JPH01271450A - Automobile outside sheet member comprising polyolefin resin composition - Google Patents
Automobile outside sheet member comprising polyolefin resin compositionInfo
- Publication number
- JPH01271450A JPH01271450A JP10017988A JP10017988A JPH01271450A JP H01271450 A JPH01271450 A JP H01271450A JP 10017988 A JP10017988 A JP 10017988A JP 10017988 A JP10017988 A JP 10017988A JP H01271450 A JPH01271450 A JP H01271450A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- resin composition
- weight
- propylene
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 8
- 229920005672 polyolefin resin Polymers 0.000 title abstract 2
- 239000000454 talc Substances 0.000 claims abstract description 15
- 229910052623 talc Inorganic materials 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 229920001971 elastomer Polymers 0.000 claims abstract description 6
- 239000005060 rubber Substances 0.000 claims abstract description 6
- 239000004033 plastic Substances 0.000 claims abstract description 5
- 229920003023 plastic Polymers 0.000 claims abstract description 5
- 229920001400 block copolymer Polymers 0.000 claims abstract description 4
- 239000000155 melt Substances 0.000 claims abstract description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 4
- 230000000704 physical effect Effects 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 229920001038 ethylene copolymer Polymers 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 20
- 235000012222 talc Nutrition 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010332 dry classification Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000010333 wet classification Methods 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010049933 Hypophosphatasia Diseases 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(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 JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 210000003195 fascia Anatomy 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting 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
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は表面外観が優れ、且つ成形加工性および機械的
性質、特に低温衝撃特性に優れ、高度な寸法安定性と塗
装性をあわせもつ剛性に優れた自動車外板部材に関する
ものである。Detailed Description of the Invention (Field of Industrial Application) The present invention has excellent surface appearance, excellent moldability and mechanical properties, especially low-temperature impact properties, and rigidity that combines high dimensional stability and paintability. The present invention relates to an automobile exterior panel member with excellent properties.
（従来の技術）
近年バンバ等の自動車外装部品にポリプロピレン（ＰＰ
）系の樹脂材料の使用が増加してきており、特開昭５８
−２１３０４３号公報、特開昭６０−１８８４５３号公
報および特開昭６１−４３６５０号公報に見られるよう
に、塗装性能の向上および剛性向上の改良も図られてき
ている。(Prior technology) In recent years, polypropylene (PP
) type resin materials have been increasing in use, and
As seen in Japanese Patent Application Laid-open No. 213043, Japanese Patent Application Laid-open No. 60-188453, and Japanese Patent Application Laid-Open No. 61-43650, improvements have been made to improve coating performance and rigidity.
（発明が解決しようとする課題）
しかしこのようなＰＰ系複合材料にあっては配合Ｆ優れ
た外板特性を有するものの、車体同時焼（づけ塗装可能
な剛性及び耐低温衝撃特性を兼備する事は困難であった
。特にアクリルメラミン系の様な硬い塗料に対しては極
度に耐低温衝撃特性が低下する現象が生じていた。その
為、従来においては、ポリフェニレンオキシド（ＰＰＯ
） ／ポリアミド（ＰＡ）系アロイ材を使用し、ており
材料価格も高いものとなるという問題点があった。(Problem to be Solved by the Invention) However, although such PP-based composite materials have excellent properties for the outer skin, they do not have the same rigidity and low-temperature impact resistance that can be applied to the car body at the same time. In particular, for hard paints such as acrylic and melamine paints, there was a phenomenon in which the low-temperature impact resistance deteriorated extremely.Therefore, in the past, polyphenylene oxide (PPO)
)/Polyamide (PA) based alloy material is used, which has the problem of high material cost.
（課題を解決するための手段）
本発明は、特定の結晶性プロピレン・エチレンブロック
共重合体（以下ＥＰＰと略称する）、エチレン・プロピ
レン系共重合ゴム（以下Ｐ、ＰＲと略称する）、タルク
を特定割合で配合した樹脂組成物を用いることにより、
優れた外観、成形加工性、剛性−低温衝撃強度バランス
を発現しつつ、極めて優れた耐熱剛性と塗装性を有する
車体同時焼付塗装可能な自動車外板部材を成形し得るこ
とを見い出したことに基づくものである。(Means for Solving the Problems) The present invention provides a specific crystalline propylene/ethylene block copolymer (hereinafter abbreviated as EPP), ethylene/propylene copolymer rubber (hereinafter abbreviated as P, PR), talc By using a resin composition containing a specific proportion of
Based on the discovery that it is possible to mold an automobile exterior panel member that exhibits an excellent appearance, moldability, rigidity-low-temperature impact strength balance, and has extremely excellent heat-resistant rigidity and paintability and can be baked and painted at the same time as the vehicle body. It is something.
