WO2011090101A1 - Contenant multicouche moulé par soufflage et son procédé de fabrication - Google Patents

Contenant multicouche moulé par soufflage et son procédé de fabrication Download PDF

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Publication number
WO2011090101A1
WO2011090101A1 PCT/JP2011/050939 JP2011050939W WO2011090101A1 WO 2011090101 A1 WO2011090101 A1 WO 2011090101A1 JP 2011050939 W JP2011050939 W JP 2011050939W WO 2011090101 A1 WO2011090101 A1 WO 2011090101A1
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Prior art keywords
ethylene
propylene
olefin copolymer
olefin
measured
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PCT/JP2011/050939
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English (en)
Japanese (ja)
Inventor
弘幸 上北
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株式会社プライムポリマー
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Publication date
Application filed by 株式会社プライムポリマー filed Critical 株式会社プライムポリマー
Priority to KR1020127021432A priority Critical patent/KR101333450B1/ko
Priority to CN201180006278.4A priority patent/CN102712186B/zh
Priority to JP2011550944A priority patent/JP5379247B2/ja
Publication of WO2011090101A1 publication Critical patent/WO2011090101A1/fr

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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
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • 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
    • B32B1/00—Layered products having a non-planar shape
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/07—Preforms or parisons characterised by their configuration
    • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3032—Preforms or parisons made of several components having components being injected
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06—Injection blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • 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
    • B32B2323/00—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging

Definitions

  • the present invention relates to a multilayer blow container and a manufacturing method thereof.
  • resins such as vinyl chloride resin, polycarbonate resin, ethylene resin, and propylene resin are used depending on applications.
  • the resulting blow-molded product is relatively inexpensive to manufacture, and is more glossy and transparent than high-density polyethylene. Therefore, containers for liquid detergents, cosmetics, foods, medicines, etc. Is widely used.
  • the gloss of the blow molded product is a physical property that has been studied in order to meet the market demand for a good appearance, but it still has sufficient gloss, good moldability and impact resistance at the same time. Has not been proposed.
  • a propylene / ⁇ -olefin copolymer is used as a base resin, and a linear low density polyethylene having a crystalline melting point of 110 to 125 ° C. is used as a compounding resin, and these resins and a nucleating agent are contained.
  • a multilayer blow molded article having an olefin polymer composition as an outermost layer has been proposed (see, for example, Patent Document 1).
  • Patent Document 1 As a result of investigations by the present inventors, it was found that even the multilayer blow molded article described in Patent Document 1 is still insufficient in gloss and impact resistance and needs further improvement.
  • Patent Document 2 As a multilayer bottle excellent in cold resistance, a multilayer bottle having a gas barrier resin core layer and having an outermost layer formed of a polyolefin resin and a linear ultra-low density polyethylene resin has been proposed (for example, Patent Document 2).
  • Patent Document 2 As a result of studies by the present inventors, it was found that even the multilayer bottle described in Patent Document 2 still has insufficient gloss and moldability, and further improvement is necessary.
  • a composition comprising a polypropylene resin obtained using a metallocene catalyst and an ethylene / ⁇ -olefin copolymer obtained using a metallocene catalyst as the outermost layer.
  • a high-gloss blow container formed by a multilayer blow molding method is known (for example, see Patent Document 4).
  • Patent Document 4 the high-gloss blown container described in Patent Document 4 is superior in gloss when compared to conventional containers, but further improved in terms of heat resistance and gloss. I found that there was room.
  • An object of the present invention is to provide a multi-layer blow container having high gloss, excellent surface appearance, excellent impact resistance, and excellent balance between impact resistance and stickiness resistance.
  • a multilayer blow container using a specific olefin polymer composition as the outermost layer has high gloss, excellent surface appearance, and is resistant to damage.
  • the present invention has been completed by finding out that it has excellent impact resistance and also has an excellent balance between impact resistance and stickiness resistance.
  • the resin used in the outermost layer is 80 to 98 parts by weight of the propylene resin (A) and 2 to 20 parts by weight of the ethylene / ⁇ -olefin copolymer (B) (however, (A) and (B) are 100 parts by weight) and a nucleating polymer composition (E) formed from 0.01 to 0.5 parts by weight of the nucleating agent (D),
  • the propylene resin (A) satisfies the following requirements (A-1) and (A-2), and the ethylene / ⁇ -olefin copolymer (B) satisfies the following requirements (B-1) and (B-2):
  • a multilayer blow container characterized in that the olefin polymer composition (E) satisfies the following requirement (E-1).
  • A-2 The crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is in the range of 140 to 155 ° C.
  • (B-1) A copolymer of ethylene and one or more ⁇ -olefins having 4 to 20 carbon atoms.
  • the crystal melting point measured by DSC in accordance with JIS-K7121 is in the range of 85 ° C. or higher and lower than 110 ° C.
  • melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes.
  • the olefin polymer composition (E) is further formed using 0.1 to 20 parts by weight of a low density ethylene / ⁇ -olefin copolymer (F).
  • the polymer (F) satisfies the following requirements (F-1) and (F-2), and the density (d B [g / cm] measured by the density gradient method of the ethylene / ⁇ -olefin copolymer (B): 3 ]) and the density (d F [g / cm 3 ]) measured by the density gradient method of the low density ethylene / ⁇ -olefin copolymer (F) satisfy the following requirement (X-1), the multilayer blow It is preferable from the viewpoint of the low temperature impact resistance of the container.
  • (F-1) A copolymer of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms.
  • the ethylene / ⁇ -olefin copolymer (B) preferably further satisfies the following requirement (B-4).
  • the density measured by the density gradient tube method is in the range of 0.880 to 0.910 g / cm 3 .
  • the ethylene / ⁇ -olefin copolymer (B) further satisfies the following requirement (B-4a), and the low-density ethylene / ⁇ -olefin copolymer (F) further satisfies the following requirement (F-3). Is preferable from the viewpoint of low-temperature impact resistance of the multilayer blow container.
  • (B-4a) density measured by a density gradient tube method (d B [g / cm 3 ]) is in the range of 0.890 ⁇ 0.910g / cm 3.
  • the density (d F [g / cm 3 ]) measured by the density gradient tube method is in the range of 0.865 to 0.900 g / cm 3 .
  • the propylene resin (A) further satisfies the following requirement (A-4).
  • the propylene resin (A) further satisfies the following requirement (A-3).
  • the ethylene / ⁇ -olefin copolymer (B) further satisfies the following requirement (B-5).
  • the ethylene / ⁇ -olefin copolymer (B) preferably further satisfies the following requirement (B-3).
  • the nucleating agent (D) is one or more compounds selected from the group consisting of aromatic phosphate ester compounds, carboxylic acid metal salt nucleating agents, polymer nucleating agents, sorbitol nucleating agents and inorganic compound nucleating agents. It is preferable that
  • the propylene-based resin (A) is 95.5 to 98 parts by weight, and the ethylene / ⁇ -olefin copolymer (B) is 2 to 4.5 parts by weight (provided that (A) and (B) The total is preferably 100 parts by weight.
  • the multilayer blow container has a layer formed from a propylene polymer (G) or an ethylene polymer (H) as at least one inner layer.
  • G propylene polymer
  • H ethylene polymer
  • the multilayer blow container is preferably obtained by molding by a direct blow molding method or an injection stretch blow molding method.
  • the multilayer blow container of the present invention uses a thermoplastic resin composition other than the olefin polymer composition (E) and the olefin polymer composition (E) described above, and the olefin polymer composition (E) has the outermost layer. And formed by a direct blow molding method or an injection stretch blow molding method so that the thermoplastic resin composition other than the olefin polymer composition (E) forms at least one inner layer.
  • the resin used for the outermost layer is an olefin polymer formed of a propylene resin (A), an ethylene / ⁇ -olefin copolymer (B), and a nucleating agent (D). It consists of a composition (E), It is characterized by the above-mentioned.
  • the multilayer blow container of the present invention has high gloss, excellent surface appearance, and excellent impact resistance, but the olefin polymer composition (E) is further reduced in density ethylene / ⁇ -olefin copolymer (F). In the embodiment formed using 0.1 to 20 parts by weight, the low temperature impact resistance is further excellent.
  • the propylene resin (A) used in the present invention preferably satisfies the following requirements (A-1) and (A-2), and preferably satisfies at least one of the following requirements (A-3) and (A-4): More preferably, the following requirements (A-3) and (A-4) are satisfied.
  • Propylene-type resin (A) may be used individually by 1 type, or may use 2 or more types.
  • olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
  • the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene and 4-methyl.
  • -1-pentene 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene , 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3-methyl- Examples include 1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, ethyl-1-octene, and methyl-1-nonene. .
  • the propylene-based resin (A) used in the present invention is composed of propylene and one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 10 carbon atoms in view of the balance between physical properties and economy. It is preferably a copolymer, more preferably a copolymer of propylene and one or more ⁇ -olefins selected from the group consisting of ethylene and 1-butene, and a copolymer of propylene and ethylene It is particularly preferred that
  • the propylene resin (A) used in the present invention is preferably a random copolymer.
  • the crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is in the range of 140 to 155 ° C. It is preferable that the crystal melting point is in the above-mentioned range since the multilayer blow container is excellent in gloss and impact resistance and is excellent in moldability when producing the multilayer blow container.
  • the crystal melting point measured by a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is higher than 155 ° C., the impact resistance of the multilayer blow container is inferior.
  • the moldability at the time of producing the multilayer blow container is inferior and the surface of the multilayer blow container is sticky. .
  • the crystalline melting point of the propylene-based resin (A) can be determined by measuring under the following measurement conditions using a differential scanning calorimeter (DSC) (for example, Diamond TM DSC manufactured by Perkin Elmer) according to JIS-K7121. it can.
  • DSC differential scanning calorimeter
  • the top of the endothermic peak in the third step when the measurement was performed under the following measurement conditions was defined as the crystalline melting point (Tm).
  • Tm crystalline melting point
  • Measurement condition Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg Sample shape: Press film (230 ° C molding, thickness 200-400 ⁇ m) First step: The temperature is raised from 30 ° C to 240 ° C at 10 ° C / min and held for 10 min.
  • Second step IV Decrease the temperature to 60 ° C at 10 ° C / min.
  • 3rd step IV Increase the temperature to 240 ° C at 10 ° C / min.
  • the crystal melting point of the propylene resin (A) measured by a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is, for example, propylene at the time of copolymerization in the production of the propylene resin (A), ethylene introduced, and It can be adjusted by changing the introduction ratio of one or more olefins selected from the group consisting of ⁇ -olefins having 4 to 20 carbon atoms. That is, by increasing the introduction amount of one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms with respect to the introduction amount of propylene, the differential scanning calorific value in accordance with JIS-K7121.
