; a polyamide resin layer 2 and modified polyolefin layers 3,3 for bonding the layers. When a modified polyolefin, for example, is incorporated into the resin layers 1,1 the adhesion strength between each of the layers is increased thereby increasing the mechanical strength of the multi-layered product. When the polyamide layer 2 is used as the inner layer 2, the multi-layered molding product also has excellent water proof properties.
The multi-layered molding product can be prepared for example, by a blow-molding process, in which flash formed in the production can be
recovered and kneaded with the resin for forming the resin layers 1,1. The flash contains polyolefin, modified polyolefin and polyamide resin. Since the flash has the same composition as the invention composition, it can be kneaded into the mixture without reducing compatibility. The composition ratio of the polyolefin, the modified polyolefin and the polyamide resin in the flash varies depending
upon the thickness of each of the layers of the multi-layered molding product. Thus, if resin is added to the blend composition taking the
composition of the flash into account, then flash can be readily reused.
In summary, although compatibility between polyamides and polyolefins is poor, they can be compatibilized using a polyolefin modified with an unsaturated carboxylic acid or its derivatives. In particular, the occurrence of a peeling phenomenon at the interface of the polyolefin and polyamide can be prevented by adding a modified polyolefin and reducing the average grain size of the particles of the polyamide dispersed in the polyolefin to less than about 4 microns. Carboxylic acid groups in the modified polyolefin react with terminal amines in the polyamide resin to form a polyamide-modified polyolefin copolymer uniformly distributed within the thermoplastic resin.
The following Examples are intended to
illustrate the invention as described above and claimed hereafter and do not limit the scope of the invention as described above and claimed herebelow.
Examples 1 - 6
Nylon-6 having a number average molecular weight of 30,000 and containing 8% by weight of ∊- caprolactam as a plasticizer, was dry blended in a high speed mixer with a modified polyethylene
(containing 0.4 wt.% of maleic acid anhydride and having a 0.5 g/10 min melt index) and a polyethylene (having a density of 0.955 g/cm3 and having a melt index (MI) of 0.5 g/10 min) in the blending ratios shown in Table I. These blends were then charged to a single-screw extruder and kneaded at 240°C to obtain pellets of the composition.
The resultant pellets were dried and test specimens were prepared by injection molding. The cylinder temperature in the injection molding was set to 240°C. Tensile impact tests were conducted at 23°C and -40°C according to ASTM D1822-S. The results are shown in Table I.
Examples 7 - 14
Blends were prepared wherein the Nylon-6 did not include the plasticizer, ∊-caprolactam. Blend compositions are shown in Table I. Test specimens were prepared and tested as detailed above for Examples 1-6. Comparative Examples 1 - 4
For comparison, blends were prepared using polyamides shown in Table II and the same modified polyethylene and the polyethylene as the blends of Example 1. The blending ratios are shown in Table II. Test specimens were prepared and tested using the procedures of Examples 1-6. The results are shown in Table II.
Examples 15 - 20
Blends shown in Table III were prepared with Nylon-6 (having a number average molecular weight of 30,000 and containing 8% by weight of ∊-caprolactam), a modified polyolefin (0.4 wt.% of addition rate of maleic acid anhydride and having a melt flow rate (MFR) of 50 g/10 min, at 230°C under 2.16 kg of load), and a propylene homopolymer
(having MFR of 9 g/10 min) using the same procedures as those in Example 1. Test specimens were prepared using the same procedures of Example 1. An Izod impact test was conducted at 23°C and -20°C
according to the JIS K-7110 method. The results are shown in Table III.
Examples 21 - 28
Blends 21-28 were prepared with the nylons shown in Table III and the same modified
polypropylene and the polypropylene as those of Example 15. Test specimens were prepared by the method of Example 15 and Izod impact tests were conducted. The results are shown in Table III.
Comparative Examples 5 - 8
For comparison, comparable blends 5-8 shown in Table IV were prepared using Nylon-6 as the
polyamide and the same modified polypropylene and the polypropylene as in Example 15. Test specimens were prepared by the same procedures as those of
Example 15 and an Izod impact test was conducted. The results are shown in Table IV.
The test specimens produced by the invention have higher values for both tensile impact and strength and Izod strength.
Example 29
70 liter volume fuel tanks comprising five layers of three components as shown in Fig. 1 were molded using the composition of Example 2 as the thermoplastic resin layer. The composition of
Example 2 was used for the innermost and the
outermost layers (layers 1,1 in Fig. 1), Nylon-6 was used for the intermediate layer (layer 2 in Fig. 1) and the modified polyethylene was used for the adhesion layer (layers 3,3 in Fig. 1).
