JP5495154B2 - Ethylene-propylene block copolymer polypropylene resin composition with excellent fluidity, rigidity and impact strength - Google Patents
Ethylene-propylene block copolymer polypropylene resin composition with excellent fluidity, rigidity and impact strength Download PDFInfo
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- JP5495154B2 JP5495154B2 JP2008182659A JP2008182659A JP5495154B2 JP 5495154 B2 JP5495154 B2 JP 5495154B2 JP 2008182659 A JP2008182659 A JP 2008182659A JP 2008182659 A JP2008182659 A JP 2008182659A JP 5495154 B2 JP5495154 B2 JP 5495154B2
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- -1 polypropylene Polymers 0.000 title claims description 49
- 239000004743 Polypropylene Substances 0.000 title claims description 47
- 229920001155 polypropylene Polymers 0.000 title claims description 47
- 239000011342 resin composition Substances 0.000 title claims description 26
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 title claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 61
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 24
- 239000005977 Ethylene Substances 0.000 claims description 24
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 23
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002667 nucleating agent Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 3
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 claims description 2
- DFXFBQFUSURGOJ-CRWXNKLISA-N (3R,4S,5S,6S)-7-methyl-1-phenyloct-1-ene-2,3,4,5,6,7-hexol Chemical compound CC([C@H]([C@H]([C@@H]([C@H](C(O)=CC1=CC=CC=C1)O)O)O)O)(O)C DFXFBQFUSURGOJ-CRWXNKLISA-N 0.000 claims description 2
- CTPBWPYKMGMLGS-CIAFKFPVSA-N (3s,4s,5s,6r)-1,8-bis(4-methylphenyl)octa-1,7-diene-2,3,4,5,6,7-hexol Chemical compound C1=CC(C)=CC=C1C=C(O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=C(C)C=C1 CTPBWPYKMGMLGS-CIAFKFPVSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 229940087101 dibenzylidene sorbitol Drugs 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- DLAHAXOYRFRPFQ-UHFFFAOYSA-N dodecyl benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1 DLAHAXOYRFRPFQ-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000001451 organic peroxides Chemical class 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000012899 standard injection Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- AZSKHRTUXHLAHS-UHFFFAOYSA-N tris(2,4-di-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C AZSKHRTUXHLAHS-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、流動性、剛性および衝撃強さに優れたエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂組成物に関する。さらに具体的には、本発明は、高結晶性ホモポリプロピレン、エチレン−プロピレン弾性共重合体および剛性核剤を含むポリプロピレン樹脂組成物に関し、既存のエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂に比べて流動性および後加工性に優れ、大型成形品または薄膜製品の成形が容易な高剛性エチレン−プロピレンブロック共重合体系ポリプロピレン樹脂組成物に関する。 The present invention relates to an ethylene-propylene block copolymer polypropylene resin composition excellent in fluidity, rigidity and impact strength. More specifically, the present invention relates to a polypropylene resin composition comprising a highly crystalline homopolypropylene, an ethylene-propylene elastic copolymer and a rigid nucleating agent, and has a fluidity compared to existing ethylene-propylene block copolymer-based polypropylene resins. The present invention relates to a high-rigidity ethylene-propylene block copolymer-based polypropylene resin composition that is excellent in properties and post-processing properties, and is easy to mold a large molded product or thin film product.
一般に、プロピレンが単独で重合されたホモポリプロピレンは、衝撃強さが低いため、重合の際にα−オレフィン、例えばエチレンと共に共重合することにより、衝撃強さを補完する技術が用いられている。このようなエチレン−プロピレンブロック共重合体は、優れた剛性および衝撃特性によって自動車部品、家電器具、工業部品、日常生活用品および包装容器などの射出成形品、包装用フィルムおよびシートなどに広範囲に用いられている。 In general, homopolypropylene obtained by polymerizing propylene alone has a low impact strength. Therefore, a technique for complementing the impact strength by copolymerizing with an α-olefin such as ethylene at the time of polymerization is used. Such ethylene-propylene block copolymers are widely used in automobile parts, home appliances, industrial parts, daily life products, packaging products such as packaging containers, packaging films and sheets, etc. due to their excellent rigidity and impact properties. It has been.
エチレン−プロピレンブロック共重合体系ポリプロピレン樹脂は、エチレン−プロピレン共重合体の含量が増加すると、衝撃強さは増加するが、剛性および耐熱性は低下するという問題点がある。したがって、一定の水準の衝撃強さを維持すると同時に剛性および耐熱性を向上させるために、いろいろな技術が提案されている。 The ethylene-propylene block copolymer-based polypropylene resin has a problem that when the content of the ethylene-propylene copolymer is increased, the impact strength is increased, but the rigidity and the heat resistance are decreased. Accordingly, various techniques have been proposed to maintain a certain level of impact strength and at the same time improve rigidity and heat resistance.