  • the crystal melting point measured by a total (DSC) can be lowered, and the introduction amount of one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms is reduced with respect to the introduction amount of propylene.
  • DSC differential scanning calorimeter
  • MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes.
  • MFR means a melt flow rate.
  • the moldability and the impact resistance of the multilayer blow container are inferior.
  • the gloss of the multilayer blow container may be inferior.
  • MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is, for example, chain transfer used during copolymerization in the production of the propylene resin (A). It can adjust with the introduction amount of an agent (for example, hydrogen gas). That is, the amount of the chain transfer agent (for example, hydrogen gas) introduced is increased with respect to the amount of propylene introduced during the polymerization and one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
  • the introduction amount of chain transfer agent for example, hydrogen gas
  • the introduction amount of chain transfer agent is reduced with respect to the amount of one or more olefins selected from the group consisting of propylene introduced at the time of polymerization and ethylene and ⁇ -olefin having 4 to 20 carbon atoms.
  • the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 of the propylene resin (A) can be lowered.
  • the propylene-based resin obtained by polymerization is melt kneaded in the presence of a radical generator such as an organic peroxide, and the measurement temperature is 230 ° C. and the load is 2.16 kg according to ASTM D-1238.
  • the MFR measured in (1) can be adjusted. For example, by performing the melt-kneading process in the presence of an organic peroxide, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is increased in accordance with ASTM D-1238. Further, by increasing the amount of the organic peroxide added, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg can be further increased in accordance with ASTM D-1238.
  • Mw / Mn measured by GPC is 4.0 or more.
  • GPC means gel permeation chromatography
  • Mw means weight average molecular weight
  • Mn means number average molecular weight
  • Mw / Mn is an index of molecular weight distribution.
  • Mw / Mn is preferably 1.5 or more, more preferably 3.0 or more, but satisfies the above (A-4), that is, Mw / Mn is 4.0 or more. It is particularly preferable because a blow molded article having excellent gloss can be obtained regardless of the surface roughness of the blow mold. The reason for this is not clear, but the present inventors consider as follows.
  • Mw / Mn is not particularly limited, but is usually 50.0, preferably 30.0, more preferably 20.0, still more preferably 16.0, particularly preferably 12 from the viewpoint of productivity. 0.0, most preferably 8.0.
  • Mw / Mn by GPC can be performed by the method as described in an Example.
  • Mw / Mn measured by GPC of the propylene resin (A) can be adjusted, for example, depending on the type of catalyst used in the production of the propylene resin (A).
  • a Ziegler-Natta catalyst preferably a solid titanium catalyst
  • the propylene-based resin (A) satisfying the requirement (A-4) can be obtained.
  • Mw / Mn there is a method of blending two or more propylene resins having different molecular weights.
  • the solid titanium catalyst is advantageous from the viewpoint of forming the higher molecular weight portion.
  • the propylene resin (A) is derived from one or more olefins selected from the group consisting of propylene-derived structural units and ethylene and ⁇ -olefins having 4 to 20 carbon atoms, calculated from 13 C-NMR.
  • the weight of the propylene-derived structural unit when the total amount of the structural units is 100% by weight is usually in the range of 80 to 99% by weight, and preferably in the range of 90 to 99% by weight.
  • the weight of the structural unit derived from one or more olefins selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 20 carbon atoms is usually in the range of 1 to 20% by weight, preferably 1 to It is in the range of 10% by weight. Within the above range, it is preferable because the balance between the moldability when producing a multilayer blow container and physical properties such as stickiness of the multilayer blow container is good.
  • the total of the structural unit derived from propylene calculated from 13 C-NMR and the structural unit derived from one or more olefins selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 20 carbon atoms is 100% by weight.
  • the weight of the structural unit derived from propylene was measured and calculated under the following conditions.
  • the mole fraction of the structural unit derived from ethylene in the propylene resin (A) (mol%) (hereinafter referred to as E (mol%))
  • the molar fraction (mol%) of constituent units derived from propylene (hereinafter referred to as P (mol%))
  • the weight percent of the structural unit derived from propylene and the weight percent of the structural unit derived from ethylene in the propylene-based resin (A) are calculated by converting from the obtained E (mol%) and P (mol%) to weight percent. be able to.
  • the molar fraction (mol%) of the structural unit derived from (hereinafter referred to as A (mol%)) and the molar fraction (mol%) of the structural unit derived from propylene (hereinafter referred to as P (mol%)) are calculated. be able to. Converted from the calculated A (mol%) and P (mol%) to wt%, derived from propylene-based constituent units in propylene resin (A) and derived from ⁇ -olefin having 4 to 20 carbon atoms The weight% of the structural unit to be calculated can be calculated.
  • Adjustment of the weight of the structural unit derived from propylene can be made into arbitrary quantity by adjusting the manufacturing conditions mentioned later. More specifically, introduction of one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms with respect to the amount of propylene introduced during copolymerization in the production of propylene-based resin (A). By reducing the amount, the weight of the structural unit derived from propylene can be increased.
  • the weight of the structural unit derived from propylene is reduced. be able to.
  • the propylene resin (A) is preferably a random copolymer of propylene and one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
  • the propylene resin (A) is a copolymer of propylene and one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms, preferably in the presence of a Ziegler-Natta catalyst or a metallocene catalyst. Can be obtained by random copolymerization.
  • the requirement (A-4) can be satisfied. It is also possible to adjust to satisfy the requirement (A-4) by blending two or more propylene resins (A) having different molecular weights.
  • a chain transfer agent represented by hydrogen gas can be introduced.
  • the propylene-based resin (A) can also be obtained by subjecting the propylene-based resin obtained by polymerization to melt-kneading in the presence of a radical generator such as an organic peroxide.
  • the organic peroxide is not particularly limited, but benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5 -Di- (benzoylperoxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-diperadipate, t-butylperoxy-3, 5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di- (t -Butylperoxy) hexane, 2,5, -di-methyl-2,5-di- (t-butylperoxy) hexyne-3,1,
  • 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane and 1,3-bis- (t-butylperoxyisopropyl) benzene are more preferred.
  • an organic peroxide it is desirable to use it at 0.1 parts by weight or less with respect to 100 parts by weight of the propylene-based resin obtained by polymerization.
  • the mixture is introduced into a mixer such as a Henschel mixer, a Banbury mixer, or a tumbler mixer, and then mixed.
  • a mixer such as a Henschel mixer, a Banbury mixer, or a tumbler mixer
  • the resulting mixture is then converted into a single-screw extruder,
  • molding with extruders, such as a twin-screw extruder, and obtaining the strand of propylene-type resin (A) is mentioned.
  • the strand is usually formed into a pellet using a pelletizer or the like before blow molding.
  • ⁇ Ethylene / ⁇ -olefin copolymer (B)> The ethylene / ⁇ -olefin copolymer (B) used in the present invention satisfies the following requirements (B-1) and (B-2), and at least one of the following requirements (B-3) and (B-4): Preferably, the following requirements (B-3) and (B-4) are satisfied. It is also preferable to satisfy the following requirement (B-5).
  • the ethylene / ⁇ -olefin copolymer (B) may be used alone or in combination of two or more.
  • (B-1) A copolymer of ethylene and one or more ⁇ -olefins having 4 to 20 carbon atoms.
  • the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene and 4-methyl.
  • -1-pentene 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene , 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3-methyl- Examples include 1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, ethyl-1-octene, and methyl-1-nonene. .
  • the ethylene / ⁇ -olefin copolymer (B) used in the present invention is at least one selected from the group consisting of ethylene and ⁇ -olefins having 4 to 10 carbon atoms from the viewpoint of a balance between physical properties and economy. It is preferably a copolymer of olefins, more preferably a copolymer of ethylene and one or more ⁇ -olefins selected from the group consisting of 1-butene, 1-hexene and 1-octene. A copolymer of ethylene and 1-hexene is particularly preferable.
  • the crystal melting point measured by DSC in accordance with JIS-K7121 is in the range of 85 ° C. or higher and lower than 110 ° C. It is preferable that the crystal melting point is in the above range because the multilayer blow container is excellent in impact resistance and adhesion between the outermost layer and other layers.
  • the crystalline melting point of the ethylene / ⁇ -olefin copolymer (B) measured by DSC in accordance with JIS-K7121 is 110 ° C. or higher, the adhesion and impact resistance are inferior, and measured by DSC in accordance with JIS-K7121.
  • the crystal melting point is lower than 85 ° C., the adhesiveness is inferior, and stickiness is generated, which is not preferable.
  • the crystal melting point is preferably 109 ° C. or lower, more preferably 108 ° C. or lower, and particularly preferably 105 ° C. or lower.
  • the crystalline melting point of the ethylene / ⁇ -olefin copolymer (B) used in the present invention measured by DSC in accordance with JIS-K7121 can be adjusted to any amount by adjusting the production conditions of the ethylene / ⁇ -olefin copolymer. It can be.
  • the polymerization of the ethylene / ⁇ -olefin copolymer (B) it is adjusted by changing the ratio of the feed amount of ethylene / ⁇ -olefin when the ethylene / ⁇ -olefin copolymer is polymerized.
  • the ratio of the feed amount of ethylene / ⁇ -olefin when the ethylene / ⁇ -olefin copolymer is polymerized Is possible. Specifically, by increasing the feed amount of ⁇ -olefin relative to the feed amount of ethylene, it is possible to lower the crystal melting point measured by DSC in accordance with JIS-K7121. Further, by reducing the feed amount of ⁇ -olefin relative to the feed amount of ethylene, it is possible to increase the crystalline melting point measured by DSC in accordance with JIS-K7121.
  • the crystal melting point of the ethylene / ⁇ -olefin copolymer (B) can be measured using a differential scanning calorimeter (DSC) according to JIS-K7121. Specifically, it can be measured by the same method as the crystalline melting point of the propylene resin (A) described above.
  • DSC differential scanning calorimeter
  • (B-3) MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is in the range of 5 to 10 g / 10 min.
  • the MFR is within the above range, the dispersibility of the ethylene / ⁇ -olefin copolymer (B) in the propylene resin (A) is good, the gloss of the multilayer blow container is excellent, and the impact resistance is excellent. Since it is excellent in adhesiveness with another layer, it is preferable.
  • the MFR of the ethylene / ⁇ -olefin copolymer (B) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is adjusted with the ethylene / ⁇ -olefin copolymer (B It can be set to an arbitrary value by adjusting the manufacturing conditions.
