JP6352320B2 - Polypropylene resin composition with low gloss and flow mark appearance defects suppressed - Google Patents
Polypropylene resin composition with low gloss and flow mark appearance defects suppressed Download PDFInfo
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- JP6352320B2 JP6352320B2 JP2016009440A JP2016009440A JP6352320B2 JP 6352320 B2 JP6352320 B2 JP 6352320B2 JP 2016009440 A JP2016009440 A JP 2016009440A JP 2016009440 A JP2016009440 A JP 2016009440A JP 6352320 B2 JP6352320 B2 JP 6352320B2
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- -1 Polypropylene Polymers 0.000 title claims description 50
- 239000004743 Polypropylene Substances 0.000 title claims description 45
- 229920001155 polypropylene Polymers 0.000 title claims description 45
- 239000011342 resin composition Substances 0.000 title claims description 45
- 230000007547 defect Effects 0.000 title description 3
- 229920001577 copolymer Polymers 0.000 claims description 23
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 claims description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 5
- 238000000862 absorption spectrum Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 229920001384 propylene homopolymer Polymers 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 239000012748 slip agent Substances 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 239000004033 plastic Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- YHGJJXWSBKQECN-UHFFFAOYSA-N 2,4-ditert-butylphenol;phosphoric acid Chemical compound OP(O)(O)=O.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 YHGJJXWSBKQECN-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- UYXLOULABOHUAJ-UHFFFAOYSA-N CO[SiH](OC)CCC1=CC=CC=C1 Chemical compound CO[SiH](OC)CCC1=CC=CC=C1 UYXLOULABOHUAJ-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- OANIYCQMEVXZCJ-UHFFFAOYSA-N ditert-butyl(dimethoxy)silane Chemical compound CO[Si](OC)(C(C)(C)C)C(C)(C)C OANIYCQMEVXZCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- 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
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
- C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
-
- 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
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/70—Organic dyes or pigments; Optical brightening agents
Description
本発明は射出成形時に成形性に優れ、剛性と耐衝撃性の均衡に優れ、低光沢およびフローマーク（ｆｌｏｗ ｍａｒｋ）の外観不良が抑制されたポリプロピレン樹脂組成物に関する。 The present invention relates to a polypropylene resin composition having excellent moldability during injection molding, excellent balance between rigidity and impact resistance, low gloss and poor appearance of a flow mark.
ポリオレフィンを利用したプラスチック射出物を自動車部品として用いる場合、部品の軽量化による高燃費性を有する自動車を生産でき、また再利用の容易性が高いという長所を持っている。しかし、プラスチック射出物を自動車部品として用いる場合、フローマークの外観不良が問題となるだけでなく、プラスチックの光沢が高くなることによって日差しに反射された光が運転者の視野を邪魔して運転中の安全に深刻な影響を与えることがある。 When a plastic injection product using polyolefin is used as an automobile part, it has an advantage that an automobile having high fuel efficiency can be produced by reducing the weight of the part, and that reuse is easy. However, when plastic injections are used as automobile parts, not only is the appearance of the flow mark inferior, but the light reflected by the sun is obstructing the driver's field of view due to the high gloss of the plastic. May have a serious impact on safety.
フローマーク、溶融樹脂の流れ跡による外観不良を防止するために、塗装方法またはエチレン−α−オレフィン系ランダム共重合体と無機充填材を含む方法があり、光沢を低くする方法としては無機物（タルク、シリカなど）の添加、プラスチックゴム成分の混合、プラスチック製品の表面を低光沢物質で塗布、射出金型表面の修正、反応容器で樹脂組成変更などのようにポリプロピレン樹脂にその他添加物を混合する方法がある。自動車の内装材部品として使用するためにはこのようなフローマークの外観不良の抑制と低光沢性が同時に要求され、この２種類の特性をいずれも満足するプラスチック製品の開発が要求されている。 In order to prevent appearance defects due to flow marks and flow marks of the molten resin, there are a coating method or a method including an ethylene-α-olefin random copolymer and an inorganic filler, and a method for reducing gloss is an inorganic substance (talc , Silica, etc.), mixing plastic rubber components, coating the surface of plastic products with a low-gloss material, modifying the injection mold surface, changing the resin composition in the reaction vessel, etc., and mixing other additives into the polypropylene resin There is a way. In order to use it as an automobile interior material part, it is required to suppress the appearance defect of such a flow mark and to have low gloss at the same time, and development of a plastic product that satisfies both of these two characteristics is required.