The outermost layer and the innermost layers comprising the composition of Example 2 were 1800 microns and 1840 microns thick, respectively. The intermediate layer comprising Nylon-6 was 120 microns thick and the adhesion layer, comprising the modified polyethylene, was 120 microns thick.
A drop impact test was conducted in the
following manner. Water was charged into 10 fuel tanks to the same weight as that of the fuel that would be required to fill the tanks. Each filled tank was then dropped from heights (6, 8, 10 and 12 meters) to determine the height from which the tank failed. The results are shown in Table V.
Example 30
70 liter volume fuel tanks, each comprising five layers composed of three ingredients, and having the same layered structure as that of Example 29, were also molded by the same procedures as those in Example 29 except that flash was incorporated into the thermoplastic resin layer. A blend
comprising 100 parts by weight of recovered flash upon molding the fuel tanks in Example 29 and 100 parts by weight of the composition in Example 2
(average grain size of polyamide of 0.5 microns) was prepared and used for the innermost layer and the outermost layers of the fuel tank.
A drop impact test was conducted by the same procedures as those in Example 29. The results are shown in Table V.
Comparative Example 9
70 liter volume fuel tanks comprising five layers and composed of three ingredients having the same layer structure as that in Example 29 were molded in the same manner except that a high density polyethylene (density: 0.955, melt index: 0.5 g/10 min) was used for the innermost and the outermost layers of the fuel tanks.
A drop impact test was conducted in the same procedures as those in Example 29. The results are shown in Table V.
TABLE III
Components Blends
15 16 17 18 19 20 21 22 23 24 25 26 27 28
Polyamide1 4 2 1 0.2 2 2 4 2 1 0.2 2 2 2 2
Modified Polyethylene2 6 3 1.5 0.3 0.5 1 6 3 1.5 0.3 3 3 3 3
Polyethylene homopolymer3 90 95 97.5 99.5 97.5 97 90 95 97.5 99.5 95 95 95 95
Izod Impact Strength4
(kg ·cm/cm2) @ 23ºC 6.5 20.3 18.0 11.0 8.5 18.7 1.5 12.6 11.5 4.3 10.4 15.3 14.6 15
@ -40ºC 3.0 7.0 6.8 4.1 3.5 6.8 0.8 1.3 1.2 1.0 1.1 1.7 1.7 2.1
Average grain size, microns 0.5 0.5 1 1 3 2 0.5 1 1 1 1 1 1 1
1 Blends 15-26 used Nylon-6, blend 25 used Nylon-66, blend 26 used Nylon-11, blend 27 used Nylon-12 and blend 28 used a random copolymer of Nylons 6 and 12, 7125U of Ube Kosan Co.
2 0.4 wt.% addition rate of maleic acid anhydride, MFR 50 g/10 min.
3 MFR 9 g/10 min.
4 According to JIS K 7110 (with notch).
TABLE IV
Component Comparative Blends
5 6 7 8
Polyamide1 8 2 - 8
Modified Polyethylene2 1 0.2 - 1
Propylene homopolymer3 91 97.8 100 91
Izod impact strength
Kg•cm/cm2 @ 23ºC 3.0 2. 7 2.8 1.3
@ -40ºC 1.7 1. 6 1.8 5 λverage grain size, microns 5 7 - 0.8
1 Blends 5, 6,8 used Nylon-6; blends 5, 6 included 8 wt.% ∊-caprolactam.
2 0.4 wt.% addition rate of maleic acid anhydride, MFR 50 g/10 min.
3 MFR 9g/10 min.
4 JIS K 7110 (with notch).
Although the invention has been described with reference to its preferred embodiments, those of ordinary skill in the art may, upon reading this disclosure, appreciate changes and modifications which do not depart from the scope and spirit of the invention as described above or claimed hereafter.
Claims (15)
1. A thermoplastic resin composition
comprising:
(a) a polyolefin resin;
(b) about 0.1 to about 5 wt.% of a polyamide, based upon the weight of the polyolefin resin, dispersed within said polyolefin resin; and
(c) a polyolefin modified with an unsaturated carboxylic acid or its anhydride, said modified polyolefin being present in an amount not less than 0.2 times the amount of the polyamide.
2. The composition of claim l wherein said polyamide resin is dispersed as fine grains of average size less than about 4 μ in the polyolefin resin.
3. The composition of claim 1 wherein said polyamide resin is dispersed as fine grains of average size less than about 2 μ in the polyolefin resin.
4. The composition of claim 1 further comprising; a plasticizer selected from the group consisting of ∊-caprolactam, N-butyl
benzenesulfonamide or octyl-p-oxybenzoate in an amount from about 0.5 to about 40 wt.%, based upon the polyamide weight.
5. The composition of claim 1 further
comprising additives selected from the group
consisting of fillers, heat stabilizers, light
stabilizers, flame retardants, anti-static agents, releasing agents, foaming agents, plasticizers and nucleating agents.
