WO2004106430A1 - プロピレン系重合体組成物およびその用途 - Google Patents
プロピレン系重合体組成物およびその用途 Download PDFInfo
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- WO2004106430A1 WO2004106430A1 PCT/JP2004/006688 JP2004006688W WO2004106430A1 WO 2004106430 A1 WO2004106430 A1 WO 2004106430A1 JP 2004006688 W JP2004006688 W JP 2004006688W WO 2004106430 A1 WO2004106430 A1 WO 2004106430A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
Definitions
- the present invention relates to a propylene polymer yarn composition, and more particularly, to a propylene polymer composition having excellent transparency, flexibility, scratch resistance, heat resistance, and rubber elasticity.
- Polypropylene is inexpensive and has excellent rigidity, moisture resistance, and heat resistance, and is therefore used in a wide range of applications such as automation and home appliance materials.
- polyolefins with flexibility and transparency have been desired.
- TP ⁇ thermoplastic polyolefin-based elastomer
- a system in which a styrene-based elastomer is added to PP for example, see JP-A-7-04.
- No. 8485/85) is flexible and transparent, but expensive, so its use is limited. Disclosure of the invention
- the present invention is intended to solve the problems associated with the prior art as described above, and is a propylene-based heavyweight which is inexpensive and has a good balance of transparency, flexibility, heat resistance, scratch resistance, and rubber elasticity. It is intended to provide a coalescing composition.
- the propylene-based polymer composition containing no St-based or ethylene-based copolymer and no propylene copolymer according to the present invention must satisfy all of the following (A), (B), (C), and (D). It is characterized by.
- the storage elastic modulus G (the ratio of (20 ° C) and G '(100 ° C) (G, (20 ° C) / G, (100 ° C)) obtained from the above dynamic viscoelasticity measurement is 5 or less
- the needle penetration temperature (° C) measured in accordance with JIS K7196 is 100 ° C to 1668 ° C.
- D 30% between chucks, 100% strain at a pulling speed of 30mm / min, and after holding for 10 minutes, unloading After 10 minutes residual strain is 20% or less.
- ⁇ isotactic polypropylene ⁇ isotactic polypropylene (i), 45 to 89 moles of propylene component 0/0, the ethylene component 10 to 25 mol%, from ⁇ - Orefin carbon number 4-20 optionally propylene 'ethylene' alpha-Orefin copolymer component units (a) containing an amount of 0 to 30 mole 0/0 (ii) (wherein ethylene component and 4 to 20 carbon atoms alpha-Orefin derived unit (a at least one of) comprises 0 mole 0/0 not) a 60 to 99 parts by weight,
- tensile modulus (YM) measured according to JIS 6301 is 100 MPa or less.
- the component unit (a) derived from ⁇ -olefin having 4 to 20 carbon atoms is 1-butene or 1-otaten.
- the propylene polymer composition according to the present invention is excellent in transparency, flexibility, heat resistance, scratch resistance and rubber elasticity in a well-balanced manner.
- This propylene polymer may be a homopolypropylene, a propylene ' ⁇ -olefin random copolymer, or a propylene block copolymer as long as it has the following properties.
- it is a homopolypropylene or a propylene-CK-olefin random copolymer.
- the melt flow rate (MFR; ASTM D1238, 230 ° C, 2.16 kg load) of the isotactic polypropylene (i) used in the present invention is 0.01 to 400 gZlO, preferably 0.5 to 90 g / min. 10 minutes. Also DSC measurement Is 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 150 ° C. or higher.
- isotactic polypropylene (i) having such an MFR value a propylene polymer composition having an excellent flowability of 1 "and capable of molding a large product can be obtained.
- an MFR value of 400 gZlO A composition formed from isotactic polypropylene exceeding the above may have poor impact resistance (IZ impact strength).
- the isotactic polypropylene (i) is a propylene. ⁇ -olefin ran- dom copolymer
- the -olefin is preferably selected from ethylene and or a olefin having 4 to 20 carbon atoms. It is preferable to contain it in an amount of 3 to 7 mol 1%, preferably 0.3 to 6 mol 1%, more preferably 0.3 to 5 mol%. .
- the content of the n-decane soluble component at room temperature in the propylene polymer was determined by immersing 5 g of a sample (propylene polymer) in 20 cc of boiling n-decane for 5 hours, cooling to room temperature.
- the precipitated solid phase is filtered through a G4 glass filter, dried, and back-calculated from the measured solid phase weight.
- the isotactic polypropylene (i) used in the present invention as described above can be produced by various methods.
- it can be produced by using a stereoregular catalyst.
- the catalyst can be produced using a catalyst formed from a solid titanium catalyst component, an organometallic compound catalyst component, and, if necessary, an electron donor.
- the solid titanium catalyst component include a solid titanium catalyst component in which titanium trichloride or a titanium trichloride composition is supported on a carrier having a specific surface area of 100 m2Z or more, or magnesium, halogen, or electron donor.
- a solid titanium catalyst component which comprises a carrier (preferably an aromatic carboxylic acid ester or an alkyl group-containing ether) and titanium as essential components and which is supported on a carrier having a specific surface area of 100 m2 / g or more. It can also be produced with a meta-mouth catalyst. Of these, the latter solid titanium catalyst component is particularly preferred.