特許文献１には、重合の際にアイソタクティシティ(isotacticity)を上げて高剛性のポリプロピレンを製造する技術が開示されている。
また、特許文献２には、核磁気共鳴法による立体規則度指数がペンタッド法基準９６％であり、分子量分布が広く、絶対粘度が３．０〜６．５ｄＬ／ｇのエチレン−プロピレン共重合体からなる、溶融指数３〜３５ｇ／１０分のポリプロピレン樹脂組成物が開示されているが、ポリプロピレン樹脂の生産性、加工性および後加工性のために要求される最小限の溶融指数である８０ｇ／１０分には大きく及ばないという問題点がある。
Patent Document 1 discloses a technique for producing high-rigidity polypropylene by increasing isotacticity during polymerization.
Patent Document 2 discloses an ethylene-propylene copolymer having a stereoregularity index of 96% based on the pentad method, a broad molecular weight distribution, and an absolute viscosity of 3.0 to 6.5 dL / g. A polypropylene resin composition having a melt index of 3 to 35 g / 10 min is disclosed, which is a minimum melt index required for the productivity, processability and post-processability of polypropylene resin, 80 g / There is a problem that it does not reach much in 10 minutes.
高速または大型の射出品成形には高流動性のポリプロピレン樹脂製品が必須的に要求されるが、このためには、使用する樹脂の粘度を非常に低くしなければならない。樹脂の粘度を低めるためには射出時の温度を非常に高く設定する方法が考えられるが、この場合、高温による熱分解によって、色相の変化、物性の低下、耐熱安定性の低下などといった問題点が発生する。また、射出成形の際に十分な流動性を持たない場合には、過度な射出圧および残留応力によって、成形の後に撓んだりガス痕が生じたりするなどの問題点が発生するおそれがある。 For high-speed or large-scale injection molding, a polypropylene resin product having high fluidity is essential, but for this purpose, the viscosity of the resin used must be very low. In order to reduce the viscosity of the resin, a method of setting the temperature at the time of injection very high can be considered, but in this case, problems such as a change in hue, deterioration of physical properties, deterioration of heat stability, etc. due to thermal decomposition due to high temperature. Will occur. In addition, when the injection molding does not have sufficient fluidity, there is a possibility that problems such as bending and gas marks may occur after molding due to excessive injection pressure and residual stress.
これらの問題を解決するために、低流動性の高結晶性エチレン−プロピレンブロック共重合体系ポリプロピレン樹脂を製造した後、有機過酸化物を添加して人為的にポリプロピレン鎖を切断することにより、分子量を低めて樹脂の流動性を向上させる方法が使用されている。 In order to solve these problems, after producing a low-flowability highly crystalline ethylene-propylene block copolymer polypropylene resin, an organic peroxide is added to artificially cleave the polypropylene chain to obtain a molecular weight. The method of improving the fluidity | liquidity of resin by lowering is used.
特許文献３および特許文献４には、エチレン−プロピレンブロック共重合体系ポリプロピレン樹脂に特定の有機過酸化物を特定の条件下で添加することにより、有機過酸化物の添加による剛性および衝撃強さの低下を最小化することを図った方法が開示されている。
また、特許文献５には、特定のエチレン−プロピレン共重合体に有機過酸化物を添加す
ることにより、高流動性のプロピレン−エチレンブロック共重合体系ポリプロピレン樹脂を製造する方法が開示されている。
In Patent Document 3 and Patent Document 4, by adding a specific organic peroxide to an ethylene-propylene block copolymer polypropylene resin under specific conditions, the rigidity and impact strength due to the addition of the organic peroxide are reduced. A method is disclosed that seeks to minimize degradation.
Patent Document 5 discloses a method for producing a highly fluid propylene-ethylene block copolymer polypropylene resin by adding an organic peroxide to a specific ethylene-propylene copolymer.
ところが、有機過酸化物を添加して流動性、すなわちポリプロピレン系樹脂の溶融指数を向上させた場合、狭い分子量分布によって加工性が低下し、後加工の際に臭いおよび塗装性不良などが発生するという問題点がある。 However, when an organic peroxide is added to improve the fluidity, that is, the melt index of the polypropylene resin, the processability deteriorates due to the narrow molecular weight distribution, and odor and poor paintability occur during post-processing. There is a problem.
特許文献６には、溶融指数８０〜１２０ｇ／１０分の高結晶性エチレン−プロピレンブロック共重合体系ポリプロピレン樹脂組成物が開示されているが、高溶融指数による剛性および衝撃強さの低下を防止するためのエチレン−プロピレン共重合体組成の最適化に対する条件について開示されていない。すなわち、ポリプロピレン樹脂組成物に高剛性および高衝撃強さの特性を与えるためのエチレン−プロピレン共重合体の分散および共重合体の大きさを制御するためには、ホモポリプロピレンとエチレン−プロピレン共重合体の界面張力の調節およびエチレン−プロピレン共重合体の分子量の調節によるエチレン−プロピレン共重合体の微細分布が必要であるが、これについては開示されたところが全くないという点で技術的限界を持つ。
本発明は、このような従来の技術の問題点を解決するためになされたものであり、その目的とするところは、エチレン−プロピレンブロック共重合体系ポリプロピレン樹脂の製造後に人為的に有機過酸化物を添加せず、流動性および後加工性に優れて大型および薄膜の射出成形製品の成形に適すると同時に、剛性と衝撃強さに優れた樹脂組成物を提供することにある。 The present invention has been made in order to solve such problems of the prior art, and the object of the present invention is to artificially produce an organic peroxide after the production of an ethylene-propylene block copolymer polypropylene resin. It is an object of the present invention to provide a resin composition which is excellent in fluidity and post-processability, is suitable for molding large-sized and thin-film injection-molded products, and has excellent rigidity and impact strength.