従来の大韓民国登録特許１０−１４３１９０６号公報においては剛性と衝撃特性が優れ、かつ低い表面光沢度を表すことができるポリプロピレン樹脂組成物が記載されており、日本国特開２００８−１９３４６号公報においてはフローマークの外観が優れ、流動性が優れ、剛性と耐衝撃性バランスが良好なポリプロピレン樹脂組成物が記載されている。当該組成物は結晶性プロピレン−エチレンブロック共重合体を含有するポリプロピレン樹脂、エチレン−α−オレフィン共重合体ゴムと少量の有機過酸化物、無機充填剤を含む。しかし、有機過酸化物を利用することによって流動性は向上したが、射出成形体の剛性と耐衝撃性のバランス、耐加熱変形性、硬度、臭いなどに対しては改善が要求されている。 The conventional Korean Patent No. 10-1431906 discloses a polypropylene resin composition that is excellent in rigidity and impact properties and can exhibit low surface glossiness. In Japanese Patent Laid-Open No. 2008-19346, A polypropylene resin composition is described in which the appearance of the flow mark is excellent, the fluidity is excellent, and the rigidity and impact resistance balance is good. The composition contains a polypropylene resin containing a crystalline propylene-ethylene block copolymer, an ethylene-α-olefin copolymer rubber, a small amount of an organic peroxide, and an inorganic filler. However, although fluidity has been improved by using an organic peroxide, improvements are required for the balance between rigidity and impact resistance, heat distortion resistance, hardness, odor, and the like of the injection molded body.
前記問題点を解決するための本発明の目的は、剛性と衝撃特性に優れ、かつ低い表面光沢度とフローマークの外観不良が抑制された高級自動車用内装材に適用可能なポリプロピレン樹脂組成物を提供することにある。
本発明の他の目的は、前記ポリプロピレン樹脂組成物の製造方法を提供することにある。
本発明のまた他の目的は、前記ポリプロピレン樹脂組成物から製造された成形品を提供することにある。
The object of the present invention to solve the above problems is to provide a polypropylene resin composition that is excellent in rigidity and impact characteristics, and that can be applied to interior materials for high-grade automobiles with low surface glossiness and reduced appearance of flow marks. It is to provide.
Another object of the present invention is to provide a method for producing the polypropylene resin composition.
Another object of the present invention is to provide a molded article produced from the polypropylene resin composition.
前記目的を達成するための本発明の様相は、エチレン−プロピレンブロック共重合体を含むポリプロピレン樹脂組成物において、前記エチレン−プロピレンブロック共重合体はホモポリプロピレン重合体と、エチレン−プロピレン共重合体とからなり、
前記ポリプロピレン樹脂組成物を１４０℃において１重量％でキシレンに溶かして抽出した成分の含有量（重量％）と、赤外線吸収スペクトルの７２０ｃｍ −１ 、７４０ｃｍ −１ の特性ピークを利用して測定したエチレン含有量（重量％）との比は０．５〜２．０であり、前記エチレン−プロピレンブロック共重合体の溶融指数はＡＳＴＭ Ｄ１２３８の２３０℃、２．１６ｋｇで５〜３０ｇ／１０分であり、キシレン可溶部とプロピレン単独重合体の固有粘度比（ηＸＳ／ηｈｏｍｏＰＰ）は３〜８であることを特徴とするポリプロピレン樹脂組成物を提供する。
The aspect of the present invention for achieving the object is a polypropylene resin composition containing an ethylene-propylene block copolymer, wherein the ethylene-propylene block copolymer comprises a homopolypropylene polymer, an ethylene-propylene copolymer, Consists of
Ethylene wherein the content of the polypropylene resin composition was extracted by dissolving in xylene at 1 wt% at 140 ° C. Component (weight%), infrared absorption spectra of the 720 cm -1, was measured using the characteristic peaks of 740 cm -1 The ratio to the content (% by weight) is 0.5 to 2.0, and the melt index of the ethylene-propylene block copolymer is 5 to 30 g / 10 min at 230 ° C. and 2.16 kg of ASTM D1238. The polypropylene resin composition is characterized in that the intrinsic viscosity ratio (ηXS / ηhomoPP) of the xylene-soluble part and the propylene homopolymer is 3 to 8.
本発明は、射出プラスチック製品の光沢を低くするだけでなくフローマークの外観不良を抑制し、かつ優秀な機械的物性を示すポリプロピレン樹脂組成物を提供する。前記ポリプロピレン樹脂組成物は低光沢およびフローマークの外観特性を要求する自動車用内・外装材プラスチック部品、無光沢外装部品を要求する電子製品、家電製品などに効果的に適用可能である。 The present invention provides a polypropylene resin composition that not only lowers the gloss of an injection plastic product but also suppresses poor appearance of the flow mark and exhibits excellent mechanical properties. The polypropylene resin composition can be effectively applied to automobile interior / exterior plastic parts that require low gloss and flow mark appearance characteristics, electronic products that require matte exterior parts, and home appliances.