即ち、本発明は、次の成分（ａ）〜（ｃ）（ａ）常温キ
シレン可溶分を５〜１０重量％含み、重合体全体のエチ
レン含量が３−１２モル％で、メルトフロ・・・−・Ｉ
Ｉ−） （１１１Ｐ！？）が１０〜４０ｇ／１０分であ
るプロピレン・エチレンブロック共重合体４８−６５重
重量、
（１））？ＩＦＲが０゜４へ−８，６ｇ／１０分のエチ
レン・プロピレン系共重合体ゴム１４〜２８重量％、（
ｃ）平均粒径が０．２〜２．５μｍのタルク１７〜３５
重量％、
を必須成分として含み、
（１）ヒー トサグ量（厚み３ｍｍ、１４０℃１１時間
）が３ｍｍ以下、
（ＩＩ）高速面衝撃性（厚み３ＩＩ！［［ｌ、衝突速度
２．５ｍ／ｓ）において延性破壊を示し、塑性歪エネル
ギーが１２ジ工−ル以上、
（ＩＩＩ）線膨張係数（厚み３ｆｆ１１１、長さ８０鵬
、２３℃〜８０”Ｃ）が８．’０Ｘ１０−’ （ｃ＋ｎ
／ｅｉ’ｃ ）以下、（■）ＭＦＲが５ｇ／１０分以上
、
（Ｖ）曲げ弾性率（２３℃）が１５．０００ｋｇ ／
ｅが以上の物性を有する樹脂組成物より成形されたこと
を特徴とする自動車外板部材に関するものである。That is, the present invention contains 5 to 10% by weight of the following components (a) to (c) (a) soluble in xylene at room temperature, the ethylene content of the entire polymer is 3 to 12 mol%, and the melt flow... -・I
I-) Propylene-ethylene block copolymer 48-65 weight with (111P!?) of 10-40 g/10 min, (1))? 14-28% by weight of ethylene-propylene copolymer rubber with an IFR of 0°4-8,6g/10min, (
c) Talc 17-35 with an average particle size of 0.2-2.5 μm
(1) heat sag amount (thickness 3 mm, 140°C 11 hours) is 3 mm or less, (II) high-speed surface impact resistance (thickness 3 II![[l, impact speed 2.5 m/s) ) shows ductile fracture, plastic strain energy is 12 or more, (III) coefficient of linear expansion (thickness 3ff111, length 80", 23℃~80"C) is 8.'0X10-' (c+n
/ei'c) or less, (■) MFR is 5g/10 minutes or more, (V) Flexural modulus (23℃) is 15.000kg/
The present invention relates to an automobile outer panel member characterized in that e is molded from a resin composition having the above physical properties.
本発明に用いるＥＰＰは常温キシレン可溶分を５〜ＩＯ
重量％含み、重合体全体のエチレン含量は３〜１２モル
％、好ましくは４〜６モル％で、かつ、そのＭＦＲが１
０〜４０ｇ／１０分、好ましくは２５〜３５ｇ／１０分
のものである。これらの物性以外のＨＰＰは本発明の効
果を奏さない。The EPP used in the present invention has a xylene soluble content at room temperature of 5 to IO.
% by weight, the ethylene content of the entire polymer is 3 to 12 mol%, preferably 4 to 6 mol%, and the MFR is 1
0 to 40 g/10 minutes, preferably 25 to 35 g/10 minutes. HPPs with physical properties other than these do not exhibit the effects of the present invention.
ここでエチレン含量はＮＭＲ法の常法により測定される
値であり、また常温キシレン可溶分は２ｇの試料を沸騰
キシレン６００ｇ中に２０分間浸漬して溶解させた後、
室温まで冷却し、Ｇ４型ガラスフィルターで濾過および
乾燥して求めた固相重量から逆算した値である。Here, the ethylene content is a value measured by a conventional NMR method, and the xylene soluble content at room temperature is determined by immersing 2 g of a sample in 600 g of boiling xylene for 20 minutes to dissolve it.
This value is back calculated from the solid phase weight determined by cooling to room temperature, filtering with a G4 type glass filter, and drying.
この共重合体のエチレン含量、常温キシレン可溶分が上
記範囲外のものは、組成物の高温時における寸法安定性
、塗装性、外観、物性バランスが劣り本発明の組成物成
分として不適当である。If the ethylene content and the xylene soluble content at room temperature of this copolymer are outside the above range, the composition will have poor dimensional stability, paintability, appearance, and physical property balance at high temperatures, and will be unsuitable as a component of the composition of the present invention. be.
