CA2061247C - Transparent impact-resistant molded articles - Google Patents
Transparent impact-resistant molded articlesInfo
- Publication number
- CA2061247C CA2061247C CA002061247A CA2061247A CA2061247C CA 2061247 C CA2061247 C CA 2061247C CA 002061247 A CA002061247 A CA 002061247A CA 2061247 A CA2061247 A CA 2061247A CA 2061247 C CA2061247 C CA 2061247C
- Authority
- CA
- Canada
- Prior art keywords
- polypropylene
- propylene
- ethylene
- weight
- copolymer
- 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.)
- Expired - Fee Related
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Classifications
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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
- C08L23/12—Polypropene
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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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- 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
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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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- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/22—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at neck portion
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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
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/24—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at flange portion
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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
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/26—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at body portion
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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
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/28—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at bottom portion
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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
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3024—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
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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
- B29C2949/30—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
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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
- B29K2023/12—PP, i.e. polypropylene
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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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0026—Transparent
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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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0089—Impact strength or toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7158—Bottles
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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
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/12—Syndiotactic polypropylene
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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
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
Abstract
A molded article obtained by blow molding a propylene having a substantially syndiotactic structure or a resin composition comprising a polypropylene having a substantially syndiotactic structure and a copolymer of ethylene and propylene, and a multi-layer molded article obtained from this resin composition in which at least one surface of the molded article is a polypropylene layer having the substantially syndiotactic structure.
Description
2~?~ ~ ?~ 7 SPECIFICATION
TITLE OF THE I-NV~NllON
Transparent Impàct-resistant Molded Articles BACKGROUND OF THE INVENTION
(i) Field of the Invention The present invention relates to molded articles of a polypropylene which are transparent and excellent in impact resistance. More specifically, it relates to trans-parent and impact-resistant molded articles obtained by blow molding a polypropylene having a substantially syndio-tactic structure, or a composition comprising a polypro-pylene having a substantially syndiotactic structure and a copolymer of ethylene and propylene as well as transparent multi-layer molded articles having good impact-resistance which are obtained from the above-mentioned composition and in which at least one surface of each article has a polypro-pylene layer having a substantially syndiotactic structure.
(ii) Description of the Prior Art A syndiotactic polypropylene has been known for a long period of time. However, a polypropylene obtained by polymerization at a low temperature in the presence of a conventional catalyst comprising a vanadium compound, an ether and an organic aluminum compound is poor in syndio-2~ 7 tacticity. Therefore, the thus prepared polypropylene is hardly considered to have characteristics of the syndiotac-tic polypropylene, and much less, a copolymer of ethylene and propylene which can be obtained by the use of the above-mentioned catalyst is scarcely regarded as a crystallinepolypropylene.
On the contrary, a polypropylene having good tacticity, i.e., a syndiotactic pentad fraction of more than 0.7 has been discovered for the first time by J. A.
Ewen et al. which can be obtained by the use of a catalyst comprising a transition metal compound having asymmetric ligands and an aluminoxane (J. Am. Chem. Soc., 110, 6255-6256, 1988).
Molded articles which can be prepared by molding a syndiotactic polypropylene obtained by the above-mentioned J. A. Ewen et al. method have good transparency and rela-tively excellent stiffness, but they have the problem that their impact resistance at low temperatures is bad.
On the other hand, an isotactic polypropylene is inexpensive and good in heat resistance, and therefore it can be blow molded to manufacture bottles and the like.
However, molded articles made from the isotactic polypropylene have good heat resistance, but they are poor in transparency and bad in impact resistance at low tem-peratures. Thus, for the purpose of improving the impact 2 ~ 7 resistance at the low temperatures, a block copolymer with ethylene can be used, but in this case, there is the problem that its transparency is impaired.
Sl~MMARY OF THE INVENTION
An object of the present invention is to provide a blow molded article of a polypropylene which are excellent in transparency and impact resistance.
Another object o~ the present invention is to provide a multi-layer molded article of a polypropylene which are excellent in transparency, impact resistance and surface hardness.
A first aspect of the present invention provides a transparent impact-resistant molded article obtained by blow molding a polypropylene having a substantially syndiotactic structure, or a resin composition containing such a polypropylene and a copolymer of ethylene and propylene. In one preferred embodiment, the article of the first aspect has a monolayer structure.
A second aspect of the present invention provides a transparent and impact-resistant multi-layer molded article having good stiffness which is obtained from a resin composition containing a polypropylene having a substantially syndiotactic structure and a copolymer of ethylene and propylene, at least one surface of each article being a layer of the polypropylene having the substantially syndiotactic structure.
r~
i ~ 27981-54 - 4 - ~ 2 4 7 -DESCRIPTION OF THE PREFERRED EMBODIMENTS
A polypropylene having a substantially syndiotactic structure can be obtained by, for example, the above-mentioned Ewen et al. method. A suitably usable catalyst is a catalyst system comprising a transition metal compound having asymmetric ligands such as isopropyl(cyclopenta-dienyl-1-fluorenyl)hafnium dichloride or isopropyl(cyclopentadienyl-1-fluorenyl)zirconium dichloride and an aluminoxane which are disclosed in the above-mentioned J.A. Ewen et al. literature. An example of the aluminoxane is what is obtained by condensing an alkylaluminum with water to have a polymerization degree of preferably 5 or more, and more preferably 10 or more. Methylaluminoxane having the above polymerization degree is preferably used.
Another catalyst having a structure which is different from that of the above-mentioned catalyst can also be utilized in the present invention, so long as it I-JL~ 27981-54 _ 5 _ Z0~4~
can provide a homopolymer having a relatively high tac-ticity, i.e., a syndiotactic pentad fraction of 0.7 or more when used to prepare the homopolymer of propylene [A.
Zambelli et al., Macromolecules, 6, 925 (1973j and ibid., 8, 687 (1975)]. For example, a catalyst comprising a transition metal compound having asymmetric ligands and a organic aluminum compound is effective.
The amount of the aluminoxane is from 10 to 1,000,000 mole times, particularly from 50 to 5,000 mole times as much as that of the transition metal compound having the asymmetric ligands. Furthermore, in the case that the organic aluminum compound is used, the amount of this compound is preferably from 0.1 to 100,000 mole times, more preferably from 1 to 10,000 mole times as much as that of the transition metal compound.
No particular restriction is put on a polymeriza-tion process, and there can be utilized a solvent polymeri-zation process using an inert solvent, a bulk polymeriza-tion process in which there is substantially no inert solvent, or a gas phase polymerization process.
Usually, the polymerization temperature is from -100 to 200~C and the polymerization pressure is from atmospheric pressure to 100 kg/cm2 (gauge pressure).
Preferably, the temperature is from -100 to 100~C and the pressure is from atmospheric pressure to 50 kg/cm2 (gauge 20~ 4~
pressure).
Propylene can be polymerized alone or copolymerized with 10% or less of ethylene or an a-olefin having 4 or more carbon atoms, preferably 4 to 20 carbon atoms such as butene-l, pentene-1, hexene-1, heptene-1 or 4-methyl-pentene-l. When the ratio of the above-mentioned ethylene or ~-olefin is in excess of 10% by weight, the character-istics of molded articles obtained from this copolymer, or the resin composition cont~in;ng the ethylene-propylene copolymer deteriorates unpreferably.
In the case that the polypropylene having a sub-stantially syndiotactic structure is a homopolymer of propylene, its syndiotactic pentad fraction preferably is 0.6 or more, more preferably 0.7 or more. When the pentad fraction is 0.6 or less, characteristics of the crystalline polypropylene are not sufficient and physical properties are unpreferably poor.
In the case of the copolymer of propylene and ethylene or the other ~-olefin, the copolymer is such that in the absorption spectrum of l3C-NMR measured in a 1,2,4-trichlorobenzene solution, a peak intensity observed at about 20.2 ppm is 0.3 or more, preferably 0.5 or more of a peak intensity attributed to all the methyl groups of the propylene unit. When this ratio is 0.3 or less, physical properties are unpreferably poor.