- an organoaluminum compound is preferable.
- the organoaluminum conjugate specific examples include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum compound. Lumidium muhide halide and the like.
- the organoaluminum compound can be appropriately selected according to the type of the titanium catalyst component used.
- an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom, a boron atom, or the like can be used, and preferably, an ester compound and an ether compound having the above-described atoms. Is mentioned.
- Such a catalyst may be further activated by a method such as co-milling, or the above-mentioned olefin may be prepolymerized.
- propylene-ethylene-alpha - O Les fins random copolymer (ii) propylene 'ethylene' alpha - O Les fins random copolymer, 4 5 the propylene component 8 9 mole 0/0, preferably 4 5 8 0 mol 0/0, preferably 5 0-7 5 mol 0/0, 1 ethylene component 0-2 5 mol 0/0, preferably 1 0-2 3 mole 0/0, more preferably 1 2 to 2 3 mol %, optionally number 4-2 0 of ⁇ - Orefuin derived component single-position carbon (a) 0-3 0 mole 0/0, preferably 0-2 5 Monore%, more preferably 0 ⁇ Contains 20 mole%.
- Such a propylene.ethylene-a-olefin random copolymer (ii) has an intrinsic viscosity measured in 135 ° C. dephosphorus [] force, usually 0.01 to 10 dl Zg, preferably Preferably, it is in the range of 0.05 to 10 d1 / g.
- the intrinsic viscosity [ ⁇ ] 1S of the propylene / ethylene 'a-olefin random copolymer (ii) is within the above range, the propylene / ethylene' a-olefin random copolymer may have weather resistance, ozone resistance, heat aging resistance, low temperature properties, dynamic fatigue resistance, etc.
- This propylene'ethylene ⁇ ⁇ -olefin random copolymer (ii) was prepared by using a JIS No. 3 dumbbell in accordance with JIS K6301, using a distance between spans of 30 mm and a pulling speed of 30 mm / min.
- the stress (M100) at 100% strain measured at ° C is 4 Mpa or less, preferably 3 Mpa or less, more preferably 2 Mpa or less.
- the propylene 'ethylene ⁇ When the -olefin random copolymer (ii) is in such a range, flexibility, transparency and rubber production are excellent.
- the propylene 'ethylene' CK-olefin random copolymer (ii) has a crystallinity of not more than 20%, preferably 0 to 15%, as measured by X-ray diffraction.
- the propylene ethylene- ⁇ -olefin random copolymer (ii) has a single glass transition temperature, and the glass transition temperature Tg measured by a differential scanning calorimeter (DSC) is usually -10 °. It is desirable that the temperature be in the range of not more than C, preferably not more than 15 ° C. When the glass transition temperature Tg of the propylene-ethylene-co-olefin random copolymer (ii) is within the above-mentioned range, excellent cold resistance and low-temperature properties are obtained.
- This propylene 'ethylene'c (-olefin random copolymer (ii)) has a heat of fusion ⁇ T when a melting point (Tm, ° C) exists in an endothermic curve of a differential scanning calorimeter (DSC).
- H is 30 J / g or less, and the following relational expression is satisfied in the relationship between the C 3 content (mol%) and the heat of fusion ⁇ H (J / g).
- the molecular weight distribution (Mw / Mn, in terms of polystyrene, Mw: weight average molecular weight, Mn: number average molecular weight) measured by GPC should be 4.0 or less, preferably 3.0 or less, more preferably 2.5 or less. Is preferred.
- the propylene 'ethylene'-olefin copolymer (ii) as described above may be partially modified by grafting with a polar monomer.
- a polar monomer include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid or a derivative thereof, and a vinyl ester.
- the polar monomer include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid or a derivative thereof, and a vinyl ester.
- Compounds, vinyl chloride, and the like are examples of the polar monomer.
- the modified propylene 'ethylene' ⁇ -olefin copolymer is obtained by graft-polymerizing a polar monomer to the above-mentioned propylene-ethylene-hydroolefin copolymer (ii).
- the polar monomer is propylene.
- ethylene-hydroolefin copolymer (ii) 100 parts by weight , Usually 1 ⁇ It is used in an amount of 100 parts by weight, preferably 5 to 80 parts by weight. This graft polymerization is usually performed in the presence of a radical initiator.
- An organic peroxide, an azoich compound, or the like can be used as the radical cane opening agent.
- the radical initiator can be used as it is, mixed with the propylene / ethylene / ⁇ -olefin copolymer (ii) and the polar monomer, or can be used after being dissolved in a small amount of an organic solvent.
- organic solvent any organic solvent that can dissolve the radical initiator can be used without particular limitation.
- a reducing substance may be used.
- the graft amount of the polar monomer can be improved.
- Graphitic modification of the propylene 'ethylene' ⁇ -olefin copolymer (ii) with a polar monomer can be carried out by a conventionally known method, for example, by dissolving the propylene 'ethylene' -olefin copolymer (ii) in an organic solvent. Then, a polar monomer and a radical initiator, etc. are added to the solution, and at a temperature of 70 to 200 ° C., preferably 80 to 190 ° C., for 0.5 to 15 hours, preferably The reaction can be performed for 1 to 10 hours.