また、ＭＦＲはＪＩＳ−Ｋ ７２１０ （２３０℃，２
，１６ｋｇ荷重）により測定した値で、１０ｇ／１０分
未満のものは成形加工性、外観が劣り、４０ｇ／ｉｏ分
超過のものは物性バランスが不良となる。In addition, MFR is JIS-K 7210 (230℃, 2
, 16 kg load), if it is less than 10 g/10 min, the moldability and appearance will be poor, and if it is more than 40 g/io min, the balance of physical properties will be poor.
本発明において（ａ）成分として用いられる共重合体は
、先の性状範囲内であれば２種以上の樹脂の併用混合物
であっても一向に差支えなく、その際、先の性状範囲外
のプロピレン系樹脂を先のＥＰＰＯ量・（重量）を超え
ない範囲で用いることもできる。In the present invention, the copolymer used as component (a) may be a mixture of two or more resins as long as the properties are within the above property range; The resin can also be used within a range that does not exceed the above-mentioned amount of EPPO (weight).
また、このＰＰＰは、本発明の効果を著しく損なわない
範囲で他の不飽和単量体（例えばブテン−１、ヘキセン
−１、オクテン−１，４−メチルペンテン−１等のα−
オレフィン；酢酸ビニルの如きビニルエステル； （メ
タ）アクリル酸（エステル）、無水マレイン酸等の不飽
和有機酸またはその誘導体等）をも含有する共重合体（
グラフト型、ランダム型、ブロック型いずれでも構わな
い）や変性物であってもよい。更にはこれらの混合物で
あってもよい。In addition, this PPP may contain other unsaturated monomers (for example, α-1, hexene-1, octene-1,4-methylpentene-1, etc.) to the extent that the effects of the present invention are not significantly impaired.
Copolymers (olefins; vinyl esters such as vinyl acetate; unsaturated organic acids such as (meth)acrylic acid (ester), maleic anhydride, or derivatives thereof) (
It may be of a graft type, random type, or block type) or a modified product. Furthermore, a mixture of these may be used.
次に本発明で用いる上記（ｂ）成分であるＥＰＲはエチ
レン・プロピレン二元共重合体ゴム（ＥＰＭ）であって
、ＭＦＲが０．４〜８．６ ｇ／１０分が適当である。Next, EPR, which is the component (b) used in the present invention, is an ethylene-propylene binary copolymer rubber (EPM), which has a suitable MFR of 0.4 to 8.6 g/10 minutes.
ここで、ＭＦＲが０．４〜８．６ ｇ／１０分（好まし
くは０．６〜５．０ ｇ／１０分）であれば、そのＥＰ
Ｒは２成分以上の併用であってもよい。例えば、高粘度
品と低粘度品のブレンドであっｔもよ（、その際、粘度
範囲外のものを併用しても差し支えない。Here, if the MFR is 0.4 to 8.6 g/10 min (preferably 0.6 to 5.0 g/10 min), the EP
R may be a combination of two or more components. For example, it may be a blend of a high viscosity product and a low viscosity product (in that case, it is also possible to use products outside the viscosity range in combination).
本発明で用いる上記（ｃ）成分であるタルクは、平均粒
径が０．２〜２．５μ閑のもので、好ましくは比表面積
が３５，０００ｃｍ”／ ｇ以上で、粒度分布が、実質
的に１５μｍ以下であって、粒子寸法１０μｍ以下が９
５％以上、５μｍ以下が８０％以上、１μｍ以下が５〜
５０％であり、平均アスペクト比が５以上のものである
。上記の範囲に入らないものを用いた場合は、組成物の
高温時における寸法安定性が劣る他、剛性と低温衝撃性
とのバランス、塗装性、外観が劣り好ましくない。Talc, which is the component (c) used in the present invention, has an average particle size of 0.2 to 2.5μ, preferably a specific surface area of 35,000 cm”/g or more, and a particle size distribution of substantially The particle size is 15 μm or less, and the particle size is 10 μm or less.
5% or more, 5μm or less is 80% or more, 1μm or less is 5~
50%, and the average aspect ratio is 5 or more. If a composition that does not fall within the above range is used, the composition will have poor dimensional stability at high temperatures, as well as poor balance between rigidity and low-temperature impact resistance, paintability, and appearance, which is undesirable.