以下、本発明をさらに詳しく説明する。
エチレン−プロピレンブロック共重合体を含むポリプロピレン樹脂組成物において、前記エチレン−プロピレンブロック共重合体はホモポリプロピレン重合体と、エチレン−プロピレン共重合体とからなり、前記エチレン−プロピレン共重合体に対するエチレン含有量の重量比は０．５〜２．０であり、前記エチレン−プロピレンブロック共重合体の溶融指数はＡＳＴＭ Ｄ１２３８の２３０℃、２．１６ｋｇで５〜３０ｇ／１０分であり、キシレン可溶部とプロピレン単独重合体の固有粘度比（ηＸＳ／ηｈｏｍｏＰＰ）は３〜８であることを特徴とするポリプロピレン樹脂組成物を提供する。
Hereinafter, the present invention will be described in more detail.
In the polypropylene resin composition containing an ethylene-propylene block copolymer, the ethylene-propylene block copolymer comprises a homopolypropylene polymer and an ethylene-propylene copolymer, and contains ethylene relative to the ethylene-propylene copolymer. The weight ratio of the amount is 0.5 to 2.0, and the melt index of the ethylene-propylene block copolymer is 5 to 30 g / 10 min at 230 ° C. and 2.16 kg of ASTM D1238, And a propylene homopolymer having an intrinsic viscosity ratio (ηXS / ηhomoPP) of 3 to 8 is provided.
本発明は低光沢ポリプロピレン樹脂組成物を提供するものであり、前記ポリプロピレン樹脂組成物はエチレン−プロピレンブロック共重合体樹脂を含むことができる。 The present invention provides a low gloss polypropylene resin composition, and the polypropylene resin composition may include an ethylene-propylene block copolymer resin.
本発明の一実施例により、前記エチレン−プロピレンブロック共重合体樹脂はホモポリプロピレン重合体部分とゴム成分としてエチレン−プロピレン共重合体部分とからなることができる。 According to an embodiment of the present invention, the ethylene-propylene block copolymer resin may include a homopolypropylene polymer portion and an ethylene-propylene copolymer portion as a rubber component.
本発明において、前記エチレン−プロピレンブロック共重合体においてエチレン−プロピレン共重合体とエチレン含有量の重量比は０．５〜２．０であり、望ましくは１．０〜２．０であり、さらに望ましくは１．０〜１．５である。前記重量比が０．５未満であれば前記ポリプロピレン樹脂の低光沢特性を示し難く、２．０を超えれば光沢性は低くすることができるが、前記組成物のベンディング剛性が低下してベンディング剛性および低光沢度を同時に満足するポリプロピレン樹脂組成物を得難くなる。前記エチレン−プロピレン共重合体とエチレン含有量の重量比はキシレン抽出物および赤外線吸収スペクトルで測定することができる。 In the present invention, in the ethylene-propylene block copolymer, the weight ratio of the ethylene-propylene copolymer and the ethylene content is 0.5 to 2.0, preferably 1.0 to 2.0, Desirably, it is 1.0-1.5. If the weight ratio is less than 0.5, it is difficult to show the low gloss characteristics of the polypropylene resin, and if it exceeds 2.0, the gloss can be lowered, but the bending rigidity of the composition is lowered and the bending rigidity is reduced. In addition, it is difficult to obtain a polypropylene resin composition that satisfies both the low glossiness and the glossiness. The weight ratio between the ethylene-propylene copolymer and the ethylene content can be measured by a xylene extract and an infrared absorption spectrum.
本発明において、前記エチレン−プロピレンブロック共重合体樹脂組成物の溶融指数は５〜３０ｇ／１０分（ＡＳＴＭ Ｄ１２３８、２３０℃、２．１６ｋｇ、Ｍｅｌｔ Ｉｎｄｅｘ、ＭＩ）であり、望ましくは１５〜３０ｇ／１０分であり、さらに望ましくは２０〜３０ｇ／１０分である。 In the present invention, the ethylene-propylene block copolymer resin composition has a melt index of 5 to 30 g / 10 min (ASTM D1238, 230 ° C., 2.16 kg, Melt Index, MI), preferably 15 to 30 g / min. 10 minutes, and more desirably 20 to 30 g / 10 minutes.
本発明において、前記エチレン−プロピレンブロック共重合体のキシレン可溶部（ＸＳ）とプロピレン単独重合体の固有粘度比（ηＸＳ／ηｈｏｍｏＰＰ）は３〜８であり、望ましくは４ないし６である。前記固有粘度比（ηＸＳ／ηｈｏｍｏＰＰ）が３未満の場合には前記ポリプロピレン樹脂組成物の射出時に成形品の外観にフローマークが非常に発生することができ、８を超える場合には流動性が低下して成形性の改善効果が得られない。 In the present invention, the intrinsic viscosity ratio (ηXS / ηhomoPP) of the xylene-soluble part (XS) and the propylene homopolymer of the ethylene-propylene block copolymer is 3 to 8, preferably 4 to 6. When the intrinsic viscosity ratio (ηXS / ηhomoPP) is less than 3, a flow mark can be very generated on the appearance of the molded product at the time of injection of the polypropylene resin composition, and when it exceeds 8, the fluidity decreases. Therefore, the improvement effect of formability cannot be obtained.