- Orefuin copolymer polymer and (ii) by reacting a polar monomer, a modified propylene' ethylene 'alpha - O les fin copolymer (ii) Can also be manufactured.
- This reaction is usually performed at a temperature equal to or higher than the melting point of the propylene / ethylene / ⁇ -olefin copolymer (ii), specifically at a temperature of 120 to 250 ° C, usually for 0.5 to 10 minutes. It is desirable that this be done.
- the thus obtained modified propylene 'ethylene alpha -... Modification amount of Orefin copolymer is usually 0 1-5 0 weight 0/0, preferably 0 2 to 3 0 wt %, More preferably 0.2 to 10% by weight.
- the propylene-based polymer composition of the present invention contains the above-mentioned modified propylene 'ethylene' ⁇ -olefin copolymer, the propylene-based polymer composition has excellent adhesiveness and compatibility with other resins, and is excellent in the propylene-based polymer composition. In some cases, the wettability of the surface of the obtained molded body is improved.
- the propylene 'ethylene' ⁇ -olefin random copolymer (ii) is the above-mentioned (i) meta for producing isotactic polypropylene. It can be produced in the same manner using an oral catalyzed catalyst, and can also be produced using a meta-aqueous catalyzed catalyst, but is not limited thereto.
- St-based or ethylene-based; copolymer refers to an ethylene / ⁇ -olefin-based block copolymer ( ⁇ ) or an aromatic hydrocarbon-based block copolymer ( ⁇ ) described below.
- Ethylene a-olefin block copolymer (M) The ethylene-a-olefin block copolymer (M) which is not contained in the propylene polymer composition according to the present invention is defined as having 3 to 1 carbon atoms. 0 and the structural unit 5-4 0 mole 0/0 derived from Orefuin of contained the crystalline polyethylene portion comprising a constituent unit 6 0-9 5 molar% derived from ethylene low crystalline copolymer And an amorphous copolymer part.
- the molecular weight distribution measured by GPC is 1-1.5.
- the amount of n-decane soluble components at room temperature is 0 to 20 wt ° /.
- the amount of the 23 ° C. n-decane-soluble component of the ethylene ' ⁇ -olefin block copolymer is measured as follows. That is, 3 g of the polymer sample, 20 mg of 2,6-di-tert-butyl-4-methylphenol, and 500 ml of n-decane were placed in a 1-liter flask equipped with a stirrer, and then placed at 1450 ° C. And heat on an oil bath. After the polymer sample is dissolved, it is cooled to room temperature over about 8 hours, and then kept on a water bath at 23 ° C for 8 hours.
- the precipitated polymer and n-decane solution containing the dissolved polymer are combined with G-4 (or G-2) And separated by a glass filter.
- the solution thus obtained was heated at 1 O mmHg and 150 ° C to dry the polymer dissolved in the n-decane solution until the amount was determined.
- the amount of the soluble component in ethylene- ⁇ -olefin block copolymer at 23 ° Cn_decane is calculated as the percentage of the weight of the polymer sample.
- the olefin having 3 to 20 carbon atoms specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methynole-11-pen Ten, 1-Otatene, 3-Methyl-1-butene, 1-Decene, 1-Dodecene, 1-Tetradodecene, 1-Hexadecene, 1-Kutadecene, 1-Eicosene, Penn Penten, Penn Heptene, Norbornene , 5-ethyl-2-norbornene, tetracyclododecene, 2_ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene No.
- Two or more kinds of the above-mentioned structural units derived from ethylene or ethylene having 3 to 20 carbon atoms may be contained.
- the ethylene 'alpha-Orefuin based block copolymer in the present invention may have free the structural unit derived from a diene compound of carbon atoms 4-2 0 in an amount of 5 mole 0/0 or less .
- Such gen compounds include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4_hexadiene, and 1,5-pentadiene.
- Aromatic hydrocarbon block copolymer (N) The aromatic hydrocarbon block copolymer (N), which is not included in the propylene polymer composition according to the present invention, is derived from aromatic vinyl.
- An aromatic vinyl / conjugated gen block copolymer (N 1) comprising a block polymerized unit (X) and a block polymerized unit (Y) derived from a conjugated gen, and a hydrogenated product thereof (N 2).
- the form of the aromatic vinyl 'conjugated diene block copolymer (N 1) having such a structure is represented by, for example, X (YX) n or (XY) n [n is an integer of 1 or more].
- X YX
- XY conjugated gen block polymer unit
- Y conjugated gen block polymerized unit
- the conjugated gen block polymerized unit (Y) existing between the aromatic vinyl block polymerized unit (X) is a soft segment and has a rubber bullet ⁇ fe.
- aromatic vinyl forming the block polymerized unit (X) as described above examples include, in addition to styrene, ⁇ -methylstyrene, 3-methylstyrene, ⁇ -methylstyrene, 4-propynolestyrene, Styrene derivatives such as -dodecylstyrene, 4-cyclohexylstyrene, 2-ethyl-4-pentinolestyrene, and 4- (phenylenobutynole) styrene.