6. The composition of claim 1 wherein the polyolefin resin is selected from a polyethylene, having a high melt load index of greater than about 0.1 and a melt index of less than about 100, and a polypropylene, having a melt flow rate of about 0.01 to about 150.
7. A thermoplastic resin composition
comprising:
(a) a polyolefin resin selected from a polyethylene, having a high melt load index of greater than about 0.1 and a melt index of less than about 100, and a polypropylene, having a melt flow rate of about 0.01 to about 150;
(b) about 0.1 to about 5 wt.% of a polyamide, dispersed as particles of less than about 4 μ average size within said polyolefin resin, based upon the weight of the polyolefin resin; and (c) a modified polyolefin in an amount not less than about 0.2 times the weight of the polyamide.
8. The composition of claim 7 wherein the average particle size of the polyamide is less than about 2 μ.
9. A method for producing a thermoplastic resin composition comprising:
blending under melt conditions a mixture comprising:
(a) a polyolefin resin;
(b) about 0.1 to about 5 wt.% of a
polyamide dispersed within said polyolefin resin, based upon the weight of the polyolefin resin; and
(c) a polyolefin modified with an
unsaturated carboxylic acid or its anhydride, said modified polyolefin being present in an amount not less than about 0.2 times the amount of the
polyamide;
for a time sufficient to disperse the polyamide as particles within the polyolefin resin.
10. The method of claim 9 further comprising adding a radical polymerization catalyst selected from the peroxides.
11. The method of claim 9 wherein the
polyamide and modified polyolefin are melt blended together in a first step before blending with the polyolefin resin.
12. a method for producing a thermoplastic resin composition comprising:
dissolving in an organic solvent while stirring a mixture comprising:
(a) a polyolefin resin;
(b) 0.1 to 5 wt.% of a polyamide dispersed within said polyolefin resin, based upon the weight of the polyolefin resin; and
(c) a polyolefin modified with an
unsaturated carboxylic acid or its anhydride, said modified polyolefin being present in an amount not less than 0.2 times the amount of the polyamide; and removing substantially all the solvent to obtain a thermoplastic resin product.
13. The method of claim 12 further comprising aάding a radical polymerization catalyst selected from the peroxides.
14. A multi-layered laminated molding product comprising:
(i) an upper layer of thermoplastic resin comprising: (a) a polyolefin resin;
(b) about 0.1 to about 5 wt.% of a polyamide dispersed within said polyolefin resin, based upon the weight of the polyolefin resin; and
(c) a polyolefin modified with an unsaturated carboxylic acid or its anhydride, said modified polyolefin being present in an amount not less than about 0,2 times the amount of the polyamide;
(ii) a modified polyolefin layer laminated to one side of the upper thermoplastic resin layer; and
(iii) a polyamide resin layer laminated to the modified polyolefin layer.
15. The molding product of claim 1 further comprising:
(i) a second modified polyolefin layer laminated to the polyamide resin layer; and
iii) a lower thermoplastic resin layer laminated to the second modified polyolefin layer.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1202530A JPH0366735A (en) | 1989-08-04 | 1989-08-04 | Thermoplastic resin composition for laminated formed products |
JP1-202530 | 1989-08-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
AU6166290A true AU6166290A (en) | 1991-03-11 |
Family
ID=16459024
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU61662/90A Abandoned AU6166290A (en) | 1989-08-04 | 1990-08-03 | Thermoplastic resin composition used for multi-layered molding product |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0534958A1 (en) |
JP (1) | JPH0366735A (en) |
KR (1) | KR920703718A (en) |
AU (1) | AU6166290A (en) |
CA (1) | CA2063987A1 (en) |
WO (1) | WO1991002027A1 (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0503909A1 (en) * | 1991-03-14 | 1992-09-16 | Chevron Research And Technology Company | Substantially non-crosslinked maleic anhydride-modified ethylene polymers and process for preparing same |
AT399158B (en) * | 1991-09-13 | 1995-03-27 | Danubia Petrochem Polymere | USE OF MOLDED PARTS MADE OF POLYOLEFINES, POLYAMIDES AND ADHESIVES FOR HIGH-FREQUENCY WELDING, AND FILMS OF POLYOLEFINS, POLYAMIDES AND ADHESIVES |