ここで比表面積の測定は、常法のいわゆる空気透過法に
基いて恒圧通気式比表面積測定装置、例えば島津製作所
製粉体比表面積測定装置５Ｓ−１００型等で行なう。The specific surface area is measured using a constant pressure aeration type specific surface area measuring device, such as powder specific surface area measuring device 5S-100 manufactured by Shimadzu Corporation, based on the conventional so-called air permeation method.
また、粒度分布の測定は、液相沈降方式の光透過法によ
る積算分布値である。測定装置としては、例として島津
製作新製Ｓ＾−ｃｐ型（例えば５Ａ−Ｃｒ２−２０）が
ある。Further, the particle size distribution is measured by an integrated distribution value by a light transmission method using a liquid phase sedimentation method. As an example of the measuring device, there is a new S^-cp type manufactured by Shimadzu (for example, 5A-Cr2-20).
一方、平均粒径は、粒度分布の測定装置と同じ装置で測
定した粒度の累積分布曲線における５０％の点での粒径
値である。On the other hand, the average particle size is the particle size value at the 50% point in the particle size cumulative distribution curve measured with the same device as the particle size distribution measuring device.
ここで、測定に用いる分散媒は、アルコール３０％程度
の水溶液を用いると、タルクの分散度を高め、測定し易
い。また、平均アスペクト比とはタルクの縦または横の
いずれかの長さと厚みの比の平均値であり、その測定は
顕微鏡にて観察測定する方法による。Here, when the dispersion medium used in the measurement is an aqueous solution containing about 30% alcohol, the degree of dispersion of talc is increased and the measurement is easy. Further, the average aspect ratio is the average value of the ratio of the length and thickness of talc, either vertical or horizontal, and is measured by observation using a microscope.
また、樹脂中に分散しているフィラーの上記諸物性は、
この組成物を有機溶媒で沸点抽出する方法（例えばキシ
レン中１３０〜１４０℃で１０時間程浸漬溶解し、それ
を円筒濾紙を通してタルクと樹脂を分離する方法）また
はこの組成物を焼成する方法等で取り出したフィラーに
ついて上記の方法で求めることができる。In addition, the above physical properties of the filler dispersed in the resin are:
A method of boiling point extraction of this composition with an organic solvent (for example, a method of immersing and dissolving it in xylene at 130 to 140°C for about 10 hours and separating the talc and resin through a thimble filter) or a method of baking this composition, etc. The extracted filler can be determined by the method described above.
平均粒径１．５μｍ以下のタルクは湿式分級で得られ易
く、同０．７μ請以上のタルクは乾式分級で得られ易い
。Talc with an average particle size of 1.5 μm or less is easily obtained by wet classification, and talc with an average particle size of 0.7 μm or more is easily obtained by dry classification.
このようなタルクは、例えば次のような分級方法によっ
て製造される。即ち、タルク原石をチューブミル型粉砕
機、衝撃式粉砕機、ミクロンミル型粉砕機、遠心ローラ
ー型しイモンドミル等の装置で粉砕し、微粉砕を要する
場合には更に、ミクロンミル、ジェット型粉砕機、ジェ
ット・オ・マイザー、ミクロナイザー、ジェットパルペ
ライザー、撹拌摩砕ミル（タワーミル）、振動ミル、コ
ロイドミル等で乾式または湿式微粉砕する。Such talc is produced, for example, by the following classification method. That is, talc raw stone is crushed using equipment such as a tube mill type crusher, impact type crusher, micron mill type crusher, centrifugal roller type Imond mill, etc., and if fine grinding is required, a micron mill or jet type crusher is used. Dry or wet pulverization is performed using a jet-o-mizer, micronizer, jet pulpelizer, stirring mill (tower mill), vibration mill, colloid mill, etc.
次に、これらの粉砕したタルクをサイクロン、マルチロ
ン、ミクロンセパレーター、ミクロプレックス、サイク
ロンエアセパレーター、ウルトラセパレーター、ジェッ
トクロン、タラシフロン、レーキ分級機、ハイドロサイ
クロン、水力分級機、遠心分級機等の装置で、−回又は
複数回繰り返して乾式または湿式分級し、その物性を調
整する。Next, these crushed talcs are processed using equipment such as a cyclone, multilon, micron separator, microplex, cyclone air separator, ultra separator, jetclone, tarasiflon, rake classifier, hydrocyclone, hydraulic classifier, centrifugal classifier, etc. - Dry or wet classification is repeated one or more times to adjust its physical properties.