上記目的を達成するために、本発明によれば、アイソタクチックペンタッド分率(isotactic pentad fraction)が９６％以上の高結晶性ホモポリプロピレン（Ａ）８０〜９５質
量％、およびエチレン／（エチレン＋プロピレン）のモル比が０．１５〜０．４０のエチレン−プロピレン弾性共重合体（Ｂ）５〜２０質量％を含む、前記高結晶性ホモポリプロピレンと前記エチレン−プロピレン弾性共重合体の極限粘度（以下、本明細書において絶対粘度とも称する）の比率（成分Ａ／成分Ｂ）が０．０９〜０．３３であるポリプロピレン樹脂１００質量部と、核剤（Ｃ）０．０５〜０．３質量部を含む、メルトフローレート（以下、本明細書において溶融指数とも称する）８０〜１２０ｇ／１０分のエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂組成物が提供される。
特に本発明の好ましい形態は、マトリックスとしてアイソタクチックペンタッド分率が９６％以上の高結晶性ホモポリプロピレン成分（Ａ）８０〜９５質量％、およびドメインとしてエチレン／（エチレン＋プロピレン）のモル比が０．１５〜０．３０のエチレン−プロピレン弾性共重合体成分（Ｂ）５〜２０質量％からなるエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂１００質量部と、核剤（Ｃ）０．０５〜０．３質量部からなり、
ここで、前記高結晶性ホモポリプロピレン成分（Ａ）と前記エチレン−プロピレン弾性共重合体成分（Ｂ）の極限粘度比率（Ａ／Ｂ）が０．０９〜０．３３であり、
前記エチレン−プロピレン弾性共重合体成分（Ｂ）は、水素濃度（水素／エチレン）が０．００５〜０．０３０のモル比で共重合させて作られ、
前記エチレン−プロピレン弾性共重合体成分（Ｂ）は、０．５〜２．０μｍの大きさを有する、ポリプロピレン樹脂組成物であって、前記ポリプロピレン樹脂組成物は、
衝撃強さが５．０ｋｇ・ｃｍ／ｃｍ以上であり、引張強度が３００ｋｇ／ｃｍ ２ 以上であり、そしてメルトフローレートが８５〜１２０ｇ／１０分であるエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂組成物である。
In order to achieve the above object, according to the present invention, 80 to 95% by mass of highly crystalline homopolypropylene (A) having an isotactic pentad fraction of 96% or more, and ethylene / (ethylene + Propylene) molar ratio of 0.15-0.40 ethylene-propylene elastic copolymer (B) 5-20% by mass of the high crystalline homopolypropylene and the ethylene-propylene elastic copolymer 100 parts by mass of a polypropylene resin having a viscosity (component A / component B) ratio (component A / component B) of 0.09 to 0.33 and a nucleating agent (C) of 0.05 to 0.00. An ethylene-propylene block copolymer based polypropylene having a melt flow rate (hereinafter also referred to as a melt index in the present specification) of 80 to 120 g / 10 minutes, comprising 3 parts by mass Resin composition is provided.
In particular, a preferred embodiment of the present invention is a high crystalline homopolypropylene component (A) having an isotactic pentad fraction of 96% or more as a matrix and a molar ratio of ethylene / (ethylene + propylene) as a domain. There 0.15 to 0.30 of the ethylene - propylene elastic copolymer component (B) consists of 5 to 20 wt% ethylene - and 100 parts by weight of propylene block copolymer polypropylene resin, nucleating agent (C) 0.05 to Consisting of 0.3 parts by weight,
Here, the intrinsic viscosity ratio (A / B) of the highly crystalline homopolypropylene component (A) and the ethylene-propylene elastic copolymer component (B) is 0.09 to 0.33,
The ethylene-propylene elastic copolymer component (B) is made by copolymerization at a molar ratio of hydrogen concentration (hydrogen / ethylene) of 0.005 to 0.030,
The ethylene-propylene elastic copolymer component (B) is a polypropylene resin composition having a size of 0.5 to 2.0 μm, and the polypropylene resin composition comprises:
And the impact strength 5.0 kg · cm / cm or more, a tensile strength of at 300 kg / cm 2 or more, and the melt flow rate is 85 to 120 g / 10 min ethylene - propylene block copolymer polypropylene resin composition It is.
本発明に係るエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂組成物は、ホモポリプロピレン（Ａ）、エチレン−プロピレン共重合体（Ｂ）および核剤（Ｃ）を含んでなる樹脂組成物であって、既存のエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂に比べて流動性に優れる上、高結晶性ホモポリプロピレンおよびエチレン−プロピレン共重合体の優秀な特性によって剛性および衝撃強さに優れるという特徴を有する。このため、本発明の樹脂組成物は、自動車用部品や家電製品などの大型製品または薄膜製品の成形材料として適する。 An ethylene-propylene block copolymer-based polypropylene resin composition according to the present invention is a resin composition comprising a homopolypropylene (A), an ethylene-propylene copolymer (B), and a nucleating agent (C), In addition to being excellent in fluidity as compared with the above-mentioned ethylene-propylene block copolymer polypropylene resin, it has the characteristics of excellent rigidity and impact strength due to the excellent properties of highly crystalline homopolypropylene and ethylene-propylene copolymer. For this reason, the resin composition of the present invention is suitable as a molding material for large products such as automobile parts and home appliances or thin film products.