- conjugated gen forming the block polymerized unit ( ⁇ ) examples include butadiene, isoprene, pentadiene, 2,3-dimethynolebutadiene, and combinations thereof.
- the conjugated diene block polymerization unit ( ⁇ ) is derived from butadiene and isoprene, it contains units derived from isoprene and butadiene in an amount of 40 mol% or more.
- the conjugated diene block copolymer unit ( ⁇ ) may be a random copolymer unit, a block copolymer unit, or a tapered copolymer unit.
- the content of the aromatic butyl polymerized unit can be measured by a conventional method such as infrared spectroscopy and NMR spectroscopy.
- the hydrogenated aromatic vinyl conjugated gen block copolymer ( ⁇ 2) is obtained by hydrogenating the above aromatic vinyl conjugated gen block copolymer (N 1) by a known method. It can be obtained in some cases.
- the hydrogenated product ( ⁇ 2) of the aromatic butyl 'conjugated gemrock copolymer usually has a hydrogenation ratio of 90% or more. This hydrogenation ratio is a value when the total amount of carbon-carbon double bonds in the conjugated gen-block polymerized unit ( ⁇ ) is 100%.
- the propylene pyrene polymer composition containing no St- or ethylene-based hook copolymer according to the present invention satisfies all of the following (A), (B), (C), and (D). Let's do it.
- St- or ethylene-based polymer does not include a St- or ethylene-based copolymer; the content of the St- or ethylene-based copolymer in the present propylene-based polymer composition is 10 wt. %, Preferably 5 wt% or less, more preferably 2 wt% or less.
- the storage elastic modulus G obtained from the above dynamic viscoelasticity measurement (the ratio of (20 ° C) to G '(100 ° C) (G' (20 ° C) / G '(100 ° C)) is 5 or less
- the needle penetration temperature (° C) measured in accordance with JIS K7196 is 100 ° C to 168 ° ⁇ .
- the loss tangent tan ⁇ is 0.5 or more, and preferably in the range of 0.5 to 2.5. Is preferably in the range of 0.6 to 2. -When the loss tangent tan 8 in the range of 25 ° C to 25 ° C is less than 0.5, the flexibility tends to be insufficient, and even if it has flexibility, the scratch resistance may be reduced. It tends to be inferior.
- G ′ (20 ° C.) / G ′ (100 ° O) is 5 or less, preferably 4 or less, more preferably 3.5 or less.
- the needle penetration temperature (° C) measured in accordance with JIS K7196 is from 100 ° C to 168 ° C, preferably from 120 ° C to 168 ° C. C, more preferably in the range of 140 ° C. to 168 ° C. If the temperature of the gold fit is less than 100 ° C, it cannot be used for applications requiring heat sterilization.
- a dumbbell piece with a thickness of 50 ram and a width of 5 mm and a thickness of lmmt was given 100% strain at 30 arms between the marked lines and at a pulling speed of 30 mm / min, and after holding for 10 minutes
- the residual strain 10 minutes after unloading is 20% or less, preferably 18% or less, and more preferably 16% or less. If the residual strain exceeds 20%, the rubber elasticity tends to decrease, and it cannot be used for applications requiring elasticity and resilience.
- ⁇ isotactic polypropylene (i) 1 to 40 parts by weight, preferably 1-30 by weight parts, including more preferably from 1 to 25 parts by weight, 45 to the propylene component 89 mol 0/0, 10 the ethylene component 25 Monore%, 0 to the number of carbon atoms. 4 to 20 alpha-Orefi down from the component units (a) optionally 30 mol 0 /.
- the amount includes propylene 'ethylene' ct Orefin copolymer (ii) (where at least one of 0 mol 0/0 At a record of the ethylene component and 4 to 20 carbon atoms CK Orefi down from the component units (a) )) Is contained in an amount of 60 to 99 parts by weight, preferably 70 to 99 parts by weight, more preferably 75 to 99 parts by weight.
- the molded article made of such a propylene polymer composition preferably has a haze power of 25% or less, preferably 20% or less, measured according to ASTM D1003.
- the molded article made of such a propylene-based polymer composition preferably has a tensile modulus (YM) force of not more than 10 OMPa, preferably not more than 8 OMPa, measured in accordance with JIS 6301.
- YM tensile modulus
- the propylene polymer composition according to the present invention has a melt flow rate (ASTM D 1238, 230 ° C, load 2.16 kg) power of usually 0001 to 1000 gZl O, preferably 0.0001 to 900 gZl 0 min. More preferably from 0.0001 to 800 g / 10 min, the intrinsic viscosity measured in decahydronaphthalene at 135 ° C. [] force usually from 0.01 to: L 0 dl / g, preferably from 0. 05 to 10 dlZg, more preferably 0.1 to: L0 dlZg.
- the 7 ° P pyrene-based polymer composition according to the present invention has a maximum peak of melting point (Tm, ° C) at 100 ° C or higher in an endothermic curve of a differential scanning calorimeter (DSC).
- the heat of fusion is preferably in the range of 5 to 4 OJ / g, more preferably in the range of 5 to 35 J / g.