本発明において、前記エチレン−プロピレン共重合体のエチレン含有量は４０〜７０ｍｏｌ％である。前記エチレン含有量が４０ｍｏｌ％未満であれば、樹脂組成物の耐衝撃性が低下して望ましくないし、７０ｍｏｌ％超えれば硬度、耐熱性などが低下し、射出物表面のべたつきがあって望ましくない。 In the present invention, the ethylene content of the ethylene-propylene copolymer is 40 to 70 mol%. If the ethylene content is less than 40 mol%, the impact resistance of the resin composition is undesirably lowered, and if it exceeds 70 mol%, the hardness, heat resistance and the like are lowered, and the surface of the injection is not desirable.
本発明において、前記ゴム成分としてのエチレン−プロピレン共重合体はエチレン−プロピレンブロック共重合体全体の重量に対して５〜２０重量％であり、望ましくは１０〜１７重量％である。前記含有量が５重量％未満であれば低いゴム成分の含有量により光沢低下および衝撃強度が低下することがあり、２０重量％を超えれば屈曲強度と引張強度が相対的に低下することがあって望ましくない。前記エチレン−プロピレン共重合体の含有量は溶剤抽出物を利用して測定でき、前記溶剤はキシレン抽出物であることができる。 In the present invention, the ethylene-propylene copolymer as the rubber component is 5 to 20% by weight, preferably 10 to 17% by weight, based on the total weight of the ethylene-propylene block copolymer. If the content is less than 5% by weight, the gloss and impact strength may decrease due to the low rubber component content. If the content exceeds 20% by weight, the flexural strength and the tensile strength may decrease relatively. Is not desirable. The ethylene-propylene copolymer content may be measured using a solvent extract, and the solvent may be a xylene extract.
本発明において、前記ポリプロピレン樹脂組成物から製造された２ｍｍ厚さの無色平板試片（２ｍｍのシート）の６０°角度の光沢度を測定したときの表面光沢度（Ｇｌｏｓｓ、６０°）は７０％以下が望ましい。また、前記ポリプロピレン樹脂組成物のフローマークの外観不良は厚さ１．５ｍｍ、幅３ｃｍのスパイラルフローモールド（ｓｐｉｒａｌ ｆｌｏｗ ｍｏｌｄ）を射出機を通して射出して肉眼で評価したときに不良のない樹脂組成物である。 In the present invention, the surface glossiness (Gloss, 60 °) when measuring the glossiness at 60 ° angle of a 2 mm-thick colorless flat plate specimen (2 mm sheet) produced from the polypropylene resin composition is 70%. The following is desirable. Further, the poor appearance of the flow mark of the polypropylene resin composition is a resin composition that is not defective when a spiral flow mold having a thickness of 1.5 mm and a width of 3 cm is injected through an injection machine and evaluated with the naked eye. It is.
本発明において、前記ポリプロピレン樹脂組成物は発明の範囲を逸脱しない範囲内で通常の添加剤をさらに含むことができ、例えば補強剤、充填材、耐候安定剤、帯電防止剤、滑剤、スリップ剤、核剤、難燃剤、顔料、染料などを含むことができるが、これに限定されるものではない。 In the present invention, the polypropylene resin composition may further contain conventional additives within a range not departing from the scope of the invention, such as reinforcing agents, fillers, weathering stabilizers, antistatic agents, lubricants, slip agents, Nucleating agents, flame retardants, pigments, dyes and the like can be included, but are not limited thereto.
本発明において、前記ポリプロピレン樹脂組成物は射出成形品の耐熱安定性を増加させるために前記ポリプロピレン樹脂組成物１００重量部に対して０．１〜０．５重量部の耐熱安定剤をさらに含むことができ、望ましくは０．０２〜０．３重量部である。前記耐熱安定剤の含有量が０．１重量部未満であれば長期耐熱安定性を確保し難く、０．５重量部を超えれば耐熱安定剤の溶出が発生したり価格の経済性が低下して望ましくない。前記耐熱安定剤としてはフェノール系酸化防止剤、ホスフェート系酸化防止剤などが用いられ、具体的にテトラキス（メチレン（３、５−ジ−ｔ−ブチル−４−ヒドロキシ）ヒドロシリル化）、１、３、５−トリメチル−トリス（３、５−ジ−ｔ−ブチル−４−ヒドロキシベンゼン）およびトリス（２、４−ジ−ｔ−ブチルフェノール）ホスフェートのうち１種以上であることができる。 In the present invention, the polypropylene resin composition further includes 0.1 to 0.5 parts by weight of a heat stabilizer relative to 100 parts by weight of the polypropylene resin composition in order to increase the heat stability of the injection molded product. The amount is preferably 0.02 to 0.3 parts by weight. If the content of the heat stabilizer is less than 0.1 parts by weight, it is difficult to ensure long-term heat stability, and if it exceeds 0.5 parts by weight, elution of the heat stabilizer may occur or the cost may be reduced. Is not desirable. As the heat stabilizer, a phenolic antioxidant, a phosphate antioxidant, or the like is used. Specifically, tetrakis (methylene (3,5-di-t-butyl-4-hydroxy) hydrosilylation), 1, 3 , 5-trimethyl-tris (3,5-di-t-butyl-4-hydroxybenzene) and tris (2,4-di-t-butylphenol) phosphate.