2(~6~7 The molecular weight of the polypropylene having the substantially syndiotactic structure is such that its intrinsic viscosity measured in a tetrahydronaphthalene solution at 135~C is from 0.1 to 20, preferably from 0.5 to about 10Ø
The ethylene-propylene copolymer preferably con-tains 10 to 95% by weight of ethylene. When the copolymer having an ethylene content outside this range is blended with the polypropylene having a substantially syndiotactic structure, the improvement effect of impact resistance cannot be obtained. Above all, the ethylene content is preferably from 15 to 90% by weight. In this copolymer, 50% or less of ethylene can be replaced with a-olefin having 4 or more carbon atoms.
The above-mentioned copolymer preferably has a glass transition temperature of -10~C or less, more prefer-ably -20~C or less. An particularly preferable example of the copolymer is such a copolymer as to be sufficiently compatible with the polypropylene having a substantially syndiotactic structure or such a copolymer as to be dis-persible as fine particles in the syndiotactic propylene.
The above-mentioned sufficiently compatible copolymer has propylene chains in a racemic state. The degree of this racemic state can be represented by a racemic fraction of a serial of 2 or 3 propylene monomers, when 6 monomer units 20~ 24~
in the polymer chain are observed, and this structure can be elucidated by l3C-NMR. For example, this detail has been reported in Asakura et al.[Polymer, 129, 2208 (1988)].
Furthermore, the above-mèntioned copolymer which is dis-persible as fine particles preferably has a relatively lowmelt viscosity and is dispersible in the state of fine particles smaller than the wave length of visible light when mixed.
Such a copolymer can be prepared by the use of a certain kind of catalyst such as a titanium compound-containing catalyst, a vanadium compound-cont~in;ng cata-lyst or a metallocene-cont~ining catalyst. The copolymer is also commercially available under various trademarks.
The molecular weight of this copolymer is such that its intrinsic viscosity measured in a tetrahydronaphthalene solution at 135~C is preferably from 0.1 to 20, more prefer-ably from 0.5 to 10.
In the resin composition comprising the polypro-pylene having a substantially syndiotactic structure and the copolymer of ethylene and propylene, the weight ratio of the polypropylene to the copolymer is preferably not less than 30/70, more preferably not less than 45/55, and the upper limit of the weight ratio is preferably 99/1.
When the above-mentioned weight ratio is less than 30/70, the molded articles obtained from such a resin 2~ 7 g composition are poor in stiffness.
When the upper limit of the weight ratio is in excess of 99/1, the molded articles obtained from such a resin composition scarceiy exert the improvement effect of impact resistance, and the impact resistance of these molded articles is substantially equal to that of molded articles obtained from the polypropylene having a syndio-tactic structure.
The particularly preferable weight ratio is present in the range of from 55/45 to 98/2.
The resin composition which can be used in the present invention can be prepared by mixing the polypro-pylene having the substantially syndiotactic structure and the copolymer of ethylene and propylene in the above-mentioned ratio by the use of a kneader which can achieve good mixing. Alternatively, the resin composition can be obtained by the so-called block copolymerization process which comprises first polymerizing propylene to form the polypropylene having a substantially syndiotactic struc-ture, and then copolymerizing ethylene and propylene in this polymerization system. A method which can provide better results comprises vigorously kneading the copolymer having racemic propylene chains with the polypropylene having the substantially syndiotactic structure.
As the above-mentioned kneader, there can be used a 20~ 47 kneader which can carry out relatively vigorous kneading, for example a twin-screw extruder or a Bumbury's kneader.
A kneading temperature lS preferably from 150 to 350~C, more preferably 180 to 300~C. In the case that the copoly-mer in which the propylene chain is racemic is kneaded withthe polypropylene having the substantially syndiotactic structure so as to obtain the good results, a glass transi-tion temperature is measured by analyzing dynamic visco-elasticity, and the kneading operation should be carried out until the transition attributed to the ethylene-propylene copolymer is not observed any more. Here, the observation of no transition means that a peak of tan attributed to the copolymer of ethylene and propylene decreases to about 1/3 of a value before the kneading, when the measurement is made by a dynamic mechanical thermal analysis.
The thus obtained resin composition, or a polypro-pylene having a substantially syndiotactic structure is then blow molded. In the present invention, any blow molding process can be employed, so long as it basically comprises the steps of forming a parison, feeding the same to a mold, injecting compressed air or the like thereinto, and then blowing it. Particularly, with regard to the formation of the parison, various improved processes are known, and they can be employed in the present invention.
;~06~2A 7 For example, there are a process of molding the material into a cylindrical form by extrusion molding, and then blowing it; a process of cooling and cutting the cylin-drical material, and then heating and blowing it; and a process of molding the material into a cylindrical form by injection molding, and then blowing it.
The molded articles which are obtained from the resin composition comprising the polypropylene having the substantially syndiotactic structure and the copolymer of ethylene and propylene are excellent in impact resistance at low temperatures, but they have the problem that surface hardness is slightly poor. This problem can be solved by allowing at least one surface of the molded article from the above-mentioned resin composition to be made from the polypropylene having the substantially syndiotactic struc-ture.
No particular restriction is put on a method for preparing such multi-layer molded articles, and a suitable method such as multi-layer blow molding, multi-layer injec-tion molding or multi-layer extrusion can be employed.
Here, it is important that the surface on which hardness is required is made from the polypropylene having the substan-tially syndiotactic structure. A particularly preferable example of the polypropylene having the substantially syndiotactic structure is a propylene homopolymer having 2~ 247 such a structure.
The thickness ratio of the layer of the above-mentioned resin composition to the layer of the polypro-pylene is preferably in the range of from 1/1 to 1/0.001, more preferably from 1/0.5 to 1/0.05 in view of the improve-ment of the impact resistance at low temperatures.
In the case of molded articles such as bottles which can be obtained by blow molding, only the outer layers of these molded articles may be made from the poly-propylene having the substantially syndiotactic structure and the inner portions thereof may be free from the polypro-pylene layer having the substantially syndiotactic struc-ture.
The molded articles according to the present invention are excellent in transparency and luster regard-ing appearance, and they are also excellent in impact resistance. In addition, they are also excellent in sur-face hardness, if they are prepared in the form of multi-layer molded articles.
The present invention will be described in refer-ence to examples and comparative examples. It should be noted that the scope of the present invention is not limited to these examples.
In the examples, G at the rear of pressure values represents a gauge pressure, and wt.% means % by weight.
~06~7 Example 1 (a) 15 mg of isopropyl(cyclopentadienyl-1-fluo-renyl)zirconium dichloride and 2 g of methylaluminoxane (polymerization degree 16.1) made by Toso Akzo Co., Ltd were dissolved in 3 liters of toluene in a 7-liter auto-clave. This isopropyl(cyclopentadienyl-1-fluorenyl)zirco-nium dichloride was obtained by converting, into a lithium salt, isopropylcyclopentadienyl-1-fluorene synthesized in an ordinary manner, reacting the same with zirconium tetra-chloride, and then recrystallizing the resultant reactionproduct. Afterward, propylene was fed to the autoclave at 20~C, until a pressure of 4 kg/cm2-G was attained, and polymerization was then carried out for 1 hour, while propylene was additionally fed so as to keep up 4 kg/cm2-G.
Next, propylene was purged from the autoclave, until 0.5 kg/cm2-G was attained. A part of the resultant slurry was sampled, filtered, and then dried to obtain a polymer, and this polymer was dissolved in 1,2,4-trichlorobenzene and then analyzed by l3C-NMR. As a result, the ratio of syndio-tactic pentad was 0.93.