- the maximum endothermic peak (melting point) of the propylene-based polymer composition according to the present invention is at least 130 ° C, preferably at least 140 ° C, more preferably at least 160 ° C.
- the melt tension (MT) of the propylene-based polymer composition according to the present invention is usually 0.5 to 10 g, preferably 1 to L 0 g. Are better.
- the melt tension (MT) was measured at a measurement temperature of 200 using a melt tension measurement tester [manufactured by Toyo Seiki Seisaku-sho, Ltd.] C, It was determined as the tension applied to the filament when the extruded strand was pulled at a constant speed (10 mZ) at an extrusion speed of 15 mm / min.
- each component is mixed in various known manners within the above range, for example, a multi-stage polymerization method, a Henschel mixer, a V-plender, a ribbon blender, a tumbler blender, or the like. After mixing, melt kneading with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, etc., and then granulating or pulverizing can be employed.
- the isotactic propylene-based copolymer composition of the present invention includes a weather-resistant stabilizer, a heat-resistant stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, and an anti-fog within a range not to impair the object of the present invention.
- Additives such as agents, lubricants, pigments, dyes, plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants, and the like may be added as necessary.
- “other copolymers” (elastomers) and the like described in detail below may be blended without departing from the gist of the present invention, as long as the object of the present invention is not impaired.
- the propylene-based polymer composition according to the present invention may contain "other copolymers” (elastomer, elastomer resin) as necessary.
- Such as “other copolymers” include ethylene - like 'a old Refinranda arm copolymer (iii) ethylene' Gen copolymer (iv), and ethylene Toryen copolymer (V) and the like. . These copolymers are used alone or in combination of two or more.
- copolymers are usually used in an amount of 0 to 30 parts by weight, preferably 0 to 20 parts by weight, based on 100 parts by weight of the isotactic polypropylene polymer of the present invention. Even if it is included in the quantity of parts.
- other copolymers are used in the above amounts, a composition capable of producing a molded article having an excellent balance between flexibility, transparency and low-temperature impact resistance can be obtained.
- the ethylene' ⁇ -olefin random copolymer (iii) used in the present invention has a density of 0.860 gZcm3 or more and less than 0.895 gZcm3, preferably 0.860-0.SSO gZcmS.
- a is, Menoretofurore one bets (MFR; ASTM D 1238, 190 ° C, load 2.16 kg) is 0. 5 to 30 ⁇ Roh 1 0 minute, soft ethylene 'a- Orefin preferably. 1 to 20 GZL 0 minutes Copolymers are preferred.
- Olefins copolymerized with ethylene are ⁇ -olefins having 3 to 20 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- Examples include otaten, 1-nonene, 1-decene, 1-pendecene, 1-dodecene, 1-hexadodecene, 1-octadecene, 1-nonadecene, 1-eicosene, 4-methyl-1-pentene, and the like. Of these, preferred are those having 3 to 10 carbon atoms. These ⁇ -olefins are used alone or in combination of two or more.
- Ethylene 'alpha-O-les fins random copolymer (iii) is present in an amount of 60 to 90 mole 0/0 units in which the majorIncr derived from ethylene, 1 units derived from alpha-Orefin having 3 to 20 carbon atoms Desirably, it is contained in an amount of 0 to 40 mol%.
- the ethylene'a-olefin random copolymer (iii) may contain, in addition to these units, units derived from other polymerizable monomers as long as the object of the present invention is not impaired. Good.
- Such other polymerizable monomers include, for example, styrene compounds, butyl compounds, butyl compounds such as vinylcyclohexane and vinylnorbornane; vinyl esters such as butyl acetate;
- Unsaturated organic acids such as maleic anhydride or derivatives thereof;
- Conjugated dienes such as butadiene, isoprene, pentadiene and 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methinole-1,5-hexadiene, 6-methinole-1,5-hexadiene, 7-methyl-1,6-octadiene, dicyclopentene, Cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-bier norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2_nonolevonorenene, 6-chloromethyl-5- Non-producing compounds such as isopropyl-2-en-norpolene, 2,3-diisopropylidene-5-norpolene, 2-ethylidene-3-isopropylidene-5-norborn
- Alpha-O-les fins random copolymer (iii) has such other units guiding force is from a polymerizable monomer, 1 0 mol% or less, preferably 5 mol 0/0 or less, good Ri preferably 3 good record, also contain a mole 0/0 or less of the amount.
- ethylene 'oc_olefin random copolymer (iii)' include: ethylene 'propylene random copolymer, ethylene / 1-butene random copolymer, ethylene / 1-propylene / 1-butene random copolymer Coalesced ethylene, propylene '. Ethylidene norbornene random copolymer, ethylene / 1-hexene random copolymer, ethylene / 1-octene random copolymer and the like.
- a copolymer of ethylene and propylene a random copolymer of ethylene / 1-butene, a random copolymer of ethylene / 1-hexene and a random copolymer of ethylene / 1-otene are particularly preferred. Used. Two or more of these copolymers may be used in combination.
- the ethylene olefin random copolymer (iii) used in the present invention has a crystallinity measured by an X-ray diffraction method of usually 40% or less, preferably 0 to 39%, more preferably 0 to 39%. ⁇ 35%.