本発明において、前記エチレン−プロピレンブロック共重合体樹脂はホモプロピレン重合体部分とエチレン−プロピレン共重合体部分が段階的に重合された樹脂であり、前記重合はチーグラ−ナッタ（Ｚｉｅｇｌｅｒ−Ｎａｔｔａ）触媒の存在下で行うことができる。また、前記重合方法はスラリー法、バルク法、気相法などのような本発明の技術分野において通常知られている方法および反応条件を利用することができる。具体的に、前記エチレン−プロピレンブロック共重合体樹脂は第１重合段階で２つ以上の反応器を通してホモポリプロピレンを重合し、第２重合段階で前記製造されたホモポリプロピレンにエチレンおよびプロピレンを投入してエチレン−プロピレン共重合体部分を重合することができる。前記第１重合段階および第２重合段階は互いに同一の重合反応器または異なる重合反応器で行うことができる。 In the present invention, the ethylene-propylene block copolymer resin is a resin in which a homopropylene polymer portion and an ethylene-propylene copolymer portion are polymerized stepwise, and the polymerization is a Ziegler-Natta catalyst. Can be carried out in the presence of The polymerization method may use methods and reaction conditions that are generally known in the technical field of the present invention, such as a slurry method, a bulk method, and a gas phase method. Specifically, the ethylene-propylene block copolymer resin polymerizes homopolypropylene through two or more reactors in the first polymerization stage, and injects ethylene and propylene into the produced homopolypropylene in the second polymerization stage. Thus, the ethylene-propylene copolymer portion can be polymerized. The first polymerization stage and the second polymerization stage may be performed in the same polymerization reactor or in different polymerization reactors.
例えば、前記重合はチーグラ−ナッタ（Ｚｉｅｇｌｅｒ−Ｎａｔｔａ）触媒および外部電子供与体を含む触媒系および水素ガスの存在下でホモポリプロピレンを合成する２つ以上のバルク重合反応器とエチレン−プロピレン共重合体を合成する気相重合反応器から構成された重合設備で行うことができる。前記ホモポリプロピレンを合成する２つ以上の反応器で合成されるホモポリプロピレンの最後の反応器での溶融指数は２０〜１００ｇ／１０分（ＡＳＴＭ Ｄ１２３８の２３０℃、２．１６ｋｇ）であることができる。２つ以上のホモポリプロピレンを合成する各反応器での溶融指数が順に小さくなるように運転することができ、それとは相反して、各反応器での溶融指数を同一に運転することができる。次に、前記合成されたホモポリプロピレンをエチレン−プロピレン共重合が行われる気相反応器に移動させ、エチレンとプロピレンを同時に投入することによってホモポリプロピレン固体成分と継続して共重合してエチレン−プロピレンブロック共重合体を製造することができる。前記気相反応器での全体ガスに対するエチレン含有量の比率は０．３０〜０．９０（モル比率）、望ましくは０．４０〜０．８０、さらに望ましくは０．５０〜０．７０であることができる。前記チーグラ−ナッタ（Ｚｉｅｇｌｅｒ−Ｎａｔｔａ）触媒はＭｇＣｌ２担体にＴｉＣｌ３またはＴｉＣｌ４を担持して生成された化合物を使用することができる。共触媒としてアルキルアルミニウム化合物が用いられ、その例として、トリエチルアルミニウム、ジエチルクロロアルミニウム、トリブチルアルミニウム、トリスイソブチルアルミニウム、トリオクチルアルミニウムなどが挙げられるが、本発明はこれらに限定されるものではない。前記外部電子供与体として有機シラン化合物が用いられ、例えばジフェニルジメトキシシラン、フェニルトリメトキシシラン、フェニルエチルジメトキシシラン、フェニルメチルジメトキシシラン、メトキシトリメチルシラン、イソブチルトリメトキシシラン、ジイソブチルジメトキシシラン、ジイソプロピルジメトキシシラン、ジ−ｔ−ブチルジメトキシシラン、ジシクロペンチルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、ジシクロヘキシルジメトキシシランなどが挙げられるが、これらに限定されるものではない。 For example, the polymerization may include a catalyst system comprising a Ziegler-Natta catalyst and an external electron donor, and two or more bulk polymerization reactors that synthesize homopolypropylene in the presence of hydrogen gas and an ethylene-propylene copolymer. Can be carried out in a polymerization facility composed of a gas phase polymerization reactor for synthesizing. The melt index in the last reactor of homopolypropylene synthesized in two or more reactors synthesizing the homopolypropylene can be 20-100 g / 10 min (ASTM D1238 230 ° C., 2.16 kg). . It is possible to operate so that the melt index in each reactor for synthesizing two or more homopolypropylenes decreases in order, and in contrast, the melt index in each reactor can be operated identically. Next, the synthesized homopolypropylene is transferred to a gas phase reactor in which ethylene-propylene copolymerization is carried out, and ethylene and propylene are added simultaneously to continuously copolymerize with the homopolypropylene solid component, thereby producing ethylene-propylene. Block copolymers can be produced. The ratio of ethylene content to the total gas in the gas phase reactor is 0.30 to 0.90 (molar ratio), preferably 0.40 to 0.80, and more preferably 0.50 to 0.70. be able to. The Ziegler-Natta catalyst may be a compound formed by supporting TiCl 3 or TiCl 4 on an MgCl 2 support. An alkylaluminum compound is used as the cocatalyst, and examples thereof include triethylaluminum, diethylchloroaluminum, tributylaluminum, trisisobutylaluminum, and trioctylaluminum, but the present invention is not limited to these. An organic silane compound is used as the external electron donor, such as diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane, phenylmethyldimethoxysilane, methoxytrimethylsilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, diisopropyldimethoxysilane, Examples thereof include, but are not limited to, di-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclohexyldimethoxysilane.