(b) Ethylene was added to the autoclave so as tobe 3 kg/cm2-G, and polymerization was then carried out for 20 minutes. After completion of the polymerization, the unreacted monomer was purged, and the resulting polymerization mixture was filtered to obtain a powder. This powder was 20~2~7 washed 5 times with 1 liter of hexane every time, and then dried at 80~C under reduced pressure to obtain 220 g of a polymer. Afterward, this polymer was analyzed by l3C-NMR, and as a result, the content of ethylene in the polymer was 12.4 wt.%, and the ratio of the syndiotactic pentad was 0.78. Furthermore, an intrinsic viscosity (hereinafter referred to as "~") measured in a tetrahydronaphthalene solution at 135~C was 1.24, and a ratio of the weight average molecular weight to the number average molecular weight of the polymer (hereinafter referred to as "MW/MN") measured in a 1,2,4-trichlorobenzene solution at 135~C was 6.7. The ratio of the ethylene-propylene copolymer to the total polymer was calculated from concentrations of the slurries before and after the commencement of the copoly-merization of ethylene and propylene, and as a result, thisratio was 32 wt.%. In consequence, it can be presumed that the ethylene content in the copolymer was 41 wt.%.
(c) The thus obtained polymer was further kneaded at 210~C by means of an extruder having a cylinder diameter of 30 mm made by Ikegai Iron Works, Ltd., and it was then molded at a parison molding temperature of 195~C and at a mold temperature of 20~C at the time of blowing by a blow molding machine made by Placo Co., Ltd. to prepare a blown bottle of an internal volume of 750 ml. For the thus molded article, haze (%) was measured in accordance with Z~ 47 ASTM D1003, and Izod impact strength (kg-cm/cm) was mea-sured in accordance with ASTM D256 (23~C, -10~C) for sam-ples which were prepared by cutting the blown bottle. As a result, Metsuke (the weight of the blown bottle) was 41 g, the haze was 12.4%, and the Izod impact strength was 58 and 49 kg-cm/cm, respectively.
Example 2 (a) Propylene was polymerized by the same pro-cedure as in Example 1 (a) to obtain a polymer having ~ of 1.38, a syndiotactic pentad ratio of 0.93, and MW/MN of 2.1. Next, this polymer was molded in the same molding manner as in Example 1 (c) to obtain a blown bottle.
Physical properties of this blown bottle were as follows:
Metsuke was 37 g, haze was 10.8%, and Izod impact strength was 58 and 3.5 kg-cm/cm, respectively.
(b) A catalyst obtained in Example 1 (a) was used, and propylene was fed to an autoclave until 0.5 kg/cm2 (gauge) was attained and ethylene was fed thereto until 3 kg/cm2 was attained. Polymerization was then carried out to prepare a copolymer of ethylene and propylene. ~ of this copolymer was 0.88, and an ethylene content was 45 wt.%.
(c) 30 parts by weight of this copolymer were mixed with 70 parts by weight of syndiotactic polypropylene obtained in the above-mentioned paragraph (a) by the use of 206~ 7 the same extruder and in the same manner as used in Example 1 (c) to obtain a composition. Next, this composition was molded into a blown bottle. With regard to physical pro-perties of this blown bottle, Metsuke was 42 g, haze was 12.1%, and Izod impact strength was 58 and 59 kg-cm/cm, respectively.
Example 3 70 parts by weight of a polymer obtained in Example 2 (a) were mixed with 30 parts by weight of Tafmer (trade-mark) SPO370 (~ was 1.41, and an ethylene content was 70.6 wt.%) made by Mitsui Petrochemical Industries, Ltd. which was a random copolymer of ethylene and propylene in the same manner as in Example 2 (a) to obtain a composition.
Next, this composition was molded into a blown bottle in the same manner as in Example 1. With regard to physical properties of this blown bottle, Metsuke was 49 g, haze was 13.1%, and Izod impact strength was 61 and 63 kg-cm/cm, respectively.
Comparative Example 1 A commercially available isotactic polypropylene (MJS 5.1 made by Mitsui Toatsu Chemicals, Inc; a random copolymer of propylene and ethylene having an ethylene content of 4.9 wt.% and a melt index of 1.5 g/minute) was blow molded in the same manner as in Example 1 (c). Physi-cal properties of the thus molded article were as follows:
- 17 - ~ q7 Metsuke was 69 g, haze was 51.5%, and Izod impact strength was 48 and 2.8 kg-cm/cm, respectively.
Examples 4 to 7 and Comp. Example 2 A syndiotactic polypropylene obtained in Example 2 (a) was kneaded with an ethylene-propylene copolymer obtained in Example 2 (b) in ratios shown in Table 1 in the same manner as in Example 1 (c), followed by blow molding in the same manner as in Example 1 (c). For the thus obtained blown bottles, physical properties were measured.
The results are set forth in Table 1. In this connection, the composition of Comparative Example 2 could not be molded.
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Examples 8 to 11 and comP. Example 3 Ethylene-propylene copolymers having ethylene contents shown in Table 2 were prepared in accordance with the procedure of Example 2 (b). Each copolymer was kneaded with a syndiotactic polypropylene obtained in Example 2 (a) in a ratio of 50/50 in the same manner as in Example 1 (c), followed by blow molding in the same manner as in Example 1 (c). Physical properties of the thus obtained blown bottles are shown in Table 2.
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Example 12 A polymer obtained in Example 1 (b) was kneaded in the same manner as in Example 1 (c), and the polymer was then blow molded at a parison molding temperature of 195~C
and at a blow mold temperature of 20~C by the use of a multi-layer blow molding machine made by Placo Co., Ltd., an outer layer of an article to be molded being made from a syndiotactic polypropylene obtained in Example 2 (a), and an inner layer being made from the above-mentioned polymer.
With regard to physical properties of the thus obtained blown bottle of an internal volume of 750 ml, Metsuke was 41 g, haze was 12.4%, Izod impact strength was 58 and 49 kg-cm/cm, respectively, and surface hardness was 51 gf.
Furthermore, according to observation and calculation of a sectional view of a specimen prepared by cutting the bottle, the thickness of the outer layer was 0.15 mm, and that of the inner layer was 0.6 mm.
In addition, for the blown bottle obtained in Example 1, surface hardness was measured. As a result, it was 23 gf.
Example 13 30 parts by weight of an ethylene-propylene copoly-mer obtained in Example 2 (b) were kneaded with 70 parts by weight of a syndiotactic polypropylene obtained in Example 2 (a) in the same manner as in Example 1 (c), thereby - 22 - 2~ 7 obt~ining a resin composition. This resin composition was then molded in the same manner as in Example 12 to obtain a blown bottle, the inner layer of this bottle being made from the above-mentioned resin composition. With regard to physical properties of the thus obtained blown bottle, Metsuke was 42 g, haze was 12.1%, Izod impact strength was 58 and 59 kg-cm/cm, respectively, and surface hardness was 51 gf. In this bottle, the thickness of the outer layer was 0.2 mm, and that of the inner layer was 0.6 mm.
Example 14 The same procedure as in Example 12 was effected except that a resin composition in Example 3 was used as an inner layer, thereby molding a multi-layer blown bottle.
With regard to physical properties of the thus molded blown bottle, Metsuke was 49 g, haze was 13.1~, and Izod impact strength was 61 and 63 kg-cm/cm. In this bottle, the thickness of the outer layer was 0.2 mm and that of the inner layer was 0.65 mm, and surface hardness was 53 gf.
Comparative Example 4 For a blown bottle made from an isotactic polypro-pylene in Comparative Example 1, surface hardness was measured. As a result, it was 60 gf.
In a resin composition which can be used in the present invention, various usual additives can be contained which are, for example, an antioxidant, an ultraviolet 20~ 17 absorber, an antiblocking agent, a slip agent and a nucleat-ing agent.
Examples of multi-layer molded articles in which at least one surface is made from the polypropylene having a substantially syndiotactic structure include various molded articles such as plates, extruding materials, sheets, films and pipes, in addition to the blown bottles shown in the above-mentioned examples.