  • the amount of hydrogen gas is controlled by adjusting the feed amount of ethylene and / or ⁇ -olefin at the time of polymerization. It is possible. Measurement temperature in accordance with ASTM D-1238 by increasing the feed amount of ethylene gas during polymerization or when feeding ethylene and ⁇ -olefin, by increasing the feed amount of hydrogen gas relative to the feed amount of ethylene and ⁇ -olefin It is possible to increase the MFR measured at 230 ° C. and a 2.16 kg load. In the case of feeding ethylene gas or ethylene and ⁇ -olefin, the measurement temperature is 230 ° C. according to ASTM D-1238 by reducing the amount of hydrogen gas to ethylene and ⁇ -olefin. It is possible to lower the MFR measured with a 16 kg load.
  • the density measured by the density gradient tube method is in the range of 0.880 to 0.910 g / cm 3 . It is preferable for the density to be in the above-mentioned range since the multilayer blow container is excellent in gloss and impact resistance and adhesion between the outermost layer and other layers.
  • the low-density ethylene / ⁇ -olefin copolymer (F) described later is used and the ethylene / ⁇ -olefin copolymer is used.
  • the polymer (B) preferably satisfies the following requirement (B-4a).
  • (B-4a) density measured by a density gradient tube method (d B [g / cm 3 ]) is in the range of 0.890 ⁇ 0.910g / cm 3.
  • the multi-layer blow container has excellent gloss, impact resistance, low temperature impact resistance, adhesion between the outermost layer and other layers, low stickiness, and further, impact resistance and low temperature resistance. It is preferable because the balance between impact resistance such as impact properties and resistance is good.
  • the density measured by the density gradient tube method of the ethylene / ⁇ -olefin copolymer (B) used in the present invention should be an arbitrary amount by adjusting the production conditions of the ethylene / ⁇ -olefin copolymer (B). Can do.
  • the ratio of the feed amount of ethylene and ⁇ -olefin when the ethylene / ⁇ -olefin copolymer is polymerized is changed.
  • the density measured by the density gradient tube method can be lowered by increasing the feed amount of ⁇ -olefin relative to the feed amount of ethylene.
  • the density measured by the density gradient tube method can be increased by reducing the feed amount of ⁇ -olefin relative to the feed amount of ethylene.
  • the density measured by the density gradient tube method of the ethylene / ⁇ -olefin copolymer (B) used in the present invention is the same as that of the ethylene / ⁇ -olefin copolymer (B) strand obtained at the time of the MFR measurement. It is a measured value measured with a density gradient tube after heat treatment at 120 ° C. for 1 hour and linearly cooling to room temperature over 1 hour.
  • Mw / Mn measured by GPC is 1.2 to 3.0.
  • the ethylene / ⁇ -olefin copolymer (B) preferably has Mw / Mn of 1.5 to 3.0. It is preferable that Mw / Mn is within the above range because the multilayer blow container of the present invention is excellent in gloss.
  • Mw / Mn measured by GPC of the ethylene / ⁇ -olefin copolymer (B) can be adjusted, for example, depending on the type of catalyst used in the production of the ethylene / ⁇ -olefin copolymer (B). .
  • a metallocene catalyst as the catalyst, an ethylene / ⁇ -olefin copolymer (B) satisfying the requirement (B-5) can be obtained.
  • the ethylene / ⁇ -olefin copolymer (B) can be obtained by copolymerizing ethylene and an ⁇ -olefin, but the ethylene / ⁇ -olefin copolymer is obtained using a metallocene catalyst. A polymerized one is preferred. In the polymerization, a chain transfer agent represented by hydrogen gas can be introduced.
  • the ethylene / ⁇ -olefin copolymer (B) used in the present invention is an ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst, an ethylene polymerized using a conventional so-called Ziegler-Natta catalyst is used. Since the composition distribution is more uniform than that of the ⁇ -olefin copolymer, the dispersibility with respect to the propylene-based resin (A) is improved, and the olefin polymer composition (E) having better gloss can be obtained.
  • an ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst has a narrower molecular weight distribution than that of an ethylene / ⁇ -olefin copolymer polymerized using a Ziegler-Natta catalyst. Low molecular weight components that cause deterioration are reduced.
  • an ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst has a more uniform composition distribution of the copolymer than an ethylene / ⁇ -olefin copolymer polymerized using a Ziegler-Natta catalyst. The amorphous component that causes stickiness is also reduced. Further, adhesion unevenness between the outermost layer and the other layers is reduced, and it is expected to suppress deterioration in appearance over time.
  • the olefin polymer composition (E) has excellent gloss, impact resistance, and low stickiness. ) Can be obtained.
  • the olefin polymer composition (E) the propylene resin (A) and the ethylene / ⁇ -olefin copolymer ( In addition to B) and the nucleating agent (D), it is preferable to use a composition formed using a low-density ethylene / ⁇ -olefin copolymer (F).
  • the low-density ethylene / ⁇ -olefin copolymer (F) preferably satisfies the following requirements (F-1) and (F-2), and further satisfies the following requirement (F-3).
  • the low density ethylene / ⁇ -olefin copolymer (F) may be used alone or in combination of two or more.
  • (F-1) A copolymer of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms.
  • the ⁇ -olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4 -Methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1 -Butene, 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3- Methyl-1-hexen
  • the low density ethylene / ⁇ -olefin copolymer (F) includes at least one selected from the group consisting of ethylene and ⁇ -olefins having 3 to 10 carbon atoms from the viewpoint of a balance between physical properties and economy. It is preferably a copolymer with olefin, and is a copolymer of ethylene and one or more ⁇ -olefins selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene. More preferred.
  • the low density ethylene / ⁇ -olefin copolymer (F) is preferably a copolymer of ethylene and propylene, a copolymer of ethylene and 1-butene, or a copolymer of ethylene and 1-octene. More preferred is a copolymer of ethylene and 1-butene, and a copolymer of ethylene and 1-octene, and particularly preferred is a copolymer of ethylene and 1-butene.
  • the crystal melting point measured by DSC according to JIS-K7121 is 89 ° C. or lower, or no peak based on the crystal melting point is observed. When it has a crystalline melting point, it is preferably 75 ° C. or lower. A crystal melting point within the above range is preferable because a multilayer blow container is excellent in low-temperature impact resistance.
  • the crystal melting point of the low density ethylene / ⁇ -olefin copolymer (F) can be measured using a differential scanning calorimeter (DSC) according to JIS-K7121. Specifically, it can measure by the method as described in the below-mentioned Example.
  • DSC differential scanning calorimeter
  • the density (d F [g / cm 3 ]) measured by the density gradient tube method is in the range of 0.865 to 0.900 g / cm 3 .
  • the density is more preferably in the range of 0.870 to 0.900 g / cm 3 . It is preferable for the density to be in the above-mentioned range since the gloss of the multilayer blow container is excellent and the low-temperature impact resistance is particularly excellent.
  • the density (d F [g / cm 3 ]) measured by the public law satisfies the following requirement (X-1).
  • the density difference (d B -d F ) from the density ethylene / ⁇ -olefin copolymer ( F ) is 0.010 to 0.050 [g / cm 3 ].
  • the density difference (d B ⁇ d F ) is preferably 0.010 to 0.040 [g / cm 3 ].
  • the density difference (d B ⁇ d F ) be in the above range because the multilayer blow container is excellent in gloss and further excellent in low-temperature impact resistance.
  • the low-density ethylene / ⁇ -olefin copolymer (F) has an MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 in the range of 0.1 to 50 g / 10 min. It is preferably in the range of 0.5 to 30 g / 10 minutes, and more preferably in the range of 5 to 10 g / 10 minutes.
  • the MFR is within the above range, the dispersibility of the low-density ethylene / ⁇ -olefin copolymer (F) becomes good, and the gloss and low-temperature impact properties are improved.
  • the low-density ethylene / ⁇ -olefin copolymer (F) can be obtained by copolymerizing ethylene and ⁇ -olefin, and the ethylene / ⁇ -olefin copolymer is a Ziegler-Natta catalyst.
  • the polymer may be polymerized using a metallocene or may be polymerized using a metallocene catalyst.
  • nucleating agent (D) In the present invention, the nucleating agent (D) is used.
  • the nucleating agent (D) one or more compounds selected from the group consisting of aromatic phosphate ester compounds, carboxylic acid metal salt nucleating agents, polymer nucleating agents, sorbitol nucleating agents and inorganic compound nucleating agents. Is mentioned. It is preferable that the nucleating agent (D) does not deteriorate the odor of the multilayer blow container.
  • a nucleating agent (D) may be used individually by 1 type, or may use 2 or more types together.
  • the aromatic phosphate compound is preferably a compound represented by the following formula [III] and / or [IV].
  • R 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms
  • R 2 and R 3 are each independently a hydrogen atom or 1 to 10 carbon atoms.
  • a hydrocarbon group, M is a monovalent to trivalent metal atom, n is an integer of 1 to 3, and m is 1 or 2.
  • aromatic phosphate compound represented by the general formula [III] include sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2 , 2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2 , 2'-Butyliden
  • a hydroxyaluminum phosphate compound represented by the general formula [IV] can also be used.
  • the compound represented by the general formula [V] in which R 2 and R 3 are both tert-butyl groups. are preferred.
  • R 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and m is 1 or 2.
  • a particularly preferred aromatic phosphate compound is a compound represented by the general formula [VI].
  • R 1 is a methylene group or an ethylidene group.
  • hydroxyaluminum-bis [2,2-methylene-bis (4,6-di-t-butyl) phosphate] (also known as bis (2, 4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide salt), or hydroxyaluminum Bis [2,2-ethylidene-bis (4,6-di-t-butyl) phosphate].
  • carboxylic acid metal salt nucleating agent for example, pt-butyl aluminum benzoate, aluminum adipate, or sodium benzoate can be used.
  • a branched ⁇ -olefin polymer is preferably used as the polymer nucleating agent.
  • branched ⁇ -olefin polymers include 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, a homopolymer of 3-ethyl-1-hexene, or a copolymer thereof, Can include copolymers of these with other ⁇ -olefins.
  • polymer nucleating agents can be blended directly when the olefin polymer composition (E) is produced, and when the propylene resin (A) is produced, the propylene resin (A) is produced.
  • the above branched ⁇ -olefin is polymerized before or after the polymerization in a block manner, and blended by using the propylene resin (A) containing the branched ⁇ -olefin polymer as the nucleating agent (D). It is also possible to use a polymer nucleating agent-containing propylene resin (A ′).
  • the polymer nucleating agent contained in the polymer nucleating agent-containing propylene resin (A ′) Let the amount be the blending amount of the nucleating agent (D) in the olefin polymer composition (E). Moreover, let the part which reduced the quantity of the polymer nucleating agent from the polymer nucleating agent mixing
  • the polymer nucleating agent can also be formed by prepolymerization when producing the polymer (A), the polymer (B), and the polymer (F) using a known method. ), When the polymer (F) is produced, it can also be formed by a block copolymerization method.
  • a polymer nucleating agent-containing propylene resin (A ′) and a propylene resin (A) containing no polymer nucleating agent may be used in combination.