- the ethylene'a-olefin random copolymer as described above can be produced by a conventionally known method using a vanadium-based catalyst, a titanium-based catalyst, a meta-aqueous catalyst, or the like.
- Ethylene 'alpha-O-les fins random copolymer (iii) is present in the syndiotactic Teitsu click polypropylene composition, usually 0-4 0 weight 0/0, contains preferably Ho amount of 0-3 5 weight 0/0 May be.
- Ethylene ' ⁇ -olefin random copolymer (iii) When is used in the above amount, a composition that can prepare a molded article having an excellent balance of rigidity and hardness, transparency, and impact resistance can be obtained.
- the ethylene / gen copolymer (iv) used as the elastomer in the present invention is a random copolymer of ethylene and jen. '
- Non-conjugated genes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene nonolevonorene, ethylidene nonorebornene;
- the content of structural units withers guide from Jen, usually from 0.1 to 30 mole 0/0, preferably from 0.1 to 2 0 mole 0/0 , still more preferably in the range of 0.5 to 15 mole 0/0. It is desirable that the iodine value is usually 1 to 150, preferably 1 to 100, and more preferably 1 to 50.
- the intrinsic viscosity [ ⁇ ] of the ethylene 'gen copolymer (: ⁇ ) measured in dehydrohydrophthalene at 1' 35 ° ⁇ is 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g.
- Such an ethylene'gen copolymer (iv) can be prepared by a conventionally known method.
- the 'ethylene' gen copolymer (iv) may be contained in the isotactic polypropylene composition in an amount of usually 0 to 40% by weight, preferably 0 to 35% by weight.
- the ethylene / gen copolymer ( iv ) is used in the above amount, a composition that can prepare a molded article having a good balance of rigidity and hardness, transparency and impact resistance can be obtained.
- the ethylene / triene copolymer (V) used as the elastomer in the present invention is a random copolymer of ethylene and triene.
- triene to be copolymerized with ethylene specifically, 6,10-dimethyl-1,5,9-indene triene,
- Non-conjugated trienes such as 4-ethylidene-1,7-pentadecane
- ⁇ 3 ⁇ 4trienes such as 1,3,5-hexatriene
- trienes can be used alone or in combination of two or more.
- the above-mentioned triene can be prepared by a conventionally known method as described in, for example, EP0691354A1 and WO96 / 20150.
- the content of constituent units derived from Toryen is usually from 0.1 to 30 mole 0/0, preferably from 0.1 to 20 mole 0/0, more preferably Shi wishing to be within the scope of 0.5 to 15 mole 0/0 Les ,.
- the iodine value is usually from 1 to 200, preferably from 1 to 100, and more preferably from 1 to 50.
- the intrinsic viscosity [] of ethylene / triene copolymer (v) measured in decahydronaphthalene at 135 ° C. is 0.01 to 10 dl Zg, preferably 0.05 to It is desirable that the ratio be in the range of 10 d 1 / g, more preferably 0.1 to 10 d 1 Z g.
- the ethylene'triene copolymer (V) as described above can be prepared by a conventionally known method.
- the ethylene-triene copolymer (V) may be contained in the isotactic polypropylene composition in an amount of usually 0 to 40% by weight, preferably 0 to 35% by weight.
- a composition can be obtained which can prepare a molded article having a good balance of rigidity and hardness, transparency and impact resistance.
- a softener (vi) and an inorganic filler (vii) can be used as necessary.
- the softener (vi) include petroleum-based substances such as process oils, lubricating oils, paraffin, liquid paraffin, petroleum asphalt, petrolatum; coal tars such as cornole letter and corn letter pitch; Fatty oils such as oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as tall oil, beeswax, carnaupalow, and lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, and the like Fatty acids or metal salts thereof; Synthetic polymer substances such as petroleum resin, coumarone indene resin, atactic polypropylene; Ester plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate;
- the softener (vi) is used in an amount of 200 parts by weight based on 100 parts by weight of the total amount of the isotactic polypropylene (i) and the propylene 'ethylene ⁇ ⁇ -olefin copolymer (ii). Hereinafter, it is preferably used in a proportion of 2 to 100 parts by weight.
- the amount of the softener (vi) exceeds 200 parts by weight, the heat resistance and heat resistance of the obtained thermoplastic elastomer composition tend to decrease.
- inorganic filler (vii) used in the present invention as needed include calcium carbonate, calcium silicate, clay, carion, talc, silica, diatomaceous earth, mica powder, asbestos, and anoremina. , Barium sulfate, aluminum sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, calcium hydroxide, calcium aluminum hydroxide, etc. .
- the inorganic filler lj (vii) is 200 parts by weight based on 100 parts by weight of the total amount of the isotactic polypropylene (i) and the propylene 'ethylene- ⁇ -olefin copolymer (ii). 0 parts by weight or less, preferably 2 to 200 parts by weight.
- the amount of the inorganic filler (vii) used exceeds 200 parts by weight, the rubber elasticity and the moldability of the obtained thermoplastic elastomer composition tend to decrease. Molded article comprising propylene-based polymer composition
- the propylene-based polymer composition according to the present invention as described above can be widely used for conventionally known polyolefin applications.