この際、その原石は中国産、豪州産、米国産等が好まし
いが、とりわけ中国産が好ましい、また、これらのタル
クは各種エステル類やグリコール類、カップリング剤、
脂肪酸やその金属塩類、界面活性剤等で表面処理しても
よく、その処理は性能向上に有効である。In this case, the raw stones are preferably from China, Australia, the United States, etc., but especially those from China are preferred.In addition, these talcs can be used for various esters, glycols, coupling agents, etc.
Surface treatment may be performed with fatty acids, metal salts thereof, surfactants, etc., and such treatment is effective in improving performance.
以上のような（ａ）〜（ｃ）成分の配合割合は、（ａ）
＋ （ｂ） ＋ （ｃ）合計量に対して、それぞれ（
ａ）４８〜６５重量％、好ましくは５０〜６４重量％、
（ｂ） １４〜２８重量％、好ましくは１８〜２５重量
％、（ｃ） １７〜３５重量％、好ましくは１８〜３０
重景％で重量。The blending ratio of components (a) to (c) as described above is (a)
+ (b) + (c) For the total amount, respectively (
a) 48-65% by weight, preferably 50-64% by weight,
(b) 14-28% by weight, preferably 18-25%, (c) 17-35% by weight, preferably 18-30%.
Weight in weighted percentage.
（ａ）成分が４８重重量未満のものは成形性や機械的強
度が不満足であり、一方、６５重量％超過のものは寸法
安定性、剛性が劣り好ましくない。また、（ｂ）成分が
１４重量％未満のものは塗装性や低温衝撃性が劣り、２
８重量％超過のものは剛性や耐傷性が劣り、それぞれ不
適である。また、（ｃ）成分が１７重量％未満のものは
高温時の寸法安定性が大幅に劣るばか剛性が不足し、一
方、３５重量％超過のものは外観、塗装性、成形加工性
、低温衝撃性が劣り好ましくない。If the component (a) is less than 48% by weight, the moldability and mechanical strength are unsatisfactory, while if it exceeds 65% by weight, the dimensional stability and rigidity are unfavorable. In addition, those containing less than 14% by weight of component (b) have poor paintability and low-temperature impact resistance, and
If the content exceeds 8% by weight, the rigidity and scratch resistance will be poor, and these will be unsuitable. In addition, those containing component (c) less than 17% by weight have significantly inferior dimensional stability at high temperatures and insufficient rigidity, while those containing more than 35% by weight have poor appearance, paintability, moldability, and low-temperature impact. It is inferior in quality and undesirable.
本発明で用いる組成物は、上記各成分の外に、本発明の
効果を著しく損なわない範囲で、他の付加的成分を添加
することができる。In addition to the above-mentioned components, other additional components may be added to the composition used in the present invention as long as the effects of the present invention are not significantly impaired.
それらの付加的成分としては、本発明で用いる（ｃ）成
分以外の処理または無処理の無機または有機フィラー、
本発明で用いるＥＰＲ以外のゴノ、またはラテックス成
分、本発明で用いるＥＰＰ以外の熱可塑性樹脂または熱
硬化性樹脂、その他、各種安定剤、顔料、分散剤、架橋
剤、発泡剤、難燃剤、核剤、帯電防止剤、塗装性改良剤
等があるが、付加的成分としての上記フィラーの添加は
、メツキ性、塗装性、接着性、光沢、成形性、タッピン
グ性、混練性、ウェルド強度、耐クリープ性、寸法安定
性、耐熱性等の向上に有効である。なお、炭酸カルシウ
ム、硫酸バリウム、酸化チタン、酸化亜鉛、微粒ガラス
球の添加は、これらの効果の向上が顕著である。These additional components include treated or untreated inorganic or organic fillers other than component (c) used in the present invention;
Gono or latex components other than EPR used in the present invention, thermoplastic resins or thermosetting resins other than EPP used in the present invention, various stabilizers, pigments, dispersants, crosslinking agents, blowing agents, flame retardants, There are nucleating agents, antistatic agents, paintability improvers, etc., but the addition of the above-mentioned fillers as additional ingredients improves plating properties, paintability, adhesion, gloss, moldability, tapping properties, kneading properties, weld strength, Effective in improving creep resistance, dimensional stability, heat resistance, etc. Note that the addition of calcium carbonate, barium sulfate, titanium oxide, zinc oxide, and fine glass spheres significantly improves these effects.