TITLE OF THE I-NV~NllON
Transparent Impàct-resistant Molded Articles BACKGROUND OF THE INVENTION
(i) Field of the Invention The present invention relates to molded articles of a polypropylene which are transparent and excellent in impact resistance. More specifically, it relates to trans-parent and impact-resistant molded articles obtained by blow molding a polypropylene having a substantially syndio-tactic structure, or a composition comprising a polypro-pylene having a substantially syndiotactic structure and a copolymer of ethylene and propylene as well as transparent multi-layer molded articles having good impact-resistance which are obtained from the above-mentioned composition and in which at least one surface of each article has a polypro-pylene layer having a substantially syndiotactic structure.
(ii) Description of the Prior Art A syndiotactic polypropylene has been known for a long period of time. However, a polypropylene obtained by polymerization at a low temperature in the presence of a conventional catalyst comprising a vanadium compound, an ether and an organic aluminum compound is poor in syndio-2~ 7 tacticity. Therefore, the thus prepared polypropylene is hardly considered to have characteristics of the syndiotac-tic polypropylene, and much less, a copolymer of ethylene and propylene which can be obtained by the use of the above-mentioned catalyst is scarcely regarded as a crystallinepolypropylene.
On the contrary, a polypropylene having good tacticity, i.e., a syndiotactic pentad fraction of more than 0.7 has been discovered for the first time by J. A.
Ewen et al. which can be obtained by the use of a catalyst comprising a transition metal compound having asymmetric ligands and an aluminoxane (J. Am. Chem. Soc., 110, 6255-6256, 1988).
Molded articles which can be prepared by molding a syndiotactic polypropylene obtained by the above-mentioned J. A. Ewen et al. method have good transparency and rela-tively excellent stiffness, but they have the problem that their impact resistance at low temperatures is bad.
On the other hand, an isotactic polypropylene is inexpensive and good in heat resistance, and therefore it can be blow molded to manufacture bottles and the like.
However, molded articles made from the isotactic polypropylene have good heat resistance, but they are poor in transparency and bad in impact resistance at low tem-peratures. Thus, for the purpose of improving the impact 2 ~ 7 resistance at the low temperatures, a block copolymer with ethylene can be used, but in this case, there is the problem that its transparency is impaired.
Sl~MMARY OF THE INVENTION
An object of the present invention is to provide a blow molded article of a polypropylene which are excellent in transparency and impact resistance.
Another object o~ the present invention is to provide a multi-layer molded article of a polypropylene which are excellent in transparency, impact resistance and surface hardness.
A first aspect of the present invention provides a transparent impact-resistant molded article obtained by blow molding a polypropylene having a substantially syndiotactic structure, or a resin composition containing such a polypropylene and a copolymer of ethylene and propylene. In one preferred embodiment, the article of the first aspect has a monolayer structure.
A second aspect of the present invention provides a transparent and impact-resistant multi-layer molded article having good stiffness which is obtained from a resin composition containing a polypropylene having a substantially syndiotactic structure and a copolymer of ethylene and propylene, at least one surface of each article being a layer of the polypropylene having the substantially syndiotactic structure.
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i ~ 27981-54 - 4 - ~ 2 4 7 -DESCRIPTION OF THE PREFERRED EMBODIMENTS
A polypropylene having a substantially syndiotactic structure can be obtained by, for example, the above-mentioned Ewen et al. method. A suitably usable catalyst is a catalyst system comprising a transition metal compound having asymmetric ligands such as isopropyl(cyclopenta-dienyl-1-fluorenyl)hafnium dichloride or isopropyl(cyclopentadienyl-1-fluorenyl)zirconium dichloride and an aluminoxane which are disclosed in the above-mentioned J.A. Ewen et al. literature. An example of the aluminoxane is what is obtained by condensing an alkylaluminum with water to have a polymerization degree of preferably 5 or more, and more preferably 10 or more. Methylaluminoxane having the above polymerization degree is preferably used.
Another catalyst having a structure which is different from that of the above-mentioned catalyst can also be utilized in the present invention, so long as it I-JL~ 27981-54 _ 5 _ Z0~4~
can provide a homopolymer having a relatively high tac-ticity, i.e., a syndiotactic pentad fraction of 0.7 or more when used to prepare the homopolymer of propylene [A.
Zambelli et al., Macromolecules, 6, 925 (1973j and ibid., 8, 687 (1975)]. For example, a catalyst comprising a transition metal compound having asymmetric ligands and a organic aluminum compound is effective.
The amount of the aluminoxane is from 10 to 1,000,000 mole times, particularly from 50 to 5,000 mole times as much as that of the transition metal compound having the asymmetric ligands. Furthermore, in the case that the organic aluminum compound is used, the amount of this compound is preferably from 0.1 to 100,000 mole times, more preferably from 1 to 10,000 mole times as much as that of the transition metal compound.
No particular restriction is put on a polymeriza-tion process, and there can be utilized a solvent polymeri-zation process using an inert solvent, a bulk polymeriza-tion process in which there is substantially no inert solvent, or a gas phase polymerization process.
Usually, the polymerization temperature is from -100 to 200~C and the polymerization pressure is from atmospheric pressure to 100 kg/cm2 (gauge pressure).
Preferably, the temperature is from -100 to 100~C and the pressure is from atmospheric pressure to 50 kg/cm2 (gauge 20~ 4~
pressure).
Propylene can be polymerized alone or copolymerized with 10% or less of ethylene or an a-olefin having 4 or more carbon atoms, preferably 4 to 20 carbon atoms such as butene-l, pentene-1, hexene-1, heptene-1 or 4-methyl-pentene-l. When the ratio of the above-mentioned ethylene or ~-olefin is in excess of 10% by weight, the character-istics of molded articles obtained from this copolymer, or the resin composition cont~in;ng the ethylene-propylene copolymer deteriorates unpreferably.
In the case that the polypropylene having a sub-stantially syndiotactic structure is a homopolymer of propylene, its syndiotactic pentad fraction preferably is 0.6 or more, more preferably 0.7 or more. When the pentad fraction is 0.6 or less, characteristics of the crystalline polypropylene are not sufficient and physical properties are unpreferably poor.
In the case of the copolymer of propylene and ethylene or the other ~-olefin, the copolymer is such that in the absorption spectrum of l3C-NMR measured in a 1,2,4-trichlorobenzene solution, a peak intensity observed at about 20.2 ppm is 0.3 or more, preferably 0.5 or more of a peak intensity attributed to all the methyl groups of the propylene unit. When this ratio is 0.3 or less, physical properties are unpreferably poor.
2(~6~7 The molecular weight of the polypropylene having the substantially syndiotactic structure is such that its intrinsic viscosity measured in a tetrahydronaphthalene solution at 135~C is from 0.1 to 20, preferably from 0.5 to about 10Ø
The ethylene-propylene copolymer preferably con-tains 10 to 95% by weight of ethylene. When the copolymer having an ethylene content outside this range is blended with the polypropylene having a substantially syndiotactic structure, the improvement effect of impact resistance cannot be obtained. Above all, the ethylene content is preferably from 15 to 90% by weight. In this copolymer, 50% or less of ethylene can be replaced with a-olefin having 4 or more carbon atoms.
The above-mentioned copolymer preferably has a glass transition temperature of -10~C or less, more prefer-ably -20~C or less. An particularly preferable example of the copolymer is such a copolymer as to be sufficiently compatible with the polypropylene having a substantially syndiotactic structure or such a copolymer as to be dis-persible as fine particles in the syndiotactic propylene.
The above-mentioned sufficiently compatible copolymer has propylene chains in a racemic state. The degree of this racemic state can be represented by a racemic fraction of a serial of 2 or 3 propylene monomers, when 6 monomer units 20~ 24~
in the polymer chain are observed, and this structure can be elucidated by l3C-NMR. For example, this detail has been reported in Asakura et al.[Polymer, 129, 2208 (1988)].
Furthermore, the above-mèntioned copolymer which is dis-persible as fine particles preferably has a relatively lowmelt viscosity and is dispersible in the state of fine particles smaller than the wave length of visible light when mixed.