  • a polymer of 3-methyl-1-butene is particularly preferable from the viewpoints of transparency, low-temperature impact resistance, rigidity properties, and economical viewpoint.
  • nonitol, 1,2,3-trideoxy-4,6 5,7-bis-O-[(4-propylphenyl) methylene] can be preferably used.
  • inorganic compound nucleating agent for example, talc, mica, calcium carbonate can be used.
  • nucleating agents (D) nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O— is preferred in terms of transparency, low-temperature impact resistance, rigidity and low odor.
  • a commercially available product can be used as the nucleating agent (D) used in the present invention.
  • ADK STAB NA-21 manufactured by ADEKA
  • ADEKA is bis (2,4,8,10-tetra-t-butyl-6-).
  • Hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) is commercially available as a nucleating agent containing aluminum hydroxide as a main component.
  • 3-Trideoxy-4,6 5,7-bis-O-[(4-propylphenyl) methylene] is commercially available under the trade name Millard NX8000 (Milken).
  • the olefin polymer composition (E) used in the present invention is a resin used for the outermost layer of the multilayer blow container of the present invention.
  • the propylene-based resin (A) is 80 to 98 parts by weight and an ethylene / ⁇ -olefin.
  • the olefin polymer composition (E) is composed of propylene resin (A) and ethylene / ⁇ -olefin copolymer. It is preferable to use a composition formed by using 0.1 to 20 parts by weight of a low density ethylene / ⁇ -olefin copolymer (F) in addition to the coalescence (B) and the nucleating agent (D). .
  • the olefin polymer composition (E) is formed without using the low density ethylene / ⁇ -olefin copolymer (F). It is also preferable.
  • the amount of the propylene-based resin (A) and the ethylene / ⁇ -olefin copolymer (B) used is such that the propylene-based resin (A) is used from the viewpoint of good stickiness and economical and productivity. 95.5 to 98 parts by weight, and the ethylene / ⁇ -olefin copolymer (B) is 2 to 4.5 parts by weight (provided that the total of (A) and (B) is 100 parts by weight) It is preferable that
  • a multilayer blow container The propylene-based resin (A) blended in the olefin polymer composition (E) is less than 80 parts by weight, and the ethylene / ⁇ -olefin copolymer is inferior in impact resistance and adhesion to other layers.
  • (B) is more than 20 parts by weight, stickiness occurs, which is not preferable.
  • the low-density ethylene / ⁇ -olefin copolymer (E) is blended into the olefin polymer composition (E) from the viewpoints of stickiness and economy.
  • F) is preferably 3 to 15 parts by weight.
  • the nucleating agent (D) is used in an amount of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of the propylene resin (A) and the ethylene / ⁇ -olefin copolymer (B).
  • the effect of improving the glossiness of the film can be obtained.
  • the addition amount of the nucleating agent (D) is less than 0.01 parts by weight, the effect of improving the glossiness is small. Even if the addition amount of the nucleating agent (D) is more than 0.5 parts by weight, the effect is not changed, and it is not preferable because it is economically disadvantageous.
  • the olefin polymer composition (E) satisfies the following requirement (E-1).
  • the melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes.
  • MFR melt flow rate
  • the fluidity of the olefin polymer composition (E) at the time of molding becomes a range suitable for molding, and fine melt fracture (MF) generated at the time of molding can be suppressed.
  • MF fine melt fracture
  • the thickness nonuniformity of the olefin polymer composition (E) in blow molding is prevented, and the multilayer blow container excellent in smoothness can be obtained.
  • melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is higher than 10 g / 10 minutes, the moldability is inferior, and when it is lower than 5 g / 10 minutes, the glossiness is obtained.
  • the melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with the requirements (E-1) relating to the olefin polymer composition (E), that is, ASTM D-1238, is propylene used Can be adjusted by appropriately selecting the resin (A), the ethylene / ⁇ -olefin copolymer (B), and the low density ethylene / ⁇ -olefin copolymer (F) used as necessary. is there.
  • both the propylene-based resin (A) and the ethylene / ⁇ -olefin copolymer (B) used were measured in accordance with ASTM D-1238 at a measurement temperature of 230 ° C. and a load of 2.16 kg (MFR). ) In the range of 5 to 10 g / 10 min, the propylene resin (A), the ethylene / ⁇ -olefin copolymer (B), and the low-density ethylene / ⁇ -olefin copolymer used as necessary.
  • the requirement (E-1) can be satisfied by appropriately selecting the polymer (F).
  • a melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is less than 5 g / 10 minutes.
  • the propylene-based resin (A) or ethylene / ⁇ - The olefin copolymer (B) or the low density ethylene / ⁇ -olefin copolymer (F) used as necessary is modified to give an MF of the olefin polymer composition (E).
  • The can be adjusted within the above range.
  • an organic peroxide the thing similar to what was described by the term of the said ⁇ propylene-type resin (A)> is mentioned.
  • an ethylene / ⁇ -olefin copolymer (B) to be combined is necessary.
  • the MFR of the olefin polymer composition (E) can be adjusted within the above range by using a low density ethylene / ⁇ -olefin copolymer (F) used depending on
  • the olefin polymer composition (E) preferably has a crystal melting point measured by DSC according to JIS-K7121 in the range of 140 to 155 ° C. When the crystal melting point is within the above range, a multi-layer blow container having good gloss and good impact resistance can be obtained.
  • the crystal melting point of the olefin polymer composition (E) can be measured using a differential scanning calorimeter (DSC) according to JIS-K7121. Specifically, it can be measured by the same method as the crystalline melting point of the propylene resin (A) described above.
  • DSC differential scanning calorimeter
  • the olefin polymer composition (E) preferably has a half crystallization time (t 1/2 ) in the range of 50 to 1000 seconds, and more preferably in the range of 100 to 500 seconds. Within the above range, the mold transferability becomes good at the time of blow molding, and a multi-layer blow container with good gloss can be obtained.
  • the half crystallization time (t 1/2 ) was crystallized with the olefin polymer composition (E) under an isothermal condition of 125 ° C., and the calorific value associated with crystallization was measured at this time to start the heat generation (crystallization It can be measured as the time from the start) until the calorific value becomes half the total calorific value.
  • the half crystallization time (t 1/2 ) of the olefin polymer composition (E) can be adjusted by the amount of the nucleating agent (D) contained in the olefin polymer composition (E). By increasing the amount of the nucleating agent (D) contained in the olefin polymer composition (E), it is possible to increase the half crystallization time (t 1/2 ), and conversely, the amount of the nucleating agent (D). It is possible to slow down the half crystallization time (t 1/2 ) by reducing.
  • the olefin polymer composition (E) of the present invention includes the propylene resin (A), the ethylene / ⁇ -olefin copolymer (B), the low density ethylene / ⁇ -olefin copolymer (F), and Components other than the nucleating agent (D) may be contained.
  • Examples of other resins include polyolefins other than propylene resin (A), ethylene / ⁇ -olefin copolymer (B), low density ethylene / ⁇ -olefin copolymer (F), and nucleating agent (D).
  • Examples of the polyolefin resin include propylene resins (P) other than the propylene resin (A).
  • Examples of the propylene resin (P) include propylene homopolymers (including syndiotactic propylene homopolymers) different from the propylene resin (A).
  • Tm of propylene-based resin (P) measured by a differential scanning calorimeter (DSC) according to JISK7121 is 140 to 155 ° C.
  • the MFR of propylene resin (P) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is preferably 0.01 to 20 g / 10 min, particularly 0.1 to 5 g / 10 min is preferred.
  • styrene elastomers or hydrogenated products (S) thereof can be exemplified.
  • S hydrogenated product
  • the styrenic elastomer or hydrogenated product (S) thereof has a styrene content of 10 to 70% by weight, preferably 10 to 65% by weight, more preferably 10 to 40% by weight, and a conjugated diene content of 30 to 90% by weight.
  • the styrenic elastomer or the hydrogenated product (S) thereof is preferably 35 to 90% by weight, more preferably 60 to 90% by weight.
  • styrene-type elastomer or its hydrogenated substance As said styrene-type elastomer or its hydrogenated substance (S), a styrene-type polymer block component (it may hereafter be called a styrene block) and a conjugated diene-type polymer block component (it may be hereafter called a diene block). And a styrene / butadiene random copolymer, a styrene / isoprene random copolymer, a styrene / chloroprene random copolymer, and hydrogenated products thereof. Of these, styrene block copolymers are preferred.
  • the styrenic polymer block component constituting the styrenic block copolymer is composed of styrene or a derivative thereof.
  • Specific examples of the monomer include styrene, ⁇ -methylstyrene, p-methylstyrene, chlorostyrene, and vinylnaphthalene. Etc. Of these, styrene is preferred. These monomers are used alone or in combination of two or more.
  • the monomer constituting the conjugated diene polymer block include butadiene, isoprene, chloroprene and the like. Of these, butadiene and isoprene are preferred. These monomers are used alone or in combination of two or more.
  • the bonding form of the styrene block and the diene block in the styrenic block copolymer is not particularly limited, but the styrene block / diene block or styrene block / [diene block / styrene block] n (where n is 1 to 5) Form is preferred.
  • the content of the styrene polymer block component in the styrene block copolymer is 10 to 70% by weight, preferably 10 to 65% by weight, more preferably 10 to 40% by weight, and the content of the conjugated diene polymer block component
  • the amount is desirably 30 to 90% by weight, preferably 35 to 90% by weight, and more preferably 60 to 90% by weight.
  • the styrene block copolymer has a melt flow rate (MFR) measured at 230 ° C. and a load of 2160 g in accordance with ASTM D-1238 at 0.1 g / 10 min or more, preferably 0.3 to 20 g / 10 min, particularly Preferably, it is 5 to 10 g / 10 min.
  • MFR melt flow rate
  • styrenic block copolymers include styrene / ethylene / butene / styrene block copolymers (SEBS), styrene / ethylene / propylene / styrene block copolymers (SEPS), and styrene / butadiene / stin blocks.
  • SEBS styrene / ethylene / butene / styrene block copolymers
  • SEPS styrene / ethylene / propylene / styrene block copolymers
  • SEPS styrene / butadiene / stin blocks.
  • SBS copolymer
  • SIS styrene / isoprene / styrene block copolymer
  • SEP styrene / ethylene / propylene block copolymer
  • the upper limit is usually 20 parts by weight or less, more preferably with respect to 100 parts by weight of the total of (A) and (B). Is 10 parts by weight or less, more preferably 5 parts by weight or less, and the lower limit is usually 0.1 parts by weight.
  • the upper limit of the propylene resin (P) is usually 20 parts by weight with respect to a total of 100 parts by weight of the (A) and (B). Below, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less, and the lower limit is usually 0.1 parts by weight.
  • the styrene elastomer or its hydrogenated product (S) is in a total of 100 parts by weight of (A) and (B).