本発明に係るエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂は、マトリックスとしてのホモポリプロピレン（Ａ）、およびドメインとしてのエチレン−プロピレン共重合体（Ｂ）を含んでなり、エチレン−プロピレン共重合体（Ｂ）は、非結晶性のエチレン−プロピレン共重合体(Rubber)と半結晶性のエチレン共重合体(semicrystalline ethylene copolymer)（Ｂ）に区分される。 The ethylene-propylene block copolymer polypropylene resin according to the present invention comprises a homopolypropylene (A) as a matrix and an ethylene-propylene copolymer (B) as a domain, and an ethylene-propylene copolymer (B ) Are classified into non-crystalline ethylene-propylene copolymer (Rubber) and semicrystalline ethylene copolymer (B).
エチレン−プロピレンブロック共重合体系ポリプロピレン樹脂に高剛性を与えるために、ホモポリプロピレン（Ａ）は高い立体規則性を持つものでなければならない。すなわち、核磁気共鳴法(Nuclear Magnetic Resonance)上の立体規則度指数であるアイソタクチックペンタッド分率が９６％以上のホモポリプロピレンが要求される。エチレン−プロピレン共重合体の溶融指数がホモポリプロピレンの溶融指数に比べて非常に大きいから、エチレン−プロピレンブロック共重合体系ポリプロピレン樹脂に高流動性を与えるためには、エチレン−プロピレン共重合体の溶融指数より非常に大きい溶融指数を持つホモポリプロピレン（Ａ）を使用しなければならない。 In order to give high rigidity to the ethylene-propylene block copolymer polypropylene resin, the homopolypropylene (A) must have high stereoregularity. That is, a homopolypropylene having an isotactic pentad fraction of 96% or more, which is a stereoregularity index according to Nuclear Magnetic Resonance, is required. Since the melt index of ethylene-propylene copolymer is much larger than the melt index of homopolypropylene, in order to give high fluidity to the ethylene-propylene block copolymer polypropylene resin, the melt of ethylene-propylene copolymer Homopolypropylene (A) with a melt index much greater than the index must be used.
エチレン−プロピレン共重合体（Ｂ）の含量、分子量、組成、粒子サイズおよび分布はポリプロピレン樹脂組成物の物性に影響を与える主要要素となる。 The content, molecular weight, composition, particle size and distribution of the ethylene-propylene copolymer (B) are the main factors affecting the physical properties of the polypropylene resin composition.
エチレン−プロピレン共重合体（Ｂ）の含量が大きくなると、衝撃強さは増加するが、逆に引張強度および剛性は低下する。すなわち、本発明に係るポリプロピレン樹脂組成物において、エチレン−プロピレン共重合体（Ｂ）の含量が５質量％より少ないと衝撃強さが低下し、エチレン−プロピレン共重合体（Ｂ）の含量が２０質量％より多いと剛性が低下するという問題が発生する。 When the content of the ethylene-propylene copolymer (B) increases, the impact strength increases, but conversely, the tensile strength and rigidity decrease. That is, in the polypropylene resin composition according to the present invention, when the content of the ethylene-propylene copolymer (B) is less than 5% by mass, the impact strength is lowered and the content of the ethylene-propylene copolymer (B) is 20%. When the amount is more than mass%, there arises a problem that the rigidity is lowered.
エチレン−プロピレン共重合体の分子量は、エチレン−プロピレン共重合体を重合する気相反応器に注入される組成中の水素濃度（水素／エチレン）によって決定され、絶対粘度によって測定される。エチレン−プロピレン共重合体（Ｂ）の分子量が小さいとドメインであるエチレン−プロピレン共重合体の大きさが小さくなる。本発明への使用に適した分子量を持つエチレン−プロピレン共重合体（Ｂ）を生成するための水素濃度（水素／エチレン）は０．００５〜０．０３０のモル比であることが好ましい。水素／エチレンのモル比が０．０３０より大きい場合にはエチレン−プロピレン共重合体の大きさが小さくなり、衝撃の吸収に不十分となり、水素／エチレンのモル比が０．００５より小さい場合にはエチレン−プロピレン共重合体の大きさが大きくなりすぎて均一な分散が達成されず、部分的に衝撃強さが低下するという問題がある。 The molecular weight of the ethylene-propylene copolymer is determined by the hydrogen concentration (hydrogen / ethylene) in the composition injected into the gas phase reactor for polymerizing the ethylene-propylene copolymer, and is measured by absolute viscosity. When the molecular weight of the ethylene-propylene copolymer (B) is small, the size of the ethylene-propylene copolymer as a domain becomes small. The hydrogen concentration (hydrogen / ethylene) for producing an ethylene-propylene copolymer (B) having a molecular weight suitable for use in the present invention is preferably a molar ratio of 0.005 to 0.030. When the hydrogen / ethylene molar ratio is larger than 0.030, the size of the ethylene-propylene copolymer is small, which is insufficient for absorbing shock, and when the hydrogen / ethylene molar ratio is smaller than 0.005. Has a problem that the size of the ethylene-propylene copolymer becomes too large to achieve uniform dispersion, and the impact strength is partially reduced.