US5748582A (en) * | 1992-02-14 | 1998-05-05 | Sony Corporation | Information recording medium wherein digital symbols are represented by discrete shift amounts of a pit edge and tracking wobbling pits are shared between adjacent tracks and information recording and reproducing apparatus therefor |
WO1993016467A1 (en) * | 1992-02-14 | 1993-08-19 | Sony Corporation | Data recording medium, data recording apparatus, data reproducing apparatus and data recording/reproducing apparatus |
US5818805A (en) * | 1992-02-14 | 1998-10-06 | Sony Corporation | Reproducing apparatus using an information recording medium wherein multi-bit digital information is represented by a shift amount of a pit edge |
FR2697465A1 (en) * | 1992-10-30 | 1994-05-06 | Atochem Elf Sa | Laminates based on polyamide / polyolefin alloys and coextrusion binders, objects obtained therefrom, coating methods therewith. |
US5517481A (en) * | 1993-07-02 | 1996-05-14 | Sony Corporation | Optical recording and reproducing apparatus wherein data is recorded by stepwise shifting the edge position of each pit |
JPH0845188A (en) * | 1994-07-29 | 1996-02-16 | Sony Corp | Recording method and its recording device and reproducing device |
BE1012224A6 (en) * | 1998-10-08 | 2000-07-04 | Solvay | Hollow thermoplastic multilayer material and method for manufacturing. |
JP4721548B2 (en) * | 2001-05-11 | 2011-07-13 | 旭化成ケミカルズ株式会社 | Resin composition and molded body thereof |
CA2755345A1 (en) | 2009-03-26 | 2010-09-30 | Nestec S.A. | A fitment indexer for a pouch filler |
JP5914318B2 (en) * | 2011-12-22 | 2016-05-11 | トヨタ紡織株式会社 | Method for producing thermoplastic resin composition |
BR112018004849B1 (en) | 2015-12-01 | 2022-11-08 | Toyota Boshoku Kabushiki Kaisha | METHOD FOR USING A MODIFIER TO OBTAIN A MOLDED BODY |
CN108291060B (en) | 2015-12-01 | 2021-04-16 | 丰田纺织株式会社 | Molded article and method for producing same |
US11992980B2 (en) | 2016-03-11 | 2024-05-28 | Toyota Boshoku Kabushiki Kaisha | Foamed resin molded article and method for manufacturing same |
JP6288142B2 (en) | 2016-03-31 | 2018-03-07 | トヨタ紡織株式会社 | Dispersion diameter adjusting method and thermoplastic resin composition |
RU2742377C1 (en) * | 2017-03-16 | 2021-02-05 | Тойота Босоку Кабусики Кайся | Sheet of thermoplastic resin, laminated sheet and molded object |
US11643532B2 (en) | 2017-04-19 | 2023-05-09 | Toyota Boshoku Kabushiki Kaisha | Thermoplastic resin composition, molded object, and production methods therefor |
CN115584087B (en) * | 2022-09-30 | 2024-05-14 | 上海金发科技发展有限公司 | Polypropylene composite material and preparation method and application thereof |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3373224A (en) * | 1964-06-22 | 1968-03-12 | Continental Can Co | Compositions containing polyamides, polyolefins and ethylene-alpha, beta unsaturatedacid copolymers neutralized with sodium ions |
US3373222A (en) * | 1965-09-10 | 1968-03-12 | Continental Can Co | Compositions containing polyamides, polyolefins and carboxylated polyethylene |
US3373223A (en) * | 1965-09-28 | 1968-03-12 | Continental Can Co | Compositions containing polyamides, polyolefins, and ethylene-acrylic or methacrylicacid copolymers |
US3873667A (en) * | 1971-03-18 | 1975-03-25 | Continental Can Co | Process for preparing articles fabricated from polyolefin/polyamide blends having low permeability to gases |
JPS6014695B2 (en) * | 1979-03-06 | 1985-04-15 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Layered molded product and its manufacturing method |
GB8704385D0 (en) * | 1987-02-25 | 1987-04-01 | Du Pont Canada | Injection moulding of articles |
US4950513A (en) * | 1988-03-17 | 1990-08-21 | E. I. Du Pont De Nemours And Company | Laminar articles of a polyolefin and a nylon/polyvinyl alcohol blend |
-
1989
- 1989-08-04 JP JP1202530A patent/JPH0366735A/en active Pending
-
1990
- 1990-08-03 AU AU61662/90A patent/AU6166290A/en not_active Abandoned
- 1990-08-03 WO PCT/US1990/004367 patent/WO1991002027A1/en not_active Application Discontinuation
- 1990-08-03 CA CA002063987A patent/CA2063987A1/en not_active Abandoned
- 1990-08-03 KR KR1019920700249A patent/KR920703718A/en not_active Application Discontinuation
- 1990-08-03 EP EP90912253A patent/EP0534958A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
CA2063987A1 (en) | 1991-02-05 |
WO1991002027A1 (en) | 1991-02-21 |
EP0534958A1 (en) | 1993-04-07 |
JPH0366735A (en) | 1991-03-22 |
KR920703718A (en) | 1992-12-18 |
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