  • the upper limit is usually 20 parts by weight or less, more preferably 10 parts by weight or less, further preferably 5 parts by weight or less, and the lower limit is usually 0.1 parts by weight.
  • the propylene resin (P) and the styrene elastomer or hydrogenated product (S) are used as the other resin
  • the propylene resin (P) and the styrene elastomer or hydrogenated product thereof are used.
  • the upper limit of the total of (S) is usually 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less based on 100 parts by weight of the total of (A) and (B).
  • the lower limit is usually 0.1 parts by weight.
  • an embodiment in which the propylene resin (P) is not added and an embodiment in which the styrene elastomer or its hydrogenated product (S) is not added are more desirable. It is an aspect and the aspect which does not add the said propylene-type resin (P) and the said styrene-type elastomer, or its hydrogenated substance (S) is a more desirable aspect.
  • the low density ethylene / ⁇ -olefin copolymer (F) is in a small amount or not present in terms of stickiness.
  • Olefin polymer composition (E) consisting essentially of 0 to 20 parts by weight of at least one polymer selected from S) (in an amount relative to a total of 100 parts by weight of (A) and (B))
  • Olefin polymer composition (E) consisting essentially of 0 to 20 parts by weight of at least one polymer selected from S) (in an amount relative to a total of 100 parts by weight of (A) and (B))
  • the total of the propylene resin (P) having a Tm of 140 to 155 ° C. and the styrene elastomer or its hydrogenated product (S) is 0 with respect to 100 parts by weight of the total of (A) and (B).
  • the case of parts by weight is also included.
  • “substantially” means that the olefin polymer composition (E) may contain additives as other components within the range not impairing the effects of the present invention, but other components are included. Indicates no.
  • Additives include antioxidants, hydrochloric acid absorbers, heat stabilizers, light stabilizers, UV absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizing agents, Examples thereof include foaming agents, plasticizers, anti-bubble agents, crosslinkers, flowability improvers such as peroxides, weld strength improvers, and the like.
  • these additives For example, a commercial item can be used.
  • the amount of the olefin polymer composition (E) is not particularly limited as long as it is within the range where the effects of the present invention can be obtained. It is usually 0.01 to 1.00 parts by weight with respect to 100 parts by weight in total with B).
  • the olefin polymer composition (E) used in the present invention has a MFR in a specific range, it is difficult to blow mold only with the olefin polymer composition (E), but as a surface layer of a multilayer blow molded article. It can be used, and when used as a surface layer, it exhibits excellent gloss and has excellent physical properties.
  • the method for preparing the olefin polymer composition (E) is not particularly limited.
  • a propylene resin (A), an ethylene / ⁇ -olefin copolymer (B) and a nucleating agent (D) can be arbitrarily used.
  • the strand is usually formed into pellets using a pelletizer or the like before blow molding.
  • the propylene resin (A) the propylene resin (A), the ethylene / ⁇ -olefin copolymer (B) or a low-density ethylene / ⁇ -olefin copolymer (F) used as necessary may be modified.
  • a reactive additive such as a peroxide such as an organic peroxide or a crosslinking agent
  • the reason why the multilayer blow container formed using the olefin polymer composition (E) as a resin for forming the outermost layer exhibits good physical properties is not clear, but ethylene / ⁇ -olefin having a crystal melting point in a specific range.
  • the copolymer (B) it is considered that the ethylene / ⁇ -olefin copolymer (B) is finely dispersed in the propylene-based resin (A). It is considered that the impact resistance is high and the impact resistance is high, and furthermore, the impact resistance and the low stickiness are compatible.
  • the resin used for the outermost layer is composed of the above-mentioned olefin polymer composition (E).
  • the multilayer blow container of the present invention has at least one inner layer as a layer other than the outermost layer.
  • the other layer (inner layer) forming the multilayer blow container is not particularly limited and is usually made of a thermoplastic resin other than the olefin polymer composition (E).
  • examples thereof include vinyl copolymers, polyvinyl alcohol resins or polyvinyl chloride resins, polyvinyl chloride resins, and modified polyolefin resins.
  • a mixture of two or more of the above resins can also be used.
  • a propylene polymer (G) and an ethylene polymer (H) are preferable.
  • the propylene polymer (G) is a propylene polymer having a propylene-derived constitutional unit of 51 mol% or more, and the ethylene polymer (H) is an ethylene-derived constitutional unit of 51 mol% or more. It is an ethylene polymer.
  • Multi-layer blow container is formed from styrene polymer or other polar resin such as polyethylene terephthalate resin, polyamide resin, ABS resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol resin, polyvinyl chloride resin as other layer (inner layer)
  • styrene polymer or other polar resin such as polyethylene terephthalate resin, polyamide resin, ABS resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol resin, polyvinyl chloride resin as other layer (inner layer)
  • the outermost layer of the multilayer blow container of the present invention that is, the layer formed from the olefin polymer composition (E) is highly glossy.
  • the multilayer blow container is also excellent in impact resistance.
  • the MFR which is an index of fluidity of the olefin polymer composition (E) is in a specific range. Yes. For this reason, in blow molding, it is estimated that the surface of the heated molten resin immediately before contacting the mold is easily smoothed, and the surface is likely to be smooth even after blow molding, thereby providing excellent surface gloss. It is considered that a multilayer blow container can be obtained. Moreover, since MFR which is an index of fluidity of the olefin polymer composition (E) is in a specific range, the surface appearance is also good.
  • an ethylene / ⁇ -olefin copolymer (B) is used as a raw material of the composition. Since the ethylene / ⁇ -olefin copolymer (B) has a crystal melting point in a specific range, the obtained molded product exhibits excellent properties such as the above-described correlated adhesiveness and low stickiness, Even when the amount of the ethylene / ⁇ -olefin copolymer (B) used relative to the propylene resin (A) is small, the impact resistance can be improved efficiently.
  • a low density ethylene / ⁇ -olefin copolymer (F) is used as a raw material of the composition as required.
  • the low-density ethylene / ⁇ -olefin copolymer (F) can efficiently improve the low-temperature impact resistance even when the amount used for the propylene-based resin (A) is small.
  • the multilayer blow container of the present invention has high gloss and excellent impact resistance, and when the low density ethylene / ⁇ -olein copolymer (F) is used, low temperature impact resistance is achieved.
  • the present inventors have estimated that it is also excellent.
  • the multilayer blow container of the present invention Since the multilayer blow container of the present invention has excellent impact resistance, cracks and the like due to external impact are suppressed, and since the outermost layer is highly glossy, the container has gloss with a transparent feeling. In addition, since the multilayer blow container of the present invention is excellent in low-temperature impact resistance, even when the multilayer blow container is filled with contents and transported, stored, etc. under low temperature conditions, it is due to impact from the outside. Cracks and the like are suppressed.
  • the layer structure of the multilayer blow container of the present invention is not particularly limited as long as the outermost layer is a layer made of the olefin polymer composition (E).
  • the outermost layer made of the olefin polymer composition (E) A two-layer configuration with the innermost layer (layer configuration arranged in order of outermost layer / innermost layer), an outermost layer made of the olefin polymer composition (E), an intermediate layer adjacent to the outermost layer, Three-layer configuration with the innermost layer adjacent to the intermediate layer (layer configuration arranged in order of outermost layer / intermediate layer / innermost layer), outermost layer made of the olefin polymer composition (E), and adjacent to the outermost layer A four-layer structure (outermost layer / intermediate layer (1) /) of the intermediate layer (1), the intermediate layer (2) adjacent to the intermediate layer (1), and the innermost layer adjacent to the intermediate layer (2).
  • a layer located inside the outermost layer is defined as an inner layer. That is, in the present invention, the innermost layer and the intermediate layer correspond to inner layers, and the multilayer blow container of the present invention may have at least one inner layer and may have two or more layers.
  • the layer adjacent to the outermost layer is formed from the propylene polymer (G) or the ethylene polymer (H), so-called Even without using an adhesive resin, strong adhesiveness was exhibited.
  • the layer adjacent to the outermost layer made of the olefin polymer composition (E) is a propylene polymer ( G) or an ethylene polymer (H) is preferable.
  • the layer adjacent to the olefin polymer composition (E) is a layer other than the propylene polymer (G) and the ethylene polymer (H), the olefin polymer composition (E). From the viewpoint of adhesiveness with the outermost layer made of, it is preferable that the outermost layer made of the olefin polymer composition (E) and other layers are formed via the adhesive resin layer.
  • the multilayer blow container of the present invention may have any layer colored.
  • the propylene polymer (G) is not particularly limited, and examples thereof include homopolypropylene, propylene / ⁇ -olefin random copolymer, propylene / ⁇ -olefin block copolymer, and the like.
  • the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is preferably in the range of 0.1 to 20.0 g / 10 minutes. In particular, 0.1 to 5 g / 10 min is preferable.
  • the crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is preferably in the range of 100 to 168 ° C.
  • the ethylene polymer (H) is not particularly limited, and examples thereof include so-called high density polyethylene, linear low density polyethylene, and low density polyethylene.
  • the density of the ethylene polymer (H) measured by the density gradient tube method is preferably 0.860 to 0.980 g / cm 3 , and the measurement temperature is 230 ° C. according to ASTM D-1238.
  • the MFR measured under a 16 kg load is preferably 0.01 to 20 g / 10 min, and particularly preferably 0.1 to 5 g / 10 min.
  • the modified polyolefin resin (I) is not particularly limited, and generally an acid-modified polyolefin can be used.
  • the acid used for the acid modification include an ethylenically unsaturated carboxylic acid such as maleic anhydride, acrylic acid, methacrylic acid, and itaconic anhydride, or an anhydride thereof.
  • the polyolefin resin used for modification is preferably an ethylene / ⁇ -olefin copolymer, a propylene homopolymer, or a propylene / ⁇ -olefin copolymer.
  • the inner layer other than the layer adjacent to the outermost layer in the multilayer blow container is composed of a propylene polymer (G), an ethylene polymer (H), a styrene polymer, a polyethylene terephthalate resin, a polyamide resin, an ABS resin.
  • G propylene polymer
  • H ethylene polymer
  • H styrene polymer
  • polyethylene terephthalate resin a polyamide resin
  • ABS resin an ABS resin.
  • a layer formed of at least one resin selected from ethylene-vinyl acetate copolymer, polyvinyl alcohol resin or polyvinyl chloride resin is preferable.
  • any method may be used as long as it is blow molding.
  • the molding method include a direct blow molding method (hollow molding method), an injection stretch blow molding method (injection hollow molding method), an extrusion stretch blow molding method, and a sheet blow molding method.
  • the multilayer blow container is preferably obtained by molding by a direct blow molding method or an injection stretch blow molding method from the viewpoint of productivity in mass production.