- the polyolefin composition can be used, for example, in a sheet, unstretched or stretched film, filament, or other various shapes. It can be used by molding into a compact.
- the molded article comprising the propylene-based polymer composition according to the present invention may be a multilayer laminate, wherein at least one layer is a layer containing the propylene-based polymer composition, ⁇ ⁇ Composition of sheet, multilayer container, multilayer tube, water-based paint
- thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, and foam molding.
- the obtained molded article is exemplified.
- the molded product will be described below with reference to several examples.
- the molded article according to the present invention is, for example, an extruded molded article
- its shape and product type are not particularly limited, and examples thereof include a sheet, a film (unstretched), a pipe, a hose, a wire coating, a tube, Particularly, a sheet (skin material), a film, a tube, a catheter, a monofilament (non-woven fabric) and the like are preferable.
- a conventionally known extruder and molding conditions can be employed, for example, using a single screw extruder, a kneading extruder, a ram extruder, a gear extruder, or the like.
- the molten propylene composition can be formed into a desired shape by extruding it from a specific die or the like.
- the stretched film is obtained by stretching the above-described extruded sheet or extruded film (unstretched) by a known stretching method such as a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method, and a uniaxial stretching method. Can be obtained.
- the stretching ratio at the time of stretching the sheet or unstretched film is usually about 20 to 70 times in the case of biaxial stretching, and usually about 2 to 10 times in the case of uniaxial stretching. It is desirable to obtain a stretched film having a thickness of about 5 to 200 im by stretching. Further, an inflation film can be produced as a film-shaped molded product. Draw-down hardly occurs during inflation molding.
- the sheet and the film molded article made of the propylene polymer composition according to the present invention as described above are hardly charged, have rigidity such as tensile elasticity, heat resistance, stretchability, impact resistance, and aging resistance. It has excellent transparency, transparency, gloss, rigidity, and moisture barrier properties, and can be widely used as a packaging film.
- the sheet and the film formed body composed of the propylene-based polymer composition may be a multilayer molded body, and are used as a multilayer laminate containing at least one propylene-based polymer composition.
- the filament molded body can be produced, for example, by extruding a molten propylene composition through a spinneret. Specifically, the spun-pound method and the melt-pron method are preferably used. The filament thus obtained may be further drawn. This stretching may be carried out to such an extent that at least one axis of the filament is molecularly oriented, and it is usually desirable to carry out the stretching at a magnification of about 5 to 10 times. Les ,.
- the filaments made of the propylene yarn composition according to the present invention are hardly charged, and are excellent in transparency, rigidity, heat resistance, impact resistance, and stretchability.
- the injection molded article can be produced by injection molding the propylene composition into various shapes using a conventionally known injection molding apparatus under known conditions.
- the injection molded article made of the propylene composition according to the present invention is hardly charged, and is excellent in transparency, rigidity, heat resistance, street resistance, surface gloss, chemical resistance, abrasion resistance, etc. It can be used widely for trim materials, automotive exterior materials, home appliance housings and containers.
- the blow molded article can be produced by blow molding a propylene-based polymer composition using a conventionally known blow molding apparatus under known conditions.
- the molded article made of the propylene-based polymer composition may be a multilayer molded article, and contains at least one layer of the propylene-based polymer composition.
- the above-mentioned propylene polymer composition is extruded from a die in a molten state at a resin temperature of 100 ° C. to 300 ° C. to form a tubular parison, and then the parison is formed into a metal having a desired shape. After holding in the mold, air is blown, and the resin temperature is 1 3
- a hollow molded article can be produced by mounting the mold at 0 ° C. to 300 ° C. It is desirable that the blow magnification is about 1.5 to 5 times in the horizontal direction.
- the propylene polymer composition is injected into a parison mold at a resin temperature of 100 ° C. to 300 ° C. to form a parison, and then the parison is formed in a mold having a desired shape. Then, air is blown into the mold, and the resin is mounted on a mold at a resin temperature of 120 ° C. to 300 ° C., whereby a hollow molded body can be manufactured.
- the stretching (blow) magnification is desirably 1.1 to 1.8 times in the vertical direction and 1.3 to 2.5 times in the horizontal direction.
- the blow molded article comprising the propylene-based polymer composition according to the present invention is excellent in transparency, flexibility, heat resistance and impact resistance, and also excellent in moisture resistance.
- the press-formed body examples include a mold stamping-formed body.
- the base material when the base material and the skin material are press-formed at the same time and the both are subjected to composite integral shaping (mold stamping) is used in the present invention. It can be formed from such a propylene composition.
- a molded stamping molded body include automotive interior materials such as a door trim, a rear package trim, a seat back garnish, and an instrument panel.
- the press molded article comprising the propylene polymer composition according to the present invention is hardly charged, and has flexibility, heat resistance, transparency, ir impact resistance, anti-aging property, surface gloss, chemical resistance, and abrasion resistance. And so on.
- the propylene-based polymer composition which can obtain the molded product excellent in transparency, impact resistance, flexibility, heat resistance, scratch resistance, rubber elasticity, etc. with a good balance is obtained.