ところで、エチレン−プロピレン共重合体の分子量のみでエチレン−プロピレン共重合体の大きさおよび分布を調節するには限界がある。よって、エチレン−プロピレン共重合体の分子量、エチレン−プロピレン共重合体（Ｂ）とホモポリプロピレン（Ａ）の絶対粘度の比率、およびエチレン−プロピレン共重合体の組成を共に調節しなければ、優れた剛性および衝撃強さは得られない。 By the way, there is a limit in adjusting the size and distribution of the ethylene-propylene copolymer only by the molecular weight of the ethylene-propylene copolymer. Therefore, if the molecular weight of the ethylene-propylene copolymer, the ratio of the absolute viscosity of the ethylene-propylene copolymer (B) and the homopolypropylene (A), and the composition of the ethylene-propylene copolymer are not adjusted, it is excellent. Rigidity and impact strength are not obtained.
エチレン−プロピレン共重合体（Ｂ）とホモポリプロピレン（Ａ）の絶対粘度の比率は、母体であるホモポリプロピレン（Ａ）と衝撃吸収剤の役割を果たすエチレン−プロピレン共重合体（Ｂ）間の相溶性に関連する変数であって、各成分の絶対粘度の比率（＝成分Ａの絶対粘度／成分Ｂの絶対粘度）は０．０９〜０．３３であることが好ましい。絶対粘度の比率が０．０９より小さい場合、または絶対粘度の比率が０．３３より大きい場合には、エチレン−プロピレン共重合体（Ｂ）がホモポリプロピレン（Ａ）内で固まって存在するか或いは不均一に分散することになるため、優れた衝撃強さおよび剛性を持つエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂を製造することができなくなる。
The absolute viscosity ratio between the ethylene-propylene copolymer (B) and the homopolypropylene (A) is a phase between the base homopolypropylene (A) and the ethylene-propylene copolymer (B) serving as a shock absorber. It is a variable related to solubility, and the ratio of absolute viscosity of each component (= absolute viscosity of component A / absolute viscosity of component B) is preferably 0.09 to 0.33. When the absolute viscosity ratio is smaller than 0.09, or when the absolute viscosity ratio is larger than 0.33, the ethylene-propylene copolymer (B) is solidified in the homopolypropylene (A), or Since it will disperse | distribute unevenly, it will become impossible to manufacture the ethylene-propylene block copolymer polypropylene resin which has the outstanding impact strength and rigidity.
エチレン−プロピレン共重合体（Ｂ）の組成は、エチレン／（エチレン＋プロピレン）のモル比によって調節される。この比率が大きければ、主としてエチレン共重合体が生成され、その比率が小さければ、エチレン−プロピレンランダム共重合体が生成される。エチレン−プロピレン共重合体のプロピレン含量が増加すると、ホモプロピレンとエチレン−プロピレン共重合体間の界面張力が弱くなってエチレン−プロピレン共重合体の分散が良好となるため、得られるエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂が優れた剛性および衝撃強さを持つこととなる。 The composition of the ethylene-propylene copolymer (B) is adjusted by the molar ratio of ethylene / (ethylene + propylene). If this ratio is large, an ethylene copolymer is mainly produced, and if the ratio is small, an ethylene-propylene random copolymer is produced. When the propylene content of the ethylene-propylene copolymer is increased, the interfacial tension between the homopropylene and the ethylene-propylene copolymer is weakened and the dispersion of the ethylene-propylene copolymer is improved. The copolymer polypropylene resin will have excellent rigidity and impact strength.
具体的には、エチレン−プロピレン共重合体において、エチレン／（エチレン＋プロピレン）のモル比が０．１５より小さい場合には、エチレン−プロピレン共重合体の大きさが非常に小さくなるため分散は良好となるが、反面、完全に混合されて単一相を形成するので衝撃強さが弱くなるという問題がある。
逆に、エチレン／（エチレン＋プロピレン）のモル比が０．４０より大きい場合には、半結晶性のエチレン共重合体(semicrystalline ethylene copolymer)の生成およびホモポリプロピレンとエチレン−プロピレン弾性共重合体間の界面張力によって衝撃強さが弱くなるという問題がある。
Specifically, in the ethylene-propylene copolymer, when the ethylene / (ethylene + propylene) molar ratio is smaller than 0.15 , the size of the ethylene-propylene copolymer becomes very small, so that the dispersion is Although good, on the other hand, there is a problem that the impact strength is weakened because it is completely mixed to form a single phase.
Conversely, if the ethylene / (ethylene + propylene) molar ratio is greater than 0.40, the formation of a semicrystalline ethylene copolymer and the homopolypropylene and the ethylene-propylene elastic copolymer There is a problem that the impact strength is weakened by the interfacial tension.