本発明によるポリプロピレン樹脂組成物は射出成形、押出成形など通常の成形法を利用してポリプロピレン樹脂成形品を製造することができる。前記成形品は低光沢を示しながら機械的物性に優れて低光沢特性が要求されるプラスチック製品に適用可能であり、例えば、自動車用内装材プラスチック部品、無光沢外装部品を要求する電子製品、家電製品、建築材料などが挙げられる。 The polypropylene resin composition according to the present invention can be used to produce a polypropylene resin molded article using a normal molding method such as injection molding or extrusion molding. The molded article can be applied to plastic products that exhibit low gloss and excellent mechanical properties and require low gloss properties. For example, automotive interior plastic parts, electronic products that require matte exterior parts, home appliances Products and building materials.
本発明は以下の実施例によってより具体的に分かり、以下の実施例は本発明を例示するためのものであって、本発明の保護範囲を限定するものではない。 The present invention will be more specifically understood from the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the protection scope of the present invention.
実施例１〜３および比較例１〜３
（１）エチレンプロピレンブロック共重合体の重合
ＴｉＣｌ４、ＭｇＣｌ２からなるチーグラ−ナッタ（Ｚｉｅｇｌｅｒ−Ｎａｔｔａ）触媒と外部電子供与体のジシクロペンチルジメトキシシラン、そして触媒の活性化のためにトリエチルアルミニウムを添加した触媒系から直列配置された４つの重合槽のうち1番目から３番目の重合槽（バルク重合槽）にプロピレンを注入してホモポリプロピレンを製造した後、生成された重合体を４番目の気相重合槽に移して、エチレンとプロピレンを投入して気相重合を行い、表１に示したようにエチレン−プロピレンブロック共重合体を製造した。
Examples 1-3 and Comparative Examples 1-3
(1) Polymerization of ethylene propylene block copolymer Ziegler-Natta catalyst composed of TiCl 4 and MgCl 2 , external electron donor dicyclopentyldimethoxysilane, and triethylaluminum added for catalyst activation Propylene was injected into the first to third polymerization tanks (bulk polymerization tanks) among the four polymerization tanks arranged in series from the catalyst system produced to produce homopolypropylene. It moved to the phase polymerization tank, ethylene and propylene were injected | thrown-in, and vapor phase polymerization was performed, and as shown in Table 1, the ethylene-propylene block copolymer was manufactured.
（２）物性評価
前記製造されたエチレンプロピレンブロック共重合体樹脂を利用して１５０トン射出機（（株）ウジン製品）を利用して１９０〜２３０℃で射出して得た基準試片ＡＳＴＭ−１号と、２ｍｍの平板試片（２ｍｍのシート）を射出成形して試片を得た。
(2) Physical property evaluation Standard specimen ASTM- obtained by injecting at 190-230 ° C. using 150 ton injection machine (Ujin product) using the produced ethylene propylene block copolymer resin No. 1 and a 2 mm flat plate specimen (2 mm sheet) were injection molded to obtain a specimen.
フローマーク発生の程度
◎：フローマークがほとんど肉眼では見えない。
○：フローマークがかすかに見える。
△：フローマークが見える。
×：フローマークが鮮明に見える。
Degree of occurrence of flow mark A: The flow mark is hardly visible with the naked eye.
○: The flow mark looks faint.
Δ: A flow mark is visible.
X: The flow mark looks clear.