  • the olefin polymer composition (E) and other resins are used, and the olefin polymer composition (E) is the outermost layer. Then, while the obtained parison is still in a molten state, it is sandwiched between blow molds, and fluid is blown into the parison to be molded into a predetermined shape. Since the layer formed from the olefin polymer composition (E) is the outermost layer, a high gloss multilayer blow container can be obtained.
  • the molding conditions depend on the properties of the resin, but the temperature of the resin when the fluid is blown, that is, the molding temperature is preferably 120 to 260 ° C., and the fluid blowing pressure is 2 to 10 kg / cm 2.
  • a blow ratio of 1.2 to 5.0 is preferable from the viewpoint of moldability.
  • the blow ratio here refers to the outer diameter of the cylindrical molten parison extruded from the extruder die, and the value obtained by dividing the outer diameter of the bottle to be formed.
  • the olefin polymer composition (E) and other resins are injection molded so that the olefin polymer composition (E) is the outermost layer.
  • the preform is forcibly stretched longitudinally using a stretching rod or the like, and then the transverse direction.
  • a multilayer blow container can be obtained by press-fitting a pressurized fluid into the preform for further stretching.
  • the injection temperature of the olefin polymer composition (E) is usually in the range of 160 to 260 ° C.
  • the temperature of the preform immediately before the longitudinal stretching is preferably 110 to 150 ° C.
  • the longitudinal stretching ratio is preferably 1.5 to 4.0 times
  • the transverse stretching ratio is 1.5 to 3.0 times. It is preferable that
  • the thickness and size of the multilayer blow container of the present invention are appropriately determined depending on the use of the multilayer blow container and the like. Usually, the thickness is 0.3 to 10.0 mm, the size is 10 to 300 mm in diameter, and the height is 10 to 300 mm.
  • the thickness of the outermost layer of the multilayer blow container of the present invention is preferably the ratio of the thickness of the outer layer to the other inner layer (outer layer / inner layer), preferably 50/50 to 5/95, more preferably 30/70 to 10 / 90 is preferred. Within the above-mentioned range, the high gloss of the outer layer is most easily expressed and the moldability is good, which is preferable.
  • the multilayer blow container of the present invention is excellent in transparency when a transparent resin is used for layers other than the outermost layer.
  • the haze value (haze) measured using a haze meter in accordance with JIS-K7105 is preferably 30 or less, and more preferably 20 or less. Within the above range, it is possible to obtain a high value-added bottle with very good contents visibility.
  • the multilayer blow container of the present invention is excellent in gloss.
  • the 60 ° gloss measured with a gloss meter in accordance with JIS-K7105 of the outermost layer is preferably 70 or more, and 75 or more. More preferably. Within the above range, it is possible to obtain a high value-added bottle exhibiting an excellent gloss appearance.
  • the multi-layer blow container according to the present invention can be used for various applications, for example, filling containers such as sauces, dressings, juices, fruits, sweets, boiled vegetables, toiletries such as cosmetics and shampoos. It is suitable as a container for filling sanitary goods such as containers and liquid detergents.
  • the method for producing a multilayer blow container of the present invention uses a thermoplastic resin composition other than the olefin polymer composition (E) and the olefin polymer composition (E) described above, and the olefin polymer composition (E) It is preferable that the outermost layer is formed and molded by a direct blow molding method or an injection stretch blow molding method so that the thermoplastic resin composition other than the olefin polymer composition (E) forms at least one inner layer.
  • thermoplastic resin other than the coalescence composition (E) and the olefin polymer composition (E) those described in the above-mentioned section [Multilayer Blow Container] can be used.
  • Other resins and various additives described above can also be used.
  • a multilayer blow container in which the outermost layer is formed from the olefin polymer composition (E) is molded by a direct blow molding method or an injection stretch blow molding method. For this reason, the resulting multilayer blow container is highly glossy because the outermost layer of the multilayer blow container contains the ethylene / ⁇ -olefin copolymer (B). The multilayer blow container is also excellent in impact resistance.
  • the multilayer blow container obtained by the production method of the present invention has excellent impact resistance, cracks due to external impact are suppressed, and the outermost layer is highly glossy, so that the container has gloss with a transparent feeling. .
  • the solid part after washing was defined as a solid titanium catalyst component (A).
  • the solid titanium catalyst component (A) was stored as a decane slurry, but a portion thereof was dried for the purpose of examining the catalyst composition.
  • the composition of the solid titanium catalyst component (A) was 2.3 wt% titanium, 61 wt% chlorine, 19 wt% magnesium, and 12.5 wt% DIBP.
  • the free titanium compound was detected by the following method. 10 ml of the supernatant of the above solid catalyst component was collected with a syringe into a 100 ml branched Schlenk previously purged with nitrogen and charged. Next, the solvent hexane was dried in a nitrogen stream, and further vacuum-dried for 30 minutes. This was charged with 40 ml of ion-exchanged water and 10 ml of 50% by volume sulfuric acid and stirred for 30 minutes. This aqueous solution was transferred to a 100 ml volumetric flask through a filter paper, followed by conc. As a masking agent for iron (II) ions.
  • the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based resin (A-1) was calculated from 7.0 C / 10 min, 13 C-NMR.
  • the weight of the structural unit derived from ethylene is 3.2% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight, DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 145 ° C. and Mw / Mn (molecular weight distribution) was 5.3.
  • the resulting propylene-based resin (A-2) had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) calculated from 7.0 C / 10 min, 13 C-NMR.
  • MFR melt flow rate
  • the weight of ethylene-derived constitutional unit when the total of propylene-derived constitutional unit and ethylene-derived constitutional unit is 100% by weight is 4.8% by weight
  • DSC melting point measured by DSC based on JIS-K7121
  • Crystal melting point was 136 ° C.
  • Mw / Mn molecular weight distribution
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the obtained propylene resin (A-3) was calculated from 7.0 C / 10 min, 13 C-NMR.
  • the weight of the structural unit derived from ethylene is 1.0% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight.
  • DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 156 ° C. and Mw / Mn (molecular weight distribution) was 5.0.
  • the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based resin (A-4) was calculated from 13 C-NMR at 3.0 g / 10 min.
  • the weight of the structural unit derived from ethylene is 3.2% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight, DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 145 ° C. and Mw / Mn (molecular weight distribution) was 5.3.
  • the resulting propylene resin (A-5) had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) calculated from 13 C-NMR at 15.0 g / 10 min.
  • MFR melt flow rate
  • the weight of the structural unit derived from ethylene is 3.2% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight, DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 145 ° C. and Mw / Mn (molecular weight distribution) was 5.3.
  • the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours, and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.
  • the solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene to make a total volume of 160 liters.
  • ethylene supply was started again at a flow rate of 8 Nm 3 / hr. After 15 minutes, the ethylene flow rate was lowered to 2 Nm 3 / hr, and the pressure in the system was adjusted to 0.08 MPaG. During this time, the temperature in the system rose to 35 ° C. Thereafter, ethylene was supplied at a flow rate of 4 Nm 3 / hr for 3.5 hours while adjusting the temperature in the system to 32 to 35 ° C. During this time, the pressure in the system was maintained at 0.07 to 0.08 MPaG. Next, after the inside of the system was replaced with nitrogen, the supernatant was removed and washed twice with hexane. Thus, a prepolymerized catalyst (2) in which 3 g of polymer was prepolymerized per 1 g of the solid catalyst component was obtained.
  • Polymerization was started while continuously supplying 4.1 g / hr of the prepolymerized catalyst (2) prepared above and TIBA at a rate of 5 mmol / hr.
  • the yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, the DSC melting point (crystal melting point measured by DSC according to JIS-K7121) was 98 ° C., measured by the density gradient tube method. Density was 0.903 g / cm 3 , MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg) was 7.0 g / 10 min, and Mw / Mn (molecular weight distribution) was 2.6. .
  • the obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / ⁇ -olefin copolymer (B-1).
  • the yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, the DSC melting point (crystal melting point measured by DSC according to JIS-K7121) was 113 ° C., measured by the density gradient tube method. Density was 0.913 g / cm 3 , MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg) was 7.0 g / 10 min, and Mw / Mn (molecular weight distribution) was 2.6. .
  • the obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / ⁇ -olefin copolymer (B-2).
  • the yield of the obtained ethylene / 1-hexene copolymer is 5.8 kg / hr
  • DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) is 120 ° C., measured by density gradient tube method Density was 0.924 g / cm 3
  • MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg) was 7.0 g / 10 min
  • Mw / Mn molecular weight distribution
  • the obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / ⁇ -olefin copolymer (B-3).
  • Example A1 97 parts by weight of propylene-based resin (A-1), 3 parts by weight of ethylene / ⁇ -olefin copolymer (B-1), and ADEKA STAB NA-21 (manufactured by ADEKA: bis (2 , 4,8,10-Tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide as a main component 0.15 parts by weight of an aromatic phosphate ester compound nucleating agent) and a phenolic antioxidant [pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) as an additive ) Propionate]], 0.10 parts by weight of a phosphorous antioxidant [Tris (2,4-di-t-butylphenyl) phosphite], and calcium stearate as a neutralizing agent 0.09 part by weight of
  • melt flow rate (MFR) of the olefin polymer composition (E-1) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) is 7.0 g / 10 min, DSC melting point (according to JIS-K7121) Crystal melting point measured by DSC) was 147 ° C.
  • the molding temperature is set to 200 ° C. and the fluid blowing pressure is set to 5.0 kg / cm 2 .
  • a molten parison having an outer diameter of 20.0 mm was formed by a crosshead die having a die hole size of 14.0 mm and a core size of 12.5 mm, weight 34 g, inner capacity 780 ml, mouth screw outer diameter 27.0 mm, waist circumference
  • a cylindrical multilayer blow container having a two-layer structure having an outer diameter of 72 mm and a waistline average thickness of 0.5 mmt was manufactured.
  • a propylene-based random copolymer B251VT (Co., Ltd.) is used for a base material (inner layer) by using an intermediate layer and an outer layer extruder having a cylinder temperature set at 200 ° C. without using an inner layer extruder.
  • melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.2 g / 10 min
  • DSC melting point accordinging to JIS-K7121, crystal melting point measured by DSC) ) Is 146 ° C.
  • E-1 olefin polymer composition
  • blow mold After forming a molten parison in the shape of a mold, it was sandwiched between blow molds adjusted to a temperature of 25 ° C. by a water circulation circuit, stretched and adhered to the mold with compressed air, and cooled and solidified to obtain a multilayer blow container.
  • the blow mold two types of molds, that is, a mold subjected to sandblasting # 400 as a surface treatment and a mold subjected to sandblasting # 200, are used, and a multilayer blow container is formed using each mold. Obtained.