また、エチレン−プロピレン共重合体の大きさは０．５〜２．０μｍであることが好ましいが、エチレン−プロピレン共重合体の大きさが０．５μｍより小さい場合または２．０μｍより大きい場合には、衝撃を吸収することができなくて衝撃強さが不良になる。 Further, the size of the ethylene-propylene copolymer is preferably 0.5 to 2.0 μm, but when the size of the ethylene-propylene copolymer is smaller than 0.5 μm or larger than 2.0 μm. Cannot absorb the impact, resulting in poor impact strength.
完製品の機械的強度を補完するために、本発明に係るポリプロピレン樹脂組成物に添加される核剤（Ｃ）は、ジベンジリデンソルビトール、ジ（ｐ−メチルベンジリデン）ソルビトール、ジメチルベンジリデンソルビトール、アルキル安息香酸アルミニウム塩、有機リン金属塩、およびこれらの混合物から選択され得る。好ましい核剤の含量はポリプロピレン１００質量部に対して０．０５〜０．３質量部であって、核剤の含量が０．０５質量部より少ないと十分な剛性および耐熱性を確保することができなくなるが、核剤の含量が０．３質量部より多くてもそれ以上の物性向上は見られない。 In order to complement the mechanical strength of the finished product, the nucleating agent (C) added to the polypropylene resin composition according to the present invention is dibenzylidene sorbitol, di (p-methylbenzylidene) sorbitol, dimethylbenzylidene sorbitol, alkylbenzoic acid. It can be selected from acid aluminum salts, organophosphorus metal salts, and mixtures thereof. A preferable content of the nucleating agent is 0.05 to 0.3 parts by mass with respect to 100 parts by mass of polypropylene, and if the content of the nucleating agent is less than 0.05 parts by mass, sufficient rigidity and heat resistance can be secured. However, even if the content of the nucleating agent exceeds 0.3 parts by mass, no further improvement in physical properties is observed.
本発明に係る樹脂組成物には、必要に応じて公知の添加剤、例えば酸化防止剤、中和剤、安定剤などがさらに含まれてもよい。 The resin composition according to the present invention may further contain a known additive, for example, an antioxidant, a neutralizing agent, a stabilizer and the like, if necessary.
一般に、ポリプロピレン系樹脂が自動車用部品の製造に使用されるためには、５．０ｋｇ・ｃｍ／ｃｍ以上のＩｚｏｄ衝撃強さと３００ｋｇ／ｃｍ2以上の引張強度が要求され
るが、従来から使用されてきた例えばタルクなどの無機添加物の添加のみではこのような衝撃強さおよび引張強度の水準を同時に達成することはできない。本発明に示されているように、ホモポリプロピレンの立体規則性、エチレン−プロピレン共重合体の分子量および組成、界面張力、大きさおよび分布などの総合的な調節によって、エチレン−プロピレンブロック共重合体系ポリプロピレン樹脂を製造しなければならない。
In general, in order for polypropylene resin to be used in the production of automotive parts, Izod impact strength of 5.0 kg · cm / cm or more and tensile strength of 300 kg / cm 2 or more are required, but it has been used conventionally. Such a level of impact strength and tensile strength cannot be achieved at the same time only by adding inorganic additives such as talc. As shown in the present invention, the ethylene-propylene block copolymer system is controlled by comprehensive control of homopolypropylene stereoregularity, ethylene-propylene copolymer molecular weight and composition, interfacial tension, size and distribution, etc. Polypropylene resin must be produced.
以下、実施例によって本発明をさらに具体的に説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.
本発明の実施例および比較例で製造されたポリプロピレンの物性評価方法は次の通りである。
１）溶融指数：ＡＳＴＭ Ｄ１２３８に準拠して、測定温度２３０℃、荷重２．１６Ｋｇの条件下で測定した。
２）立体規則度：１３Ｃ−ＮＭＲを用いてホモポリプロピレン分子鎖のうちペンタッド
単位でアイソタクチック分率を測定した。
３）曲げ弾性率：ＡＳＴＭ Ｄ７９０に準拠して、測定温度２３℃の条件下で射出試片に対して測定した。
４）Ｉｚｏｄ衝撃強さ：ＡＳＴＤ Ｄ２５６に準拠して、測定温度２３℃の条件下で射出試片に対して測定した。
５）キシレン溶融分：重合実験で得られた一定量の試料を一定量のキシレンと共に丸底フラスコに入れ、沸点まで温度を加えて約１時間溶解させた後、常温まで徐冷して再結晶し、キシレンに溶融された部分を抽出し、キシレンを蒸発させ、残った試料の百分率を測定した。
６）絶対粘度：プロピレン−エチレン共重合体を１３５℃でデカリン（デカヒドロナフタレン）に溶かした後、粘度計で絶対粘度を測定した。
７）旋回流：１５０トンの射出機を用いて温度２１０℃でスパイラル金型に射出し、射出された試片の長さを測定した。
８）電子顕微鏡の撮影：試片を液体窒素に浸して冷却した後、マイクロトーム機で断面を切断し、シクロヘキサン溶液内に入れて超音波洗浄機内で１時間放置させて試料内のエチレン−プロピレン弾性体を溶かした後、金で蒸着させてＺＥＯＬ社の電子顕微鏡で試料内のエチレン−プロピレン弾性共重合体の大きさおよび分散を観察した。
The physical property evaluation methods of the polypropylenes produced in the examples and comparative examples of the present invention are as follows.