Such a copolymer can be prepared by the use of a certain kind of catalyst such as a titanium compound-containing catalyst, a vanadium compound-cont~in;ng cata-lyst or a metallocene-cont~ining catalyst. The copolymer is also commercially available under various trademarks.
The molecular weight of this copolymer is such that its intrinsic viscosity measured in a tetrahydronaphthalene solution at 135~C is preferably from 0.1 to 20, more prefer-ably from 0.5 to 10.
In the resin composition comprising the polypro-pylene having a substantially syndiotactic structure and the copolymer of ethylene and propylene, the weight ratio of the polypropylene to the copolymer is preferably not less than 30/70, more preferably not less than 45/55, and the upper limit of the weight ratio is preferably 99/1.
When the above-mentioned weight ratio is less than 30/70, the molded articles obtained from such a resin 2~ 7 g composition are poor in stiffness.
When the upper limit of the weight ratio is in excess of 99/1, the molded articles obtained from such a resin composition scarceiy exert the improvement effect of impact resistance, and the impact resistance of these molded articles is substantially equal to that of molded articles obtained from the polypropylene having a syndio-tactic structure.
The particularly preferable weight ratio is present in the range of from 55/45 to 98/2.
The resin composition which can be used in the present invention can be prepared by mixing the polypro-pylene having the substantially syndiotactic structure and the copolymer of ethylene and propylene in the above-mentioned ratio by the use of a kneader which can achieve good mixing. Alternatively, the resin composition can be obtained by the so-called block copolymerization process which comprises first polymerizing propylene to form the polypropylene having a substantially syndiotactic struc-ture, and then copolymerizing ethylene and propylene in this polymerization system. A method which can provide better results comprises vigorously kneading the copolymer having racemic propylene chains with the polypropylene having the substantially syndiotactic structure.
As the above-mentioned kneader, there can be used a 20~ 47 kneader which can carry out relatively vigorous kneading, for example a twin-screw extruder or a Bumbury's kneader.
A kneading temperature lS preferably from 150 to 350~C, more preferably 180 to 300~C. In the case that the copoly-mer in which the propylene chain is racemic is kneaded withthe polypropylene having the substantially syndiotactic structure so as to obtain the good results, a glass transi-tion temperature is measured by analyzing dynamic visco-elasticity, and the kneading operation should be carried out until the transition attributed to the ethylene-propylene copolymer is not observed any more. Here, the observation of no transition means that a peak of tan attributed to the copolymer of ethylene and propylene decreases to about 1/3 of a value before the kneading, when the measurement is made by a dynamic mechanical thermal analysis.
The thus obtained resin composition, or a polypro-pylene having a substantially syndiotactic structure is then blow molded. In the present invention, any blow molding process can be employed, so long as it basically comprises the steps of forming a parison, feeding the same to a mold, injecting compressed air or the like thereinto, and then blowing it. Particularly, with regard to the formation of the parison, various improved processes are known, and they can be employed in the present invention.
;~06~2A 7 For example, there are a process of molding the material into a cylindrical form by extrusion molding, and then blowing it; a process of cooling and cutting the cylin-drical material, and then heating and blowing it; and a process of molding the material into a cylindrical form by injection molding, and then blowing it.
The molded articles which are obtained from the resin composition comprising the polypropylene having the substantially syndiotactic structure and the copolymer of ethylene and propylene are excellent in impact resistance at low temperatures, but they have the problem that surface hardness is slightly poor. This problem can be solved by allowing at least one surface of the molded article from the above-mentioned resin composition to be made from the polypropylene having the substantially syndiotactic struc-ture.
No particular restriction is put on a method for preparing such multi-layer molded articles, and a suitable method such as multi-layer blow molding, multi-layer injec-tion molding or multi-layer extrusion can be employed.
Here, it is important that the surface on which hardness is required is made from the polypropylene having the substan-tially syndiotactic structure. A particularly preferable example of the polypropylene having the substantially syndiotactic structure is a propylene homopolymer having 2~ 247 such a structure.
The thickness ratio of the layer of the above-mentioned resin composition to the layer of the polypro-pylene is preferably in the range of from 1/1 to 1/0.001, more preferably from 1/0.5 to 1/0.05 in view of the improve-ment of the impact resistance at low temperatures.
In the case of molded articles such as bottles which can be obtained by blow molding, only the outer layers of these molded articles may be made from the poly-propylene having the substantially syndiotactic structure and the inner portions thereof may be free from the polypro-pylene layer having the substantially syndiotactic struc-ture.
The molded articles according to the present invention are excellent in transparency and luster regard-ing appearance, and they are also excellent in impact resistance. In addition, they are also excellent in sur-face hardness, if they are prepared in the form of multi-layer molded articles.
The present invention will be described in refer-ence to examples and comparative examples. It should be noted that the scope of the present invention is not limited to these examples.
In the examples, G at the rear of pressure values represents a gauge pressure, and wt.% means % by weight.
~06~7 Example 1 (a) 15 mg of isopropyl(cyclopentadienyl-1-fluo-renyl)zirconium dichloride and 2 g of methylaluminoxane (polymerization degree 16.1) made by Toso Akzo Co., Ltd were dissolved in 3 liters of toluene in a 7-liter auto-clave. This isopropyl(cyclopentadienyl-1-fluorenyl)zirco-nium dichloride was obtained by converting, into a lithium salt, isopropylcyclopentadienyl-1-fluorene synthesized in an ordinary manner, reacting the same with zirconium tetra-chloride, and then recrystallizing the resultant reactionproduct. Afterward, propylene was fed to the autoclave at 20~C, until a pressure of 4 kg/cm2-G was attained, and polymerization was then carried out for 1 hour, while propylene was additionally fed so as to keep up 4 kg/cm2-G.
Next, propylene was purged from the autoclave, until 0.5 kg/cm2-G was attained. A part of the resultant slurry was sampled, filtered, and then dried to obtain a polymer, and this polymer was dissolved in 1,2,4-trichlorobenzene and then analyzed by l3C-NMR. As a result, the ratio of syndio-tactic pentad was 0.93.
(b) Ethylene was added to the autoclave so as tobe 3 kg/cm2-G, and polymerization was then carried out for 20 minutes. After completion of the polymerization, the unreacted monomer was purged, and the resulting polymerization mixture was filtered to obtain a powder. This powder was 20~2~7 washed 5 times with 1 liter of hexane every time, and then dried at 80~C under reduced pressure to obtain 220 g of a polymer. Afterward, this polymer was analyzed by l3C-NMR, and as a result, the content of ethylene in the polymer was 12.4 wt.%, and the ratio of the syndiotactic pentad was 0.78. Furthermore, an intrinsic viscosity (hereinafter referred to as "~") measured in a tetrahydronaphthalene solution at 135~C was 1.24, and a ratio of the weight average molecular weight to the number average molecular weight of the polymer (hereinafter referred to as "MW/MN") measured in a 1,2,4-trichlorobenzene solution at 135~C was 6.7. The ratio of the ethylene-propylene copolymer to the total polymer was calculated from concentrations of the slurries before and after the commencement of the copoly-merization of ethylene and propylene, and as a result, thisratio was 32 wt.%. In consequence, it can be presumed that the ethylene content in the copolymer was 41 wt.%.
(c) The thus obtained polymer was further kneaded at 210~C by means of an extruder having a cylinder diameter of 30 mm made by Ikegai Iron Works, Ltd., and it was then molded at a parison molding temperature of 195~C and at a mold temperature of 20~C at the time of blowing by a blow molding machine made by Placo Co., Ltd. to prepare a blown bottle of an internal volume of 750 ml. For the thus molded article, haze (%) was measured in accordance with Z~ 47 ASTM D1003, and Izod impact strength (kg-cm/cm) was mea-sured in accordance with ASTM D256 (23~C, -10~C) for sam-ples which were prepared by cutting the blown bottle. As a result, Metsuke (the weight of the blown bottle) was 41 g, the haze was 12.4%, and the Izod impact strength was 58 and 49 kg-cm/cm, respectively.