以上の組成を有する本発明で用いる組成物は自動車外板
部材を成形する上で、前記の物性を有することが必要と
される。即ち
（Ｉ）ヒートザブ
ヒートサグ量は第１図に示すように供試体として１２０
Ｘ２５Ｘ ３ ｍｍの試験片２を治具１にて水平に固定
し７（ｌ Ｉ＝ １００ｍｍ） 、加熱直後自重による
試験片先端部の熱垂れ量（変位ρ２ｍｍ）を測定するも
のである。車体同時焼付塗装が可能なためにはヒートサ
グ量が３ｒＩｍ以下であることが必要であり、３Ｉを越
えると車体同時焼付塗装時の変形が著しく自動車外板部
材としての品質を保持できない。The composition used in the present invention having the above composition is required to have the above-mentioned physical properties in order to mold an automobile outer panel member. That is, (I) heat sag amount is 120 for the specimen as shown in Figure 1.
A test piece 2 measuring 25 x 3 mm is fixed horizontally with a jig 1 (l I = 100 mm), and the amount of heat sag (displacement ρ2 mm) at the tip of the test piece due to its own weight is measured immediately after heating. In order to be able to simultaneously bake and paint a car body, it is necessary that the heat sag amount is 3rIm or less, and if it exceeds 3I, the quality of the product as an automobile exterior panel member cannot be maintained.
（ＴＩ）高速面衝撃性
ザポート（穴径５０順）上に固定された１００ Ｘ １
００×３１Ｗｌの試験片に堅忍が一定速度が衝突し、打
抜くのに要したエネルギーを弾性歪エネルギー、塑性歪
エネルギー及び試験片の破壊形態により、材料の特性を
位置づける。(TI) 100 x 1 fixed on high speed surface impact Zaport (hole diameter 50 order)
A specimen of 00×31Wl is collided with a constant speed, and the energy required to punch it out is determined by the elastic strain energy, plastic strain energy, and fracture mode of the specimen to determine the material properties.
自動車夕１板部材（、二は、自動車が使用されるあらゆ
る環境において軽衝突時に破壊しないかあるいは、破壊
しても破片が飛散しないことが要求される。この特性を
満足するには組成物物性として一２０゛Ｃ１２，５ｍ／
ｓの衝突速度で延性破壊を示し塑性歪エネルギー・が１
２ジユール以」二であることが必要である。Automotive plate members (1, 2) are required to not break in the event of a light collision in any environment in which the car is used, or to not scatter fragments even if broken.To satisfy this property, the physical properties of the composition must be As -20゛C12,5m/
It shows ductile fracture at a collision speed of s, and the plastic strain energy is 1.
It is necessary that the amount is 2 joules or more.
（ＤＩ）線膨張係数
ＡＳＴＭ ０６９６−７９に準拠して作製された市販の
石英管式膨張計を用いて長さ８０ｍｍ、幅１０ｍ５、厚
さ３Ｉの試験片の長さの変化を２３℃〜８０℃にわたっ
て測定し、この値を平均して求められるものである。(DI) Coefficient of Linear Expansion Using a commercially available quartz tube dilatometer manufactured in accordance with ASTM 0696-79, the change in length of a test piece with a length of 80 mm, width of 10 m5, and thickness of 3I was measured from 23°C to 80°C. It is determined by measuring over ℃ and averaging these values.
自動車外板部材は金属のフレームに取り付けられるため
環境温度の変化による膨張収縮のズレがあると部品の変
形が生じ品質を著しく損う。膨張率の許容範囲は組成物
の線膨張係数が８．０Ｘ１０−’Ｃ１ｌ ／ ｃｍ ”
Ｃ以下である。Since automobile exterior panel members are attached to metal frames, any deviation in expansion and contraction due to changes in environmental temperature will cause deformation of the parts and significantly impair quality. The permissible range of expansion coefficient is that the linear expansion coefficient of the composition is 8.0X10-'C1l/cm"
C or lower.
（ＩＶ） ＭＦＲ
ＪＩＳ Ｋ７２１０に準拠し、２３０ ”Ｃにおいて測
定されたものである。外観、物性を安定して発現でき且
つ成形加工性を保持するためには５ｇ／１０分以上であ
る必要がある。(IV) MFR Measured at 230"C in accordance with JIS K7210. In order to stably develop appearance and physical properties and maintain moldability, it is necessary to be 5 g/10 minutes or more. .
（Ｖ）曲げ弾性率
ＪＩＳに７２０３に準拠し２３℃において測定されたも
のである。(V) Bending elastic modulus Measured at 23°C in accordance with JIS 7203.
製品の剛性不足は使用者に精神的不安感を与えるととも
に高速走行時のバタツキの原因にもなり品質を著しく損
う。この性能を保持するには組成物物性として１５．０
００ｋｇ ／ ｅが以」二の曲げ弾性率が必要である。Insufficient rigidity of the product not only gives the user a sense of mental anxiety, but also causes flapping during high-speed driving, significantly impairing quality. To maintain this performance, the physical properties of the composition must be 15.0
A flexural modulus of 0.00 kg/e is required.