  • haze, gloss (gross), moldability, adhesiveness, impact resistance (full water drop impact strength) and stickiness were measured by the following evaluation methods.
  • a multilayer blow container was prepared using two types of molds, and the gloss of each was evaluated. These results are shown in the table.
  • Example A2 The same procedure as in Example A1 was carried out except that the ratio of 95.5 parts by weight of the propylene resin (A-1) and 4.5 parts by weight of the ethylene / ⁇ -olefin copolymer (B-1) was changed.
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-2) obtained in Example A2 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • Example A3 At the time of multilayer blow molding, instead of propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) for the base material (inner layer), propylene random block copolymer B511QA (manufactured by Prime Polymer Co., Ltd., melt) Flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.2 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC is 158 ° C.) The same procedure as in Example A2 was carried out except that the intermediate layer was used.
  • MFR Flow rate
  • Example A4 In the case of multilayer blow molding, instead of the propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) for the base material (inner layer), PE resin HDPE, HZ-6008B (manufactured by Prime Polymer Co., Ltd.) Rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 0.7 g / 10 min, density measured by density gradient tube method is 0.958 g / cm 3 )
  • Example A2 was carried out in the same manner as in Example A2.
  • Example A5 The same procedure as in Example A1 was carried out except that the ratio of propylene resin (A-1) was 80.0 parts by weight and that of ethylene / ⁇ -olefin copolymer (B-1) was 20.0 parts by weight.
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-3) obtained in Example A5 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 148 ° C.
  • ADEKA STAB NA-21 manufactured by ADEKA
  • melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-7) obtained in Example A6 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 149 ° C.
  • Example A7 When propylene resin (A-1) is stirred and mixed with a Henschel mixer instead of propylene resin (A-4), [2,5-di-methyl-2,5- The same procedure as in Example A2 except that 0.006 part by weight of di- (benzoylperoxy) hexane] was added.
  • melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-20) obtained in Example A7 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • MFR melt flow rate
  • DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • the results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
  • Example A1 The same procedure as in Example A1 was carried out except that the proportion of propylene resin (A-1) was changed to 100 parts by weight and that of ethylene / ⁇ -olefin copolymer (B-1) was changed to 0 part by weight.
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-4) obtained in Comparative Example A1 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • Comparative Example A1 since the ethylene / ⁇ -olefin copolymer (B) is not blended, the requirements of this claim are not satisfied. Since the ethylene / ⁇ -olefin copolymer (B) is not blended, the adhesiveness and impact resistance (full water impact resistance) are inferior.
  • Example A2 The same procedure as in Example A1 was carried out except that the ratio of propylene-based resin (A-1) was changed to 70.0 parts by weight and that of ethylene / ⁇ -olefin copolymer (B-1) was changed to 30.0 parts by weight.
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-5) obtained in Comparative Example A2 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • Example A3 The same procedure as in Example A2 was conducted, except that ADK STAB NA-21 (manufactured by ADEKA) was not added as the nucleating agent (D).
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-6) obtained in Comparative Example A3 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 145 ° C.
  • Example A4 The same procedure as in Example A2 was conducted except that the propylene resin (A-2) was changed to the propylene resin (A-2).
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-8) obtained in Comparative Example A4 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, the crystalline melting point measured by DSC) was 138 ° C.
  • Example A5 The same procedure as in Example A2 was conducted except that the propylene resin (A-3) was changed to the propylene resin (A-3).
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-9) obtained in Comparative Example A5 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 158 ° C.
  • Example A6 The same procedure as in Example A2 was conducted except that the propylene resin (A-4) was changed to the propylene resin (A-4).
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-10) obtained in Comparative Example A6 is 3.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • Example A7 The same procedure as in Example A2 was carried out except that the propylene resin (A-5) was replaced with a propylene resin (A-5).
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-11) obtained in Comparative Example A7 is 15.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • melt flow rate (MFR) ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg
  • MFR melt flow rate
  • Example A8 The same procedure as in Example A2 was conducted except that the ethylene / ⁇ -olefin copolymer (B-2) was changed to the ethylene / ⁇ -olefin copolymer (B-1).
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-12) obtained in Comparative Example A8 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • the ethylene / ⁇ -olefin copolymer (B-2) used in Comparative Example A8 has a DSC melting point (crystal melting point measured by DSC according to JIS-K7121) of the ethylene / ⁇ -olefin copolymer (B). It is higher than the range specified in the claims. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.
  • Comparative Example A9 The same procedure as in Comparative Example A8 was carried out except that the ratio of propylene resin (A-1) was 90.0 parts by weight and that of ethylene / ⁇ -olefin copolymer (B-2) was 10.0 parts by weight.
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-13) obtained in Comparative Example A9 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • the ethylene / ⁇ -olefin copolymer (B-2) used in Comparative Example A9 has a DSC melting point (crystal melting point measured by DSC according to JIS-K7121) of the ethylene / ⁇ -olefin copolymer (B). It is higher than the range specified in the claims. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.
  • Comparative Example A10 The procedure was the same as Comparative Example A8 except that the ratio of propylene resin (A-1) was 80.0 parts by weight and that of ethylene / ⁇ -olefin copolymer (B-2) was 20.0 parts by weight.
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-14) obtained in Comparative Example A10 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • the ethylene / ⁇ -olefin copolymer (B-2) used in Comparative Example A10 has a DSC melting point (crystal melting point measured by DSC according to JIS-K7121) of the ethylene / ⁇ -olefin copolymer (B). It is higher than the range specified in the claims. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.
  • Example A11 The same procedure as in Example A2 was conducted, except that the ethylene / ⁇ -olefin copolymer (B-3) was replaced with the ethylene / ⁇ -olefin copolymer (B-3).
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-15) obtained in Comparative Example A11 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • the ethylene / ⁇ -olefin copolymer (B-3) used in Comparative Example A11 has a DSC melting point (crystal melting point measured by DSC according to JIS-K7121) of the ethylene / ⁇ -olefin copolymer (B). It is higher than the range specified in the claims. For this reason, gloss (gross), adhesiveness, and impact resistance (full water drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.
  • melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-16) obtained in Comparative Example A12 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • ULTRAZEX 1030L was used in place of the ethylene / ⁇ -olefin copolymer (B).
  • the DSC melting point of ULTZEX 1030L (according to JIS-K7121, crystal melting point measured by DSC) is 115 ° C., which is higher than the DSC melting point range of the ethylene / ⁇ -olefin copolymer (B) defined in the claims. .
  • Ultzex 1030L is polymerized with a Ziegler-Natta catalyst that is not a metallocene catalyst, the multilayer blow container formed from the olefin polymer composition (E-16) has adhesiveness, stickiness and impact resistance (full water). Drop impact strength is inferior. Furthermore, the balance between impact resistance and stickiness is not good.
  • melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-17) obtained in Comparative Example A13 is 8.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • HZ-2100J was used in place of the ethylene / ⁇ -olefin copolymer (B).
  • the DSC melting point of HZ-2100J (according to JIS-K7121, crystal melting point measured by DSC) is 131 ° C., which is higher than the DSC melting point range of the ethylene / ⁇ -olefin copolymer (B) specified in the claims.
  • the density measured by the density gradient tube method of HZ-2100J is 0.956 g / cm 3 .
  • the multilayer blow container formed from the olefin polymer composition (E-17) is inferior in adhesion and impact resistance (full water drop impact strength). Furthermore, the balance between impact resistance and stickiness is not good.
  • Tuffmer P-0680 polyethylene rubber (EPR), manufactured by Mitsui Chemicals, Inc., density 0. 870 g / cm 3 , melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.0 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) ) Is not measured.), And Tufmer P-0680 (manufactured by Mitsui Chemicals, Inc.) as propylene resin (A-1) as 90.0 parts by weight and ethylene / ⁇ -olefin copolymer (B) was carried out in the same manner as in Example A1, except that the ratio was changed to 10.0 parts by weight.
  • EPR polyethylene rubber
  • MFR melt flow rate
  • melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-18) obtained in Comparative Example A14 is 6.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • Tuffmer P-0680 manufactured by Mitsui Chemicals, Inc.
  • Tuffmer P-0680 does not correspond to an ethylene / ⁇ -olefin copolymer (B) because its DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) is not measured.
  • the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) was 1.0 g / 10 min, and the density measured by the density gradient tube method was 0.870 g / cm 3 . .
  • the multilayer blow container formed from the olefin polymer composition (E-18) is inferior in glossiness (gloss), adhesiveness and stickiness.
  • Tuffmer P-0180 polyethylene rubber (EPR), manufactured by Mitsui Chemicals, Inc., density 0. 0
  • EPR polyethylene rubber
  • melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 8.0 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) ) Is not measured.), And 90.0 parts by weight of propylene resin (A-1) and ethylene / ⁇ -olefin copolymer (B) as Toughmer P-0180 (manufactured by Mitsui Chemicals, Inc.) was carried out in the same manner as in Example A1, except that the ratio was changed to 10.0 parts by weight.
  • MFR melt flow rate
  • melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-19) obtained in Comparative Example A15 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
  • Tuffmer P-0180 (manufactured by Mitsui Chemicals, Inc.) is used in place of the ethylene / ⁇ -olefin copolymer (B).
  • Tuffmer P-0180 does not correspond to an ethylene / ⁇ -olefin copolymer (B) because the DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) is not measured.
  • the density was 0.870 g / cm 3 . For this reason, the multilayer blow container formed from the olefin polymer composition (E-19) has poor adhesion and stickiness.
  • Example B1 97 parts by weight of propylene-based resin (A-1), 3 parts by weight of ethylene / ⁇ -olefin copolymer (B-1), and ADEKA STAB NA-21 (manufactured by ADEKA: bis (2 , 4,8,10-Tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide as a main component Tafmer P-0280 (ethylene-propylene copolymer, manufactured by Mitsui Chemicals, Ltd.) as 0.15 parts by weight of an aromatic phosphate ester compound nucleating agent) as a low density ethylene / ⁇ -olefin copolymer (F) the density was measured by a density gradient tube method: 0.870 g / cm 3, Ziegler-Natta catalyst, DSC melting point (according to JIS-K7121, the crystalline melting point was measured by DSC): not
  • melt flow rate (MFR) of the propylene resin composition (E-21) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 7.0 g / 10 min, DSC melting point (according to JIS-K7121) Crystal melting point measured by DSC) was 147 ° C.
  • the molding temperature is set to 200 ° C. and the fluid blowing pressure is set to 5.0 kg / cm 2 .
  • a molten parison having an outer diameter of 20.0 mm was formed by a crosshead die having a die hole size of 14.0 mm and a core size of 12.5 mm, weight 34 g, inner capacity 780 ml, mouth screw outer diameter 27.0 mm, waist circumference
  • a cylindrical multilayer blow container having a two-layer structure having an outer diameter of 72 mm and a waistline average thickness of 0.5 mmt was manufactured.