Example 2 (a) Propylene was polymerized by the same pro-cedure as in Example 1 (a) to obtain a polymer having ~ of 1.38, a syndiotactic pentad ratio of 0.93, and MW/MN of 2.1. Next, this polymer was molded in the same molding manner as in Example 1 (c) to obtain a blown bottle.
Physical properties of this blown bottle were as follows:
Metsuke was 37 g, haze was 10.8%, and Izod impact strength was 58 and 3.5 kg-cm/cm, respectively.
(b) A catalyst obtained in Example 1 (a) was used, and propylene was fed to an autoclave until 0.5 kg/cm2 (gauge) was attained and ethylene was fed thereto until 3 kg/cm2 was attained. Polymerization was then carried out to prepare a copolymer of ethylene and propylene. ~ of this copolymer was 0.88, and an ethylene content was 45 wt.%.
(c) 30 parts by weight of this copolymer were mixed with 70 parts by weight of syndiotactic polypropylene obtained in the above-mentioned paragraph (a) by the use of 206~ 7 the same extruder and in the same manner as used in Example 1 (c) to obtain a composition. Next, this composition was molded into a blown bottle. With regard to physical pro-perties of this blown bottle, Metsuke was 42 g, haze was 12.1%, and Izod impact strength was 58 and 59 kg-cm/cm, respectively.
Example 3 70 parts by weight of a polymer obtained in Example 2 (a) were mixed with 30 parts by weight of Tafmer (trade-mark) SPO370 (~ was 1.41, and an ethylene content was 70.6 wt.%) made by Mitsui Petrochemical Industries, Ltd. which was a random copolymer of ethylene and propylene in the same manner as in Example 2 (a) to obtain a composition.
Next, this composition was molded into a blown bottle in the same manner as in Example 1. With regard to physical properties of this blown bottle, Metsuke was 49 g, haze was 13.1%, and Izod impact strength was 61 and 63 kg-cm/cm, respectively.
Comparative Example 1 A commercially available isotactic polypropylene (MJS 5.1 made by Mitsui Toatsu Chemicals, Inc; a random copolymer of propylene and ethylene having an ethylene content of 4.9 wt.% and a melt index of 1.5 g/minute) was blow molded in the same manner as in Example 1 (c). Physi-cal properties of the thus molded article were as follows:
- 17 - ~ q7 Metsuke was 69 g, haze was 51.5%, and Izod impact strength was 48 and 2.8 kg-cm/cm, respectively.
Examples 4 to 7 and Comp. Example 2 A syndiotactic polypropylene obtained in Example 2 (a) was kneaded with an ethylene-propylene copolymer obtained in Example 2 (b) in ratios shown in Table 1 in the same manner as in Example 1 (c), followed by blow molding in the same manner as in Example 1 (c). For the thus obtained blown bottles, physical properties were measured.
The results are set forth in Table 1. In this connection, the composition of Comparative Example 2 could not be molded.
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Examples 8 to 11 and comP. Example 3 Ethylene-propylene copolymers having ethylene contents shown in Table 2 were prepared in accordance with the procedure of Example 2 (b). Each copolymer was kneaded with a syndiotactic polypropylene obtained in Example 2 (a) in a ratio of 50/50 in the same manner as in Example 1 (c), followed by blow molding in the same manner as in Example 1 (c). Physical properties of the thus obtained blown bottles are shown in Table 2.
20Ç~247 UJ
a ~
N
U~ O
C) O
~; X
U~ N
D H
D ~U _O ~--~ N o~O ~ . . .
a 3 1 ~ ~ ~ ~ u E~
C ~1 o ~ s~
D C ~ o o o u~ co :~ O
.
o ao o~
~D ~ ~D aD a: a aD ~
W O C~ Iy ~ pq IY i~l ~
z~
Example 12 A polymer obtained in Example 1 (b) was kneaded in the same manner as in Example 1 (c), and the polymer was then blow molded at a parison molding temperature of 195~C
and at a blow mold temperature of 20~C by the use of a multi-layer blow molding machine made by Placo Co., Ltd., an outer layer of an article to be molded being made from a syndiotactic polypropylene obtained in Example 2 (a), and an inner layer being made from the above-mentioned polymer.
With regard to physical properties of the thus obtained blown bottle of an internal volume of 750 ml, Metsuke was 41 g, haze was 12.4%, Izod impact strength was 58 and 49 kg-cm/cm, respectively, and surface hardness was 51 gf.
Furthermore, according to observation and calculation of a sectional view of a specimen prepared by cutting the bottle, the thickness of the outer layer was 0.15 mm, and that of the inner layer was 0.6 mm.
In addition, for the blown bottle obtained in Example 1, surface hardness was measured. As a result, it was 23 gf.
Example 13 30 parts by weight of an ethylene-propylene copoly-mer obtained in Example 2 (b) were kneaded with 70 parts by weight of a syndiotactic polypropylene obtained in Example 2 (a) in the same manner as in Example 1 (c), thereby - 22 - 2~ 7 obt~ining a resin composition. This resin composition was then molded in the same manner as in Example 12 to obtain a blown bottle, the inner layer of this bottle being made from the above-mentioned resin composition. With regard to physical properties of the thus obtained blown bottle, Metsuke was 42 g, haze was 12.1%, Izod impact strength was 58 and 59 kg-cm/cm, respectively, and surface hardness was 51 gf. In this bottle, the thickness of the outer layer was 0.2 mm, and that of the inner layer was 0.6 mm.
Example 14 The same procedure as in Example 12 was effected except that a resin composition in Example 3 was used as an inner layer, thereby molding a multi-layer blown bottle.
With regard to physical properties of the thus molded blown bottle, Metsuke was 49 g, haze was 13.1~, and Izod impact strength was 61 and 63 kg-cm/cm. In this bottle, the thickness of the outer layer was 0.2 mm and that of the inner layer was 0.65 mm, and surface hardness was 53 gf.
Comparative Example 4 For a blown bottle made from an isotactic polypro-pylene in Comparative Example 1, surface hardness was measured. As a result, it was 60 gf.
In a resin composition which can be used in the present invention, various usual additives can be contained which are, for example, an antioxidant, an ultraviolet 20~ 17 absorber, an antiblocking agent, a slip agent and a nucleat-ing agent.
Examples of multi-layer molded articles in which at least one surface is made from the polypropylene having a substantially syndiotactic structure include various molded articles such as plates, extruding materials, sheets, films and pipes, in addition to the blown bottles shown in the above-mentioned examples.
Claims (28)
1. A transparent impact-resistant monolayer molded resin bottle obtained by blow molding a molding material selected from the group consisting of:
(A) a polypropylene having a substantially syndiotactic structure, which (i) is (A-a) a homopolymer of propylene having a syndiotactic pentad fraction of 0.7 or more or (A-b) a copolymer of propylene and less than 10% by weight of ethylene or an .alpha.-olefin of 4 to 20 carbon atoms having a peak intensity observed at about 20.2 ppm of 0.5 or more of a peak intensity attributable to all the methyl groups of propylene units in the absorption spectrum of 13C-NMR as measured in a 1,2,4-trichlorobenzene solution and (ii) has an intrinsic viscosity of 0.1 to 20 as measured in a tetrahydronaphthalene solution at 135°C, and (B) a resin composition composed of the polypropylene (A) and (B-a) a copolymer of ethylene and propylene having an ethylene content of 10 to 95% by weight at a weight ratio of the polypropylene (A) to the copolymer (B-a) of from 30/70 to 99/1.