1) Melting index: Measured under the conditions of a measurement temperature of 230 ° C. and a load of 2.16 kg according to ASTM D1238.
2) Stereoregularity: The isotactic fraction was measured in pentad units in the homopolypropylene molecular chain using 13C-NMR.
3) Flexural modulus: Measured with respect to injection specimens under a measurement temperature of 23 ° C. in accordance with ASTM D790.
4) Izod impact strength: Measured with respect to an injection specimen under a measurement temperature of 23 ° C. according to ASTD D256.
5) Xylene melt: A fixed amount of the sample obtained in the polymerization experiment is placed in a round bottom flask together with a fixed amount of xylene, heated to the boiling point and dissolved for about 1 hour, then gradually cooled to room temperature and recrystallized. Then, the part melted in xylene was extracted, xylene was evaporated, and the percentage of the remaining sample was measured.
6) Absolute viscosity: The propylene-ethylene copolymer was dissolved in decalin (decahydronaphthalene) at 135 ° C, and then the absolute viscosity was measured with a viscometer.
7) Swirl flow: Using a 150-ton injection machine, the sample was injected into a spiral mold at a temperature of 210 ° C., and the length of the injected specimen was measured.
8) Photographing with an electron microscope: After immersing the specimen in liquid nitrogen and cooling, cut the cross section with a microtome machine, put it in a cyclohexane solution, and let it stand in an ultrasonic cleaner for 1 hour. Ethylene-propylene in the sample After melting the elastic body, it was vapor-deposited with gold, and the size and dispersion of the ethylene-propylene elastic copolymer in the sample were observed with an electron microscope of ZEOL.
下記の方法によって実施例および比較例で使用した組成物を製造した。
１．成分（Ａ）の製造
重合反応装置に水素およびプロピレンを順次注入した後、６０〜８０℃、３５〜４０気圧の下でスラリーバルク重合を行った。溶融指数は水素の量で調節した。
２．成分（Ｂ）の製造
前述したように、成分（Ａ）であるホモプロピレンの重合が完了した後、未反応のプロピレンを除去し、常圧に降圧した後、７０〜８０℃、１０〜１５気圧の下でモノマーとしてエチレンとプロピレンを注入し、溶融指数調節剤として水素を注入してガス相で重合を連続的に行うことにより、エチレン−プロピレン共重合体である成分（Ｂ）を得た。
この段階において、弾性共重合体内のエチレン−プロピレン組成比は、表１に示したエチレン／（エチレン＋プロピレン）のモル比で調節した。絶対粘度は水素／エチレンのモル比で調節した。
３．ペレットおよび試験試片の製造
前記段階から得た樹脂に、前記樹脂１００質量部を基準として、１次酸化防止剤としてフェノール系酸化防止剤であるペンタエリトリチル−テトラキス［３−（３，５−ジ−第三ブチル−４−ヒドロキシ−フェニル）−プロピオネート］(Pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionate])０．０５質量部、２次酸化防止
剤としてリン系酸化防止剤であるトリス（２，４−ジ−第三ブチルフェニル）ホスフェート(Tris(2,4-di-tert-butylphenyl)phosphate)０．１０質量部、中和剤としてステアリン酸カルシウム０．０５質量部、核剤としてアルキル安息香酸アルミニウム塩０．１０質量部を混合し、ツインスクリュー押出機でペレットを製造した後、東信油圧社の１５０トン射出機でＡＳＴＭ規格の射出試片を製造して物性を測定した。表１および図１〜図３にその結果を示した。
The compositions used in Examples and Comparative Examples were produced by the following method.
1. Production of Component (A) After sequentially injecting hydrogen and propylene into the polymerization reactor, slurry bulk polymerization was performed at 60 to 80 ° C. and 35 to 40 atm. The melt index was adjusted by the amount of hydrogen.
2. Production of Component (B) As described above, after the polymerization of homopropylene as component (A) is completed, unreacted propylene is removed, and the pressure is reduced to normal pressure, followed by 70 to 80 ° C. and 10 to 15 atm. The component (B) which is an ethylene-propylene copolymer was obtained by injecting ethylene and propylene as monomers and injecting hydrogen as a melt index modifier and continuously performing polymerization in the gas phase.
At this stage, the ethylene-propylene composition ratio in the elastic copolymer was adjusted by the molar ratio of ethylene / (ethylene + propylene) shown in Table 1. The absolute viscosity was adjusted by the hydrogen / ethylene molar ratio.