- Residual strain (%;) [(L-LO) / L0] X 100
- JIS No. 3 dumbbell was used and measured at a span of 30 mm and a pulling speed of 30 mm / min at 23 ° C. [Needle penetration temperature (.C)]
- test piece having a thickness of 1 mm measurement was performed using a digital turbidity meter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd.
- the measurement was carried out at 140 ° C. using GPC (genole permeation chromatography) with a benzene solvent of onoletodichloromethane.
- dimethino lemethylene (3-tert-butylinole-5-methinolecyclopentageninole) fluoreyl zirconium dichloride 0.002 mmo 1 and 0.6 mm o 1 of methylaluminoxane in terms of aluminum (Tohoku Soichi Finechem Co., Ltd.) was added to the polymerization vessel, polymerization was carried out for 20 minutes while maintaining the internal temperature at 65 ° C and the system pressure at 0.78 MPa with ethylene, and 20 ml of methanol was added to carry out the polymerization. Stopped. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C for 12 hours.
- the polymer obtained was 60.4 g, the intrinsic viscosity [ ⁇ ] was 1.81 d 1 / g, the glass transition temperature T g was _27 ° C, the ethylene content was 13 mol%, The butene content was 19 mol, and the molecular weight distribution (Mw / Mn) measured by GPC was 2.4. In addition, a clear melting peak could not be confirmed from the heat of fusion measured by DSC.
- Fluorenyl zirconium dichloride 0.000 lmmo 1 and 0.3 mmo 1 of methylaluminoxane (Tohoku Soichi Fine Chemical Co., Ltd.) in contact with aluminum are added to the polymerization reactor.
- the polymerization was continued for 20 minutes while maintaining ethylene at the internal temperature of 40 ° C and the system pressure at 0.8 MPa, and the polymerization was stopped by adding 2 Oml of methanol.
- dimethylmethylene (3-tert-butynole-5-methyl / lecyclopentageninole) fluorenyl zirconium dichloride 0.002 mmo 1 and aluminum equivalent 0.6 mmo 1 of methylaluminoxane (Available from Finechem Co., Ltd.) was added to the polymerization vessel, polymerization was carried out for 30 minutes while maintaining the internal temperature at 40 ° C and the internal pressure at 0.78 MPa with ethylene, and 20 ml of methanol was added. Then the polymerization was stopped. After depressurization, precipitate the polymer from the polymerization solution in 2 L of methanol and apply vacuum. Dried at 130 ° C for 12 hours.
- the obtained polymer was 46.4 g, the intrinsic viscosity [ ⁇ ] was S1.51 d1 Zg, the glass transition temperature Tg was 130 ° C, and the ethylene content was 17 mol. %, The butene content was 10 mol, and the molecular weight distribution (Mw / Mn) measured by GPC was 2.1. In addition, no clear melting angle ⁇ peak could be confirmed from the calorie of fusion by DSC measurement.
- TIBA triisobutylaluminum
- Example 1 was the same as Example 1 except that the propylene 'butene' ethylene copolymer (ii_l) obtained in Synthesis Example 1 was changed to the propylene 'ethylene' butene copolymer (ii-2) obtained in Synthesis Example 2. Performed in the same manner as in Example 1. The results are shown in Tables 1-2.
- Example 3 the propylene 'ethylene' butene copolymer (ii-3) obtained in Synthesis Example 3 was changed to the propyleneethylene-butene copolymer (ii-4) obtained in Synthesis Example 4. Other than that, it carried out similarly to Example 1. The results are shown in Tables 1-2.
- Example 2 Dynamic viscoelasticity
- the propylene-based polymer composition which can obtain the molded product excellent in transparency, impact resistance, flexibility, heat resistance, scratch resistance, rubber elasticity, etc. with a good balance is obtained.
Description
Claims
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DE602004031607T DE602004031607D1 (de) | 2003-05-28 | 2004-05-12 | Propylenpolymerzusammensetzung und verwendung davon |
EP04732452A EP1630197B1 (en) | 2003-05-28 | 2004-05-12 | Propylene polymer composition and use thereof |
US10/558,076 US8329824B2 (en) | 2003-05-28 | 2004-05-12 | Propylene polymer compositions and uses thereof |
JP2005506461A JP4790416B2 (ja) | 2003-05-28 | 2004-05-12 | プロピレン系重合体組成物およびその用途 |
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Also Published As
Publication number | Publication date |
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EP1630197A4 (en) | 2007-10-24 |
JPWO2004106430A1 (ja) | 2006-07-20 |
KR100777354B1 (ko) | 2007-11-28 |
JP2011174093A (ja) | 2011-09-08 |
US8329824B2 (en) | 2012-12-11 |
KR20060009922A (ko) | 2006-02-01 |
DE602004031607D1 (de) | 2011-04-14 |
TW200427764A (en) | 2004-12-16 |
US20060247381A1 (en) | 2006-11-02 |
EP1630197B1 (en) | 2011-03-02 |
TWI302158B (en) | 2008-10-21 |
EP1630197A1 (en) | 2006-03-01 |
JP4790416B2 (ja) | 2011-10-12 |
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