(A) a polypropylene having a substantially syndiotactic structure, which (i) is (A-a) a homopolymer of propylene having a syndiotactic pentad fraction of 0.7 or more or (A-b) a copolymer of propylene and less than 10% by weight of ethylene or an .alpha.-olefin of 4 to 20 carbon atoms having a peak intensity observed at about 20.2 ppm of 0.5 or more of a peak intensity attributable to all the methyl groups of propylene units in the absorption spectrum of 13C-NMR as measured in a 1,2,4-trichlorobenzene solution and (ii) has an intrinsic viscosity of 0.1 to 20 as measured in a tetrahydronaphthalene solution at 135°C, and (B) a resin composition composed of the polypropylene (A) and (B-a) a copolymer of ethylene and propylene having an ethylene content of 10 to 95% by weight at a weight ratio of the polypropylene (A) to the copolymer (B-a) of from 30/70 to 99/1.
2. The molded bottle according to Claim 1 wherein the polypropylene (A) is a homopolymer of propylene which has an intrinsic viscosity of from 0.5 to 10 as measured in a tetrahydronaphthalene solution at 135°C.
3. The molded bottle according to Claim 1 wherein the polypropylene (A) is the copolymer (A-b).
4. The molded bottle according to Claim 1, 2 or 3, wherein the content of the polypropylene (A) is from about 45% by weight to about 99% by weight of the resin composition (B).
5. The molded bottle according to Claim 1, 2 or 3, wherein the content of the polypropylene (A) is from about 55% by weight to about 98% by weight of the resin composition (B).
6. The molded bottle according to any one of Claims 1 to 5, wherein an ethylene content in the ethylene-propylene copolymer (B-a) is from 15% by weight to 90% by weight of the copolymer.
7. The molded bottle according to any one of claims 1 to 7, in which the ethylene-propylene copolymer has a glass transition temperature of -10°C or less and is sufficiently compatible with the polypropylene (A) or dispersible as fine particles in the polypropylene (A), and has an intrinsic viscosity of from 0.5 to 10 as measured in a tetrahydronaphthalene solution at 135°C.
8. The molded bottle according to any one of Claims 1 to 7, wherein the molding material is the polypropylene (A).
9. The molded bottle according to any one of Claims 1 to 7, wherein the molding material is the resin composition (B).
10. The molded bottle according to claim 9, wherein the resin composition (B) consists of the propylene homopolymer and the ethylene-propylene copolymer (B-a).
11. A transparent and impact-resistant multi-layer molded article obtained from a resin composition comprising a polypropylene having a substantially syndiotactic structure and a copolymer of ethylene and propylene, at least one structure of the article comprising a polypropylene layer having the substantially syndiotactic structure.
12. The molded article according to Claim 11 wherein the content of the polypropylene having the substantially syndiotactic structure is from 30% by weight to 99% by weight of the resin composition.
13. The molded article according to Claim 11 wherein the content of the polypropylene having the substantially syndiotactic structure is from 45% by weight to 99% by weight of the resin composition.
14. The molded bottle according to Claim 1 wherein the content of the polypropylene having the substantially syndiotactic structure is from 55% by weight to 98% by weight of the resin composition.
15. The molded article according to Claim 11 wherein the polypropylene having the substantially syndiotactic structure is a homopolymer of propylene which has a syndiotactic pentad fraction of 0.7 or more and an intrinsic viscosity of from 0.5 to 10 measured in a tetrahydronaphthalene solution at 135°C.
16. The molded article according to Claim 11 wherein the polypropylene having the substantially syndiotactic structure contains 10% by weight or less of ethylene or .alpha.-olefin units having 4 to 20 carbon atoms, and a peak intensity observed at about 20.2 ppm in the absorption spectrum of 13C-NMR measured in a 1,2,4-trichlorobenzene solution of the polypropylene is 0.5 or more of a peak intensity attributed to all the methyl groups of the propylene unit.
17. The molded article according to Claim 11 in which the glass transition temperature of the ethylene-propylene copolymer is -10°C or less, and the ethylene-propylene copolymer is sufficiently compatible with the polypropylene having the substantially syndiotactic structure or dispersible as fine particles in the polypropylene having the substantially syndiotactic structure, and has an intrinsic viscosity of from 0.5 to 10 measured in a tetrahydronaphthalene solution at 135°C.
18. The molded article according to Claim 11 wherein an ethylene content in the ethylene-propylene copolymer is from 10% by weight to 95% by weight of the copolymer.
19. The molded article according to Claim 11 wherein an ethylene content in the ethylene-propylene copolymer is from 15% by weight to 90% by weight of the copolymer.
20. The molded article according to Claim 11 which is obtained by blow molding.
21. The molded article according to Claim 11 in which an outer layer is a layer comprising the polypropylene having the substantially syndiotactic structure, and an inner layer i.s a layer made from a resin composition comprising the polypropylene having the substantially syndiotactic structure and the copolymer of ethylene and propylene.
22. The molded article according to Claim 11 wherein the layer of the polypropylene having the substantially syndiotactic structure is a propylene homopolymer having the substantially syndiotactic structure.
23. A transparent impact-resistant bottle obtained by blow molding a molding material selected from the group consisting of:
(A) a polypropylene having a substantially syndiotactic structure, which (i) is a homopolymer of propylene having a syndiotactic pentad fraction of 0.6 or more or a copolymer of propylene and 10 % by weight or less of ethylene or an .alpha.-olefin of 4 to 20 carbon atoms having a peak intensity observed at about 20.2 ppm of 0.3 or more of a peak intensity attributable to all the methyl groups of propylene units in the absorption spectrum of 13C-NMR as measured in a 1,2,4-trichlorobenzene solution, (ii) is produced using a catalyst system comprising a transition metal compound having asymmetric ligands and an aluminoxane or organic aluminum compound and (iii) has an intrinsic viscosity of 0.1 to 20 as measured in a tetrahydronaphthalene solution at 135°C, and (B) a resin composition composed of the polypropylene (A) and a copolymer of ethylene and propylene, wherein a weight ratio of the polypropylene (A) to the copolymer of ethylene and propylene is 30/70 to 99/1 and the copolymer of ethylene and propylene has an ethylene content of 15 to 95% by weight and a glass transition temperature of -10°C or less.
(A) a polypropylene having a substantially syndiotactic structure, which (i) is a homopolymer of propylene having a syndiotactic pentad fraction of 0.6 or more or a copolymer of propylene and 10 % by weight or less of ethylene or an .alpha.-olefin of 4 to 20 carbon atoms having a peak intensity observed at about 20.2 ppm of 0.3 or more of a peak intensity attributable to all the methyl groups of propylene units in the absorption spectrum of 13C-NMR as measured in a 1,2,4-trichlorobenzene solution, (ii) is produced using a catalyst system comprising a transition metal compound having asymmetric ligands and an aluminoxane or organic aluminum compound and (iii) has an intrinsic viscosity of 0.1 to 20 as measured in a tetrahydronaphthalene solution at 135°C, and (B) a resin composition composed of the polypropylene (A) and a copolymer of ethylene and propylene, wherein a weight ratio of the polypropylene (A) to the copolymer of ethylene and propylene is 30/70 to 99/1 and the copolymer of ethylene and propylene has an ethylene content of 15 to 95% by weight and a glass transition temperature of -10°C or less.
24. The bottle according to claim 23, wherein the polypropylene (A) is a homopolymer of propylene having a syndiotactic pentad fraction of 0.7 or more.
25. The bottle according to claim 23, wherein the transition metal compound is isopropyl(cyclopentadienyl-1-fluorenyl)hafnium dichloride or isopropyl(cyclopentadienyl-1-fluorenyl)zirconium dichloride.
26. The bottle according to claim 23, 24 or 25, wherein at least a surface of the bottle is made of the polypropylene (A).
27. The bottle according to claim 23, 24 or 25, which has a multi-layer structure comprising a layer of the resin composition (B) and a layer of the polypropylene (A) at a thickness ratio of the layer of the resin composition (B) to the layer of the polypropylene (A) of from 1/1 to 1/0.001.
28. The bottle according to claim 27, which has an outer layer made of the polypropylene (A) and an inner layer made of the resin composition (B).