本発明に用いられる組成物ば、−軸押出機、二軸押出機
、バンバリーミキサ−、ロール、ブラベンダープラスト
グラフ、ニーダ−等の通常の混練機を用いて製造するこ
とができる。通常は押出機等で混練してベレット状のコ
ンパウンド番こした後、成形加工に供するが、特殊な場
合は３成分を直接各種成形機に供給し、成形機で混練し
ながら成形することもできる。また、予めフィラーやＥ
ＰＲを（必要に応じて各種添加剤とともに）高濃度に混
練してマスターバッチとし、それを別途プロピレン重合
体等で希釈しながらブレンドコンパラディングしたり、
成形したりすることもできる。The composition used in the present invention can be produced using a conventional kneading machine such as a screw extruder, twin screw extruder, Banbury mixer, roll, Brabender plastograph, or kneader. Normally, the compound is kneaded in an extruder, etc. to form a pellet-like compound, and then subjected to molding. However, in special cases, the three components can be directly supplied to various molding machines and molded while being kneaded by the molding machine. . Also, filler or E
PR is kneaded to a high concentration (with various additives as necessary) to make a masterbatch, which is then separately diluted with propylene polymer etc. and blended and compounded.
It can also be molded.
本発明の自動車外板部材を前記組成物から成形加工する
方法は限定されるものではなく、押出成形、中空成形、
射出成形、シート成形、熱成形、回転成形、積層成形等
成形法の違いを問わず、成形品において本発明効果は発
揮されるが、中でも射出成形が最も通する。The method of molding the automobile outer panel member of the present invention from the composition is not limited, and includes extrusion molding, blow molding,
The effects of the present invention are exhibited in molded products regardless of the molding method used, such as injection molding, sheet molding, thermoforming, rotary molding, and lamination molding, but injection molding is the most effective among them.
（作用および効果）
このようにして得られた本発明の自動車外板部材は優れ
た耐熱剛性と低温耐衝撃性とを併せ持ち、かつ高い曲げ
弾性率と良好な流れ性と極めて低い線膨張係数を有する
ため、車体同時焼付塗装が可能であり、自動車外板部材
、たとえばバンパー、フェイシャ−等として極めて高度
な適性を有するものである。(Operations and Effects) The automobile outer panel member of the present invention thus obtained has both excellent heat-resistant rigidity and low-temperature impact resistance, and also has a high flexural modulus, good flowability, and an extremely low coefficient of linear expansion. Because of this, it is possible to simultaneously bake and paint the car body, making it highly suitable for use as automobile exterior panel members, such as bumpers, fascia, etc.
（実施例）
以下に本発明を実施例および比較例により具体的に説明
する。(Examples) The present invention will be specifically explained below using Examples and Comparative Examples.
向側において用いた（ａ）成分の８種のＥＰＰの性状を
第１表に示す。また使用した（ｂ）成分のＥＰＲを第２
表に、（ｃ）成分のタルクを第３表に示す。Table 1 shows the properties of the eight types of EPP used as component (a) on the opposite side. In addition, the EPR of the component (b) used was
Table 3 shows the talc of component (c).
１〜５および ヘ １〜１３
第１〜３表に示す各成分を第４表に示すとおり配合し、
その配合物１００重量部にさらにトリス（２，４−ジ−
ｔ−ブチルフェニル）ホスファイ１−０．０８重量部、
テトラキス〔メチレン−３−（３’。1 to 5 and F 1 to 13 Each component shown in Tables 1 to 3 is blended as shown in Table 4,
Tris (2,4-di-
t-butylphenyl) phosphite 1-0.08 parts by weight,
Tetrakis [methylene-3-(3'.
５′−ジーも一ブチルー４′−ヒドロキシフェニル）プ
ロピオネートコメタフ０．１重量部を配合して、混合し
た後、ＦＣＮ二軸混練機にて２３０ ’Ｃで混練造粒し
て組成物を得た。0.1 part by weight of 5'-di-monobutyl-4'-hydroxyphenyl)propionate cometaf was blended and mixed, and then kneaded and granulated at 230'C in an FCN twin-screw kneader to obtain a composition. I got it.
この後、スクリューインライン射出成形機にて２３０℃
で試験片を形成し、そのヒートサグ量、衝撃吸収エネル
ギー、線膨張係数、ＭＦＲ、曲げ弾性率を評価した。After that, it was heated to 230℃ using a screw in-line injection molding machine.