評価方法
（１）溶融指数（Ｍｅｌｔ ｉｎｄｅｘ、ｇ／１０分）
ＡＳＴＭ Ｄ１２３８により２３０℃、２．１６ｋｇの条件で測定した。
（２）エチレン−プロピレン共重合体ゴムキシレン抽出分（ＸｙｌｅｎｅＳｏｌｕｂｌｅ、Ｘ．Ｓ、重量％）
プロピレン系混合樹脂をキシレンに１％濃度に１４０℃で１時間溶かした後、常温で２時間経過した後に抽出してその重量を測定し、プロピレン系混合樹脂の全体の重量に対する百分率で表した。
（３）エチレン−プロピレン共重合体とエチレン含有量の比（Ｘｙｌｅｎｅ Ｓｏｌｕｂｌｅ／ｅｔｈｙｌｅｎｅ、Ｘ．Ｓ／Ｃ２、重量％／重量％）
１％濃度のプロピレン系混合樹脂をキシレンに溶かして抽出した成分の全体重量の百分率と赤外線吸収スペクトルの７２０、７４０ｃｍ−１の特性ピークを利用して測定したエチレン含有量の比である。
（４）固有粘度比（ＩＶ ｒａｔｉｏ、Ｉｎｔｒｉｎｓｉｃ Ｖｉｓｃｏｓｉｔｙ ｒａｔｉｏ）
キシレンに溶かして抽出したエチレン−プロピレン共重合体およびホモポリプロピレンを固有粘度計を利用して測定し、その比率を表した。
（５）エチレン−プロピレン共重合体のエチレン含有量（Ｅｔｈｙｌｅｎｅ−Ｐｒｏｐｙｌｅｎｅ ｒｕｂｂｅｒ、ＥＰＲ−Ｃ２、ｍｏｌ％）
キシレン抽出によって得られたエチレン−プロピレン共重合体に対するエチレン分率であって、赤外線吸収スペクトルを利用して７２０、７４０ｃｍ−１の特性ピークを利用してエチレン含有量を測定した。
（６）光沢度（Ｇｌｏｓｓ（６０°）、％）
ＡＳＴＭ Ｄ５２３方法により６０°角度で反射光量を測定した。
（７）フローマークの外観不良
フローマークの外観不良は厚さ１．５ｍｍ、幅３ｃｍのスパイラルフローモールド（ｓｐｉｒａｌ ｆｌｏｗ ｍｏｌｄ）を通じて射出機（ＬＧ ＬＧＨ１４０Ｎ）を利用して射出し、肉眼で評価した。
（８）屈曲弾性率（ｋｇｆ／ｃｍ２）
ＡＳＴＭ Ｄ７９０方法により測定した。
（９）アイゾット（ＩＺＯＤ）衝撃強度（ｋｇｆｃｍ／ｃｍ）
ＡＳＴＭ Ｄ２５６により常温（２３℃）および低温（−２０℃）で測定した。
（１０）引張強度（Ｔｅｎｓｉｌｅ ｔｅｓｔ）
ＡＳＴＭ Ｄ６３８方法により測定した。
Evaluation method (1) Melt index (Melt index, g / 10 min)
Measurement was performed under conditions of 230 ° C. and 2.16 kg according to ASTM D1238.
(2) Ethylene-propylene copolymer rubber xylene extract (Xylene Soluble, XS,% by weight)
The propylene-based mixed resin was dissolved in xylene at a concentration of 1% at 140 ° C. for 1 hour, extracted after 2 hours at room temperature, and its weight was measured, and expressed as a percentage of the total weight of the propylene-based mixed resin.
(3) Ratio of ethylene-propylene copolymer and ethylene content (Xylene Solid / Ethylene, XS / C2, wt% / wt%)
It is the ratio of the ethylene content measured using the percentage of the total weight of the component extracted by dissolving 1% -concentration propylene-based mixed resin in xylene and the characteristic peaks at 720 and 740 cm −1 of the infrared absorption spectrum.
(4) Intrinsic Viscosity Ratio (IV ratio, Intrinsic Viscosity ratio)
The ethylene-propylene copolymer and homopolypropylene extracted by dissolving in xylene were measured using an intrinsic viscometer, and the ratio was expressed.
(5) Ethylene content of ethylene-propylene copolymer (Ethylene-Propylene rubber, EPR-C2, mol%)
The ethylene content relative to the ethylene-propylene copolymer obtained by xylene extraction was measured using the infrared absorption spectrum and the characteristic peaks of 720 and 740 cm −1 to measure the ethylene content.
(6) Glossiness (Gloss (60 °),%)
The amount of reflected light was measured at an angle of 60 ° by the ASTM D523 method.
(7) Poor appearance of flow mark Poor appearance of the flow mark was evaluated using the injection machine (LG LGH140N) through a spiral flow mold having a thickness of 1.5 mm and a width of 3 cm and evaluated with the naked eye.
(8) Flexural modulus (kgf / cm 2 )
Measured by ASTM D790 method.
(9) Izod (IZOD) impact strength (kgfcm / cm)
Measurement was performed at normal temperature (23 ° C.) and low temperature (−20 ° C.) by ASTM D256.