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21991/1991 | 1991-02-15 | ||
JP2199191 | 1991-02-15 | ||
JP5188091 | 1991-03-18 | ||
JP51880/1991 | 1991-03-18 |
Publications (2)
Publication Number | Publication Date |
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CA2061247A1 CA2061247A1 (en) | 1992-08-16 |
CA2061247C true CA2061247C (en) | 1998-04-14 |
Family
ID=26359149
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002061247A Expired - Fee Related CA2061247C (en) | 1991-02-15 | 1992-02-14 | Transparent impact-resistant molded articles |
Country Status (5)
Country | Link |
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US (2) | US5637367A (en) |
EP (2) | EP0499216B1 (en) |
KR (2) | KR960006153B1 (en) |
CA (1) | CA2061247C (en) |
DE (1) | DE69223823T2 (en) |
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EP0841370B1 (en) * | 1993-01-11 | 2003-05-02 | Mitsui Chemicals, Inc. | Propylene polymer compositions |
JP3548619B2 (en) * | 1994-03-04 | 2004-07-28 | アドバンスド エラストマー システムズ,エル.ピー. | Translucent thermoplastic elastomer |
JP3258831B2 (en) * | 1994-09-29 | 2002-02-18 | 株式会社興人 | Polypropylene heat-shrinkable laminated film |
KR0159685B1 (en) * | 1995-01-19 | 1998-12-15 | 사토 아키오 | Multilayer molded article of polypropylene |
WO2002083754A1 (en) | 2001-04-12 | 2002-10-24 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
US6159612A (en) * | 1997-08-25 | 2000-12-12 | Mobil Oil Corporation | Multi-layer films with syndiotactic barrier layer containing a wax |
DE19805329A1 (en) | 1998-02-11 | 1999-08-12 | Basf Ag | Injection stretch blow molded olefin polymer containers |
EP1098934A1 (en) | 1998-07-01 | 2001-05-16 | Exxon Chemical Patents Inc. | Elastic blends comprising crystalline polymer and crystallizable polymers of propylene |
US6235781B1 (en) | 1998-07-14 | 2001-05-22 | Alcon Laboratories, Inc. | Prostaglandin product |
EP1133393B1 (en) * | 1998-11-16 | 2003-02-05 | Dupont Canada Inc. | Multilayer polyolefin laminate having non-outer layer of syndiotactic polypropylene |
JP3464405B2 (en) | 1999-02-18 | 2003-11-10 | 阪神化成工業株式会社 | Multi-layer thin-walled container |
US20010055692A1 (en) | 1999-03-17 | 2001-12-27 | Michael T. Heffelfinger | Multi-layer film with core layer of syndiotactic polypropylene |
CN1187404C (en) * | 1999-04-13 | 2005-02-02 | 三井化学株式会社 | Flexible syndiotactic polypropylene compositions and molded object |
US6632885B2 (en) | 1999-04-13 | 2003-10-14 | Mitsui Chemicals, Inc. | Soft syndiotactic polypropylene composition and molded product |
US6591285B1 (en) * | 2000-06-16 | 2003-07-08 | Shuo-Yen Robert Li | Running-sum adder networks determined by recursive construction of multi-stage networks |
US6562930B2 (en) * | 2001-09-18 | 2003-05-13 | Cornell Research Foundation, Inc. | Bis(salicylaldiminato)titanium complex catalysts, highly syndiotactic polypropylene by a chain-end control mechanism, block copolymers containing this |
WO2003040233A2 (en) * | 2001-11-06 | 2003-05-15 | Dow Global Technologies Inc. | Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers |
US6943215B2 (en) * | 2001-11-06 | 2005-09-13 | Dow Global Technologies Inc. | Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers |
EP1444276A1 (en) * | 2001-11-06 | 2004-08-11 | Dow Global Technologies, Inc. | Isotactic propylene copolymers, their preparation and use |
CN100369967C (en) | 2003-02-14 | 2008-02-20 | 三井化学株式会社 | Syndiotactic propylene polymer composition |
JP4790416B2 (en) | 2003-05-28 | 2011-10-12 | 三井化学株式会社 | Propylene polymer composition and use thereof |
US8293843B2 (en) * | 2004-04-13 | 2012-10-23 | Sumitomo Chemical Company, Limited | Process for producing propylene resin composition |
US7745526B2 (en) | 2004-11-05 | 2010-06-29 | Exxonmobil Chemical Patents Inc. | Transparent polyolefin compositions |
EP1688234A3 (en) * | 2005-02-04 | 2006-10-11 | The Procter & Gamble Company | A process for forming a container by stretch blow molding and container formed thereby |
KR101064037B1 (en) * | 2005-05-18 | 2011-09-08 | 미쓰이 가가쿠 가부시키가이샤 | Catalyst for olefin polymerization, method for producing olefin polymer, method for producing propylene copolymer, propylene polymer, propylene polymer composition, and use of those |
JP5438256B2 (en) * | 2006-11-17 | 2014-03-12 | 三井化学株式会社 | Polypropylene resin film and use thereof |
CN101838363B (en) * | 2005-05-18 | 2012-07-25 | 三井化学株式会社 | Method for producing propylene series copolymer |
US7416766B2 (en) * | 2005-08-16 | 2008-08-26 | S.C. Johnson & Son, Inc. | Bottles made from metallocene polypropylene for delivery of fragrances |
EP1870223A1 (en) * | 2006-06-21 | 2007-12-26 | Total Petrochemicals Research Feluy | Low melt flow index resins for injection-stretch-blow-moulding |
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US3835201A (en) * | 1972-08-29 | 1974-09-10 | Uniroyal Inc | Thermoplastic blend of copolymer rubber and polyolefin plastic |
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US4522982A (en) * | 1983-06-06 | 1985-06-11 | Exxon Research & Engineering Co. | Isotactic-stereoblock polymers of alpha-olefins and process for producing the same |
US4892851A (en) * | 1988-07-15 | 1990-01-09 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
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DE3907964A1 (en) * | 1989-03-11 | 1990-09-13 | Hoechst Ag | METHOD FOR PRODUCING A SYNDIOTACTIC POLYOLEFIN |
DE3917652A1 (en) * | 1989-05-31 | 1990-12-06 | Hoechst Ag | MULTILAYER TRANSPARENT POLYOLEFIN FILM FOR THE SCHRUMPFETIKETTIERANWENDUNG |
JP2818199B2 (en) * | 1989-06-12 | 1998-10-30 | 三井化学株式会社 | Syndiotactic polypropylene resin composition and method for producing the same |
DE3942365A1 (en) * | 1989-12-21 | 1991-06-27 | Hoechst Ag | METHOD FOR PRODUCING A POLYPROPYLENE MOLDING MATERIAL |
-
1992
- 1992-02-12 DE DE69223823T patent/DE69223823T2/en not_active Expired - Fee Related
- 1992-02-12 EP EP92102284A patent/EP0499216B1/en not_active Expired - Lifetime
- 1992-02-12 EP EP96120486A patent/EP0770644A1/en not_active Ceased
- 1992-02-13 KR KR1019920002137A patent/KR960006153B1/en not_active IP Right Cessation
- 1992-02-14 CA CA002061247A patent/CA2061247C/en not_active Expired - Fee Related
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1993
- 1993-09-22 US US08/124,531 patent/US5637367A/en not_active Expired - Lifetime
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1996
- 1996-02-22 KR KR1019960004170A patent/KR960006154B1/en not_active IP Right Cessation
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1997
- 1997-02-18 US US08/802,825 patent/US5840389A/en not_active Expired - Lifetime
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KR920016526A (en) | 1992-09-25 |
EP0499216A1 (en) | 1992-08-19 |
KR960006153B1 (en) | 1996-05-09 |
EP0770644A1 (en) | 1997-05-02 |
US5637367A (en) | 1997-06-10 |
DE69223823D1 (en) | 1998-02-12 |
KR960006154B1 (en) | 1996-05-09 |
DE69223823T2 (en) | 1998-05-20 |
EP0499216B1 (en) | 1998-01-07 |
CA2061247A1 (en) | 1992-08-16 |
US5840389A (en) | 1998-11-24 |
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