  • a propylene-based random copolymer B251VT (Co., Ltd.) is used for a base material (inner layer) by using an intermediate layer and an outer layer extruder having a cylinder temperature set at 200 ° C. without using an inner layer extruder.
  • melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.2 g / 10 min
  • DSC melting point accordinging to JIS-K7121, crystal melting point measured by DSC)
  • Is 146 ° C. with an intermediate layer extruder and the olefin polymer composition (E-21) is dissolved with an outer layer extruder so that the outer layer thickness ratio is 15%.
  • blow mold After forming a molten parison in the shape of a mold, it was sandwiched between blow molds adjusted to a temperature of 25 ° C. by a water circulation circuit, stretched and adhered to the mold with compressed air, and cooled and solidified to obtain a multilayer blow container.
  • the blow mold two types of molds, that is, a mold subjected to sandblasting # 400 as a surface treatment and a mold subjected to sandblasting # 200, are used, and a multilayer blow container is formed using each mold. Obtained.
  • Example B2 Low density ethylene / ⁇ -olefin copolymer (F) was measured by Mitsui Chemicals, Inc., Tafmer A-4085S (ethylene-butene copolymer, density gradient tube method) from Mitsui Chemicals, Inc., Tafmer P-0280.
  • a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
  • Example B3 The propylene resin (A-1) was changed to 90 parts by weight, the ethylene / ⁇ -olefin copolymer (B-1) was changed to 10 parts by weight, and the low density ethylene / ⁇ -olefin copolymer (F) was changed to Mitsui A strand was obtained in the same manner as in Example B1, except that Tuffmer P-0280 manufactured by Kagaku Co., Ltd. was changed to Tuffmer A-4085S manufactured by Mitsui Chemicals, and the blending amount was changed from 15 parts by weight to 5 parts by weight. It was.
  • a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
  • Example B4 The low density ethylene / ⁇ -olefin copolymer (F) was changed in the same manner as in Example B1 except that Mitsui Chemicals Co., Ltd., Tafmer P-0280 was changed to Mitsui Chemicals Co., Ltd., Tafmer A-4085S. Obtained.
  • a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
  • Example B5 A strand was obtained in the same manner as in Example B1 except that the low-density ethylene / ⁇ -olefin copolymer (F) was not used.
  • a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
  • Example B6 The propylene-based resin (A-1) was changed to 95.5 parts by weight and the ethylene / ⁇ -olefin copolymer (B-1) was changed to 4.5 parts by weight to obtain a low density ethylene / ⁇ -olefin copolymer (F ) Was used, and a strand was obtained in the same manner as in Example B1 except that 0.1 part by weight of stearic acid monoglyceride was used as an antistatic agent.
  • a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
  • Example B7 The propylene resin (A-1) was changed to 90 parts by weight and the ethylene / ⁇ -olefin copolymer (B-1) was changed to 10 parts by weight, and the low density ethylene / ⁇ -olefin copolymer (F) was not used. A strand was obtained in the same manner as in Example B1.
  • a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
  • a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
  • Tuffmer P-0275 ethylene-propylene copolymer, density measured by density gradient tube method: 0.860 g / cm 3 , DSC melting point (according to JIS-K7121, crystal melting point measured by DSC): not observed , MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg): 5.4 g / 10 min) was carried out in the same manner as in Example B1 to obtain a strand.
  • a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
  • MFR Melt flow rate
  • the MFR of the propylene resin (A), the ethylene / ⁇ -olefin copolymer (B), the low density ethylene / ⁇ -olefin copolymer (F), and the olefin polymer composition (E) is ASTM D- It was measured according to 1238, measurement temperature 230 ° C., load 2.16 kg.
  • the strand obtained at the time of MFR measurement is collected and used for the following density measurement.
  • Crystalline melting points of the propylene resin (A), the ethylene / ⁇ -olefin copolymer (B), the low density ethylene / ⁇ -olefin copolymer (F) and the olefin polymer composition (E) are in accordance with JIS-K7121.
  • the measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer).
  • the peak of the endothermic peak at the third step measured here was defined as the crystalline melting point (Tm).
  • Tm crystalline melting point
  • Measurement condition Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg Sample shape: Press film (230 ° C molding, thickness 200-400 ⁇ m) First step: The temperature is raised from 30 ° C to 240 ° C at 10 ° C / min and held for 10 min.
  • Second step IV Decrease the temperature to 60 ° C at 10 ° C / min.
  • 3rd step IV Increase the temperature to 240 ° C at 10 ° C / min.
  • the half crystallization time (T 1/2 ) of the olefin polymer composition (E) was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer (DSC7)).
  • the olefin polymer composition (E) is crystallized under an isothermal condition of 125 ° C., and the calorific value associated with the crystallization is measured at this time, and the calorific value from the start of the exotherm (crystallization start) is half the total calorific value.
  • the time (seconds) until the crystallization time was measured as the half crystallization time (t 1/2 ).
  • a smaller half crystallization time (t 1/2 ) means a faster crystallization rate.
  • Measurement condition Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg Sample shape: Press film (230 ° C molding, thickness 200-400 ⁇ m) First step: The temperature is increased from 30 ° C to 220 ° C at 10 ° C / min and held for 3 min.
  • 2nd step IV Decrease the temperature to 125 ° C at 60 ° C / min.
  • the density of the ethylene / ⁇ -olefin copolymer (B) and the low density ethylene / ⁇ -olefin copolymer (F) is the same as that of the ethylene / ⁇ -olefin copolymer (B) and the low density obtained during the MFR measurement.
  • the strands of the density ethylene / ⁇ -olefin copolymer (F) were each heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured with a density gradient tube.
  • Mw / Mn molecular weight distribution
  • Mw and Mn were measured as follows using GPC-150C Plus manufactured by Waters.
  • TSKgel GMH6-HT and TSKgel GMH6-HTL were used as separation columns, the column size was 7.5 mm in inner diameter and 600 mm in length, the column temperature was 140 ° C., and o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase.
  • Yakuhin Kogyo Co., Ltd. and 0.025% by weight of BHT (Wako Pure Chemical Industries, Ltd.) as an antioxidant, moved at 1.0 ml / min, sample concentration of 0.1% by weight, sample injection The amount was 500 microliters, and a differential refractometer was used as a detector.
  • Standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw ⁇ 1000 and Mw> 4 ⁇ 10 6 , and used by Pressure Chemical Co. for 1000 ⁇ Mw ⁇ 4 ⁇ 10 6 .
  • the glossiness was evaluated by the following gloss measurement.
  • the measurement site was cut out from the container body, and the 60-degree glossiness of the outer layer was measured with a gloss meter (NIPPON DENSHOKU (VG2000)) in accordance with JIS-K7105. It can be said that the larger the gloss value, the better the glossiness.
  • AA Appearance is poor and adhesion is good
  • BB Appearance is poor and adhesion is slightly inferior when observed closely
  • CC Clear appearance is poor and adhesion is inferior [Odor]
  • the odor of the olefin polymer composition (E) was obtained by putting 10 g of the composition pellets in a 100 ml Erlenmeyer flask, sealing with a cap, taking out after heating in an oven at 100 ° C. for 1 hour, and immediately opening the cap. The generated odor was judged as superior or inferior in the sensory test as follows.
  • AA No odor
  • BB Some odor
  • CC Some odor [impact resistance]
  • the impact resistance was evaluated based on the presence or absence of surface cracks by the full water drop impact strength measurement method described below.
  • a multi-layer blow container (with an internal capacity of 780 ml) filled with water was cooled to 5 ° C. (evaluation of impact resistance), and each of the 10 containers cooled to each temperature had a bottom of 1 m from the concrete surface. It was dropped vertically from the height position and evaluated according to the following drop criteria. The determination of the crack was made based on whether or not a surface crack was generated.
  • Weight of structural unit derived from ⁇ -olefin in propylene resin calculated from 13 C-NMR The total of the structural unit derived from propylene calculated from 13 C-NMR and the structural unit derived from one or more olefins selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 20 carbon atoms is 100% by weight.
  • the weight of the structural unit derived from one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms is measured and calculated as follows based on the measurement of 13 C-NMR. I decided.
  • E (mol%) Mole fraction of structural units derived from ethylene (mol%)
  • P (mol%) mole fraction of structural units derived from propylene (mol%)
  • the weight percent of the structural unit derived from propylene and the weight percent of the structural unit derived from ethylene in the propylene-based resin (A) were calculated from the calculated E (mol%) and P (mol%) in weight percent. .

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Abstract

Cette invention concerne un conteneur multicouche moulé par soufflage présentant un brillant élevé, un remarquable aspect de surface et une excellente résistance aux chocs. Le conteneur multicouche moulé par soufflage est caractérisé en ce que sa couche la plus extérieure comprend une résine de propylène (A), un copolymère d'éthylène α-oléfine (B) et un agent de nucléation (D). La résine de propylène (A) comprend un copolymère de propylène et une α-oléfine (A-1) et possède un point de fusion des cristaux compris entre 140 et 155 °C (A-2) ; le copolymère d'éthylène α-oléfine (B)comprend un copolymère d'éthylène et au moins une α-oléfine comptant de 4 à 20 atomes de carbone (B-1) et ayant un point de fusion des cristaux d'au moins 85 °C et au plus de 110°C (B-2). La composition de polymère d'oléfine (E) possède une valeur MFR de 6 à 10 g/10mn (E-1).
PCT/JP2011/050939 2010-01-22 2011-01-20 Contenant multicouche moulé par soufflage et son procédé de fabrication WO2011090101A1 (fr)

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CN201180006278.4A CN102712186B (zh) 2010-01-22 2011-01-20 多层吹塑容器及其制造方法
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JP2018203297A (ja) * 2017-05-31 2018-12-27 株式会社プライムポリマー 滅菌容器
JP2019031314A (ja) * 2017-08-09 2019-02-28 住友化学株式会社 中空容器およびその製造方法、ならびにブローフィルシール用ポリプロピレン樹脂組成物
JP2019119814A (ja) * 2018-01-09 2019-07-22 日本ポリプロ株式会社 プロピレン系樹脂組成物及びその成形体
US20210039364A1 (en) * 2018-03-20 2021-02-11 Prime Polymer Co., Ltd. Laminates and liquid packaging bags
WO2022006196A1 (fr) * 2020-06-30 2022-01-06 Fina Technology, Inc. Composition de polypropylène transparent pour thermoformage
US11859072B2 (en) 2020-06-30 2024-01-02 Fina Technology, Inc. Clear polypropylene composition for thermoforming
US12116475B2 (en) 2020-06-30 2024-10-15 Fina Technology, Inc. Clear polypropylene composition for thermoforming

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KR101333450B1 (ko) 2013-11-26
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