(10) Tensile test
Measured by ASTM D638 method.
表１〜３に示した通り、実施例１〜３と比較例１〜３との結果を比較したとき、実施例１〜３においてはエチレン−プロピレン共重合体とエチレン含有量の比が低くなることによって光沢度（Ｇｌｏｓｓ、６０°）が低下することが分かる。また、実施例１〜３においてはエチレン−プロピレン共重合体のエチレン含有量が比較例１〜３より高くなるが、屈曲強度（ＦＭ、Ｆｌｅｘｕｒａｌ Ｍｏｄｕｌｕｓ）は比較例１〜３と比較したとき、大きな差はない。また、アイゾット衝撃強度においても常温と低温（−２０℃）での衝撃強度がほとんど同様に維持されることが確認できた。 As shown in Tables 1 to 3, when the results of Examples 1 to 3 and Comparative Examples 1 to 3 were compared, the ratio of the ethylene-propylene copolymer and the ethylene content in Examples 1 to 3 was low. It can be seen that the glossiness (Gloss, 60 °) decreases. Moreover, in Examples 1-3, although ethylene content of an ethylene-propylene copolymer becomes higher than Comparative Examples 1-3, bending strength (FM, Flexural Modulus) is large when compared with Comparative Examples 1-3. There is no difference. It was also confirmed that the impact strength at normal temperature and low temperature (−20 ° C.) was maintained almost the same in terms of Izod impact strength.
引張物性においても降伏点引張強度（Ｔｅｎｓｉｌｅ Ｓｔｒｅｎｇｔｈ ａｔ Ｙｉｅｌｄ）とモジュラス（Ｍｏｄｕｌｕｓ）値が比較例１〜３と比較したとき、大きな差はなかったが、伸び率低下が観察された。 Also in the tensile properties, when the tensile strength at yield and the modulus value were not significantly different from those of Comparative Examples 1 to 3, a decrease in elongation was observed.
光沢性に関連して、実施例１〜３の機械的物性を比較例１〜３と比較したとき、大きな差はなかったにもかかわらず、表面光沢度（Ｇｌｏｓｓ、６０°）においてそれぞれ５７、５９、６１％で表して比較例１〜３に比べて最大３２％の光沢度が低くなる結果が得られる。 In relation to glossiness, when the mechanical properties of Examples 1 to 3 were compared with Comparative Examples 1 to 3, the surface glossiness (Gloss, 60 °) was 57, respectively, although there was no significant difference. As a result, the glossiness is reduced by up to 32% as compared with Comparative Examples 1 to 3 in terms of 59 and 61%.
本発明はホモポリプロピレン重合体およびエチレン−プロピレンゴム成分を含む低光沢およびフローマークの外観不良が抑制されたポリプロピレン樹脂組成物を提供し、前記ポリプロピレン樹脂組成物は光沢性が低く外観に優れ、剛性、衝撃特性などに優れたプラスチック成形品を提供することができる。 The present invention provides a polypropylene resin composition comprising a homopolypropylene polymer and an ethylene-propylene rubber component and having a low gloss and a poor appearance of a flow mark, wherein the polypropylene resin composition has a low gloss and an excellent appearance and is rigid. In addition, it is possible to provide a plastic molded article having excellent impact characteristics.
Claims (12)
前記エチレン−プロピレンブロック共重合体はホモポリプロピレン重合体とエチレン−プロピレン共重合体とからなり、
前記ポリプロピレン樹脂組成物を１４０℃において１重量％でキシレンに溶かして抽出した成分の含有量（重量％）と、赤外線吸収スペクトルの７２０ｃｍ−１、７４０ｃｍ−１の特性ピークを利用して測定したエチレン含有量（重量％）との比は、０．５〜２．０であり、
前記エチレン−プロピレンブロック共重合体の溶融指数はＡＳＴＭ Ｄ１２３８の２３０℃、２．１６ｋｇで５〜３０ｇ／１０分であり、キシレン可溶部とプロピレン単独重合体の固有粘度比（ηＸＳ／ηｈｏｍｏＰＰ）は３〜８であることを特徴とするポリプロピレン樹脂組成物。 In a polypropylene resin composition containing an ethylene-propylene block copolymer,
The ethylene-propylene block copolymer comprises a homopolypropylene polymer and an ethylene-propylene copolymer,
Ethylene wherein the content of the polypropylene resin composition was extracted by dissolving in xylene at 1 wt% at 140 ° C. Component (weight%), infrared absorption spectra of the 720 cm -1, was measured using the characteristic peaks of 740 cm -1 Ratio with content (weight%) is 0.5-2.0,
The melt index of the ethylene-propylene block copolymer is 5 to 30 g / 10 min at 230 ° C. and 2.16 kg of ASTM D1238, and the intrinsic viscosity ratio (ηXS / ηhomoPP) of the xylene-soluble part and the propylene homopolymer is A polypropylene resin composition, which is 3 to 8.
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