3. Manufacture of pellets and test specimens Based on 100 parts by mass of the resin, the resin obtained from the above step was converted to pentaerythrityl-tetrakis [3- (3,5- Di-tert-butyl-4-hydroxy-phenyl) -propionate] (Pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxy-phenyl) -propionate]) 0.05 parts by mass, 2 0.10 parts by mass of tris (2,4-di-tert-butylphenyl) phosphate (phosphorus antioxidant) as a secondary antioxidant, neutralizing agent After mixing 0.05 parts by weight of calcium stearate and 0.10 parts by weight of alkylbenzoic acid aluminum salt as a nucleating agent, pellets were produced with a twin screw extruder, followed by ASTM standard injection with a 150-ton injection machine manufactured by Toshin Hydraulic Co., Ltd. Make a specimen Physical properties were measured. The results are shown in Table 1 and FIGS.
表１に示すように、実施例１および実施例２は、絶対粘度の比率が０．０９〜０．３３の範囲で製造されたものである。
一方、比較例１および比較例２は絶対粘度の比率が０．０９〜０．３３の範囲を外れたものである。
また比較例３および比較例４は絶対粘度の比率が０．０９〜０．３３の範囲で製造されたものであるが、比較例３の場合はペンタッド分率が９６％より小さく、比較例４の場合は気相反応器におけるエチレン−プロピレン弾性共重合体の重合条件が本発明に係る実施例１および２とは異なる。
さらに比較例５は、全ての条件は実施例１および２と同様であるが、但し成分Ｂの含量が２１質量％と非常に高い。
また、比較例２および３においては、重合されたポリプロピレンに有機過酸化物を人為的に添加してポリプロピレン系樹脂の溶融指数を高めたものである。
As shown in Table 1, Examples 1 and 2 are manufactured in the range of 0.09 to 0.33 in absolute viscosity ratio.
On the other hand, in Comparative Example 1 and Comparative Example 2, the absolute viscosity ratio is out of the range of 0.09 to 0.33.
In Comparative Example 3 and Comparative Example 4, the absolute viscosity ratio was produced in the range of 0.09 to 0.33. In Comparative Example 3, the pentad fraction was less than 96%. In this case, the polymerization conditions of the ethylene-propylene elastic copolymer in the gas phase reactor are different from those in Examples 1 and 2 according to the present invention.
Further, in Comparative Example 5, all the conditions were the same as in Examples 1 and 2, except that the content of Component B was as high as 21% by mass.
In Comparative Examples 2 and 3, an organic peroxide was artificially added to polymerized polypropylene to increase the melt index of the polypropylene resin.
表１に示されている実験結果の如く、本発明に係る実施例１および２の組成物は、５．０ｋｇ・ｃｍ／ｃｍ以上のＩｚｏｄ衝撃強さと３００ｋｇ／ｃｍ2以上の引張強度を示し
ており、比較例１〜５に比べて全体的に優れた機械的物性、流動性、臭いおよび塗装性などの後加工特性を示すことができた。
As shown in the experimental results shown in Table 1, the compositions of Examples 1 and 2 according to the present invention exhibited an Izod impact strength of 5.0 kg · cm / cm or more and a tensile strength of 300 kg / cm 2 or more. As a result, post-processing characteristics such as mechanical properties, fluidity, odor, and paintability, which were generally superior to those of Comparative Examples 1 to 5, could be shown.
Claims (2)
ここで、前記高結晶性ホモポリプロピレン成分（Ａ）と前記エチレン−プロピレン弾性共重合体成分（Ｂ）の極限粘度比率（Ａ／Ｂ）が０．０９〜０．３３であり、
前記エチレン−プロピレン弾性共重合体成分（Ｂ）は、水素濃度（水素／エチレン）が０．００５〜０．０３０のモル比で共重合させて作られ、
前記エチレン−プロピレン弾性共重合体成分（Ｂ）は、０．５〜２．０μｍの大きさを有する、ポリプロピレン樹脂組成物であって、前記ポリプロピレン樹脂組成物は、
衝撃強さが５．０ｋｇ・ｃｍ／ｃｍ以上であり、引張強度が３００ｋｇ／ｃｍ ２ 以上であり、そしてメルトフローレートが８５〜１２０ｇ／１０分であるエチレン−プロピレンブロック共重合体系ポリプロピレン樹脂組成物。 Highly crystalline homopolypropylene component (A) having an isotactic pentad fraction of 96% or more as a matrix (A) is 80 to 95% by mass, and ethylene / (ethylene + propylene) molar ratio is 0.15 to 0.30 as a domain. Of ethylene-propylene elastic copolymer component (B) 5 to 20% by mass of ethylene-propylene block copolymer polypropylene resin 100 parts by mass and nucleating agent (C) 0.05 to 0.3 parts by mass,
Here, the intrinsic viscosity ratio (A / B) of the highly crystalline homopolypropylene component (A) and the ethylene-propylene elastic copolymer component (B) is 0.09 to 0.33,
The ethylene-propylene elastic copolymer component (B) is made by copolymerization at a molar ratio of hydrogen concentration (hydrogen / ethylene) of 0.005 to 0.030,
The ethylene-propylene elastic copolymer component (B) is a polypropylene resin composition having a size of 0.5 to 2.0 μm, and the polypropylene resin composition comprises:
And the impact strength 5.0 kg · cm / cm or more, a tensile strength of at 300 kg / cm 2 or more, and the melt flow rate is 85 to 120 g / 10 min ethylene - propylene block copolymer polypropylene resin composition .
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