A test piece was formed, and its heat sag amount, impact absorption energy, linear expansion coefficient, MFR, and flexural modulus were evaluated.
その結果、実施例１〜５の組成物は良好な品質バランス
を示した。即ち、車体同時焼付塗装に耐えうる優れた耐
熱剛性を持ち、同時に低温における極めて優れた耐衝撃
性を示し、かつ高い弾性率と極めて低い線膨張係数を持
ち、さらに生産性を損なうことなく成形可能な流れ性を
も兼ね備える。As a result, the compositions of Examples 1 to 5 showed good quality balance. In other words, it has excellent heat-resistant rigidity that can withstand simultaneous baking painting of car bodies, and at the same time exhibits extremely excellent impact resistance at low temperatures. It also has a high modulus of elasticity and an extremely low coefficient of linear expansion, and can be molded without sacrificing productivity. It also has good flowability.
したがってこれらの樹脂組成物より成形された部品は自
動車外板部材として極めて高い品質を保有する。Therefore, parts molded from these resin compositions have extremely high quality as automobile exterior panel members.
一方、比較例１〜１３は品質バランスが不良であった。On the other hand, Comparative Examples 1 to 13 had poor quality balance.
即ち、耐熱剛性が不足であったり、耐衝撃性が低かうた
り、成形性が悪いなどの問題があった。That is, there were problems such as insufficient heat-resistant rigidity, low impact resistance, and poor moldability.
第１表 第２表 （ｂ）成分（ＥＰＲ） 第３表 （ｃ）成分（タルク）Table 1 Table 2 (b) Component (EPR) Table 3 (c) Ingredient (talc)
第１図は本発明に用いる組成物のヒートサグ測定の説明
図である。
１・・・治具
２・・・試験片
特許出願人 日産自動車株式会社
同 出願人 三菱油化株式会社FIG. 1 is an explanatory diagram of heat sag measurement of the composition used in the present invention. 1...Jig 2...Test piece patent applicant Nissan Motor Co., Ltd. Applicant Mitsubishi Yuka Co., Ltd.
Claims (1)
重合体全体のエチレン含有量が３〜１２モル％でメルト
フローレートが１０〜４０ｇ／１０分のプロピレン・エ
チレンブロック共重合体４８〜６５重量％、 （ｂ）メルトフローレートが０．４〜８．６ｇ／１０分
のエチレン・プロピレン系共重合体ゴム１４〜２８重量
％、 （ｃ）平均粒径が０．２〜２．５μｍのタルク１７〜３
５重量％、 を必須成分として含み、 （ I ）ヒートサグ量（厚み３ｍｍ、１４０℃、１時間
）が３ｍｍ以下、 （II）高速面衝撃性（厚み３ｍｍ、衝突速度２．５ｍ／
ｓ）において延性破壊を示し、塑性歪エネルギーが１２
ジュール以上、 （III）線膨張係数（厚み３ｍｍ、長さ８０ｍｍ、２３
℃〜８０℃）が８．０×１０＾−＾５（ｃｍ／ｃｍ℃）
以下、 （IV）メルトフローレートが５ｇ／１０分以上、 （Ｖ）曲げ弾性率（２３℃）が１５，０００ｋｇ／ｃｍ
＾２以上の物性を有する樹脂組成物からなることを特徴
とする自動車外板部材。[Claims] 1. (a) Contains 5 to 10% by weight of xylene soluble at room temperature,
A propylene/ethylene block copolymer with a total polymer ethylene content of 3 to 12 mol% and a melt flow rate of 10 to 40 g/10 min (48 to 65% by weight), (b) a melt flow rate of 0.4 to 8 14-28% by weight of ethylene-propylene copolymer rubber for .6 g/10 minutes, (c) talc 17-3 with an average particle size of 0.2-2.5 μm
(I) heat sag amount (thickness 3mm, 140°C, 1 hour) is 3mm or less, (II) high-speed surface impact resistance (thickness 3mm, impact speed 2.5m/
s) showed ductile fracture, and the plastic strain energy was 12
Joule or more, (III) Coefficient of linear expansion (thickness 3 mm, length 80 mm, 23
℃~80℃) is 8.0 x 10^-^5 (cm/cm℃)
Below, (IV) Melt flow rate is 5 g/10 minutes or more, (V) Flexural modulus (23°C) is 15,000 kg/cm
An automobile exterior panel member comprising a resin composition having physical properties of ^2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10017988A JPH01271450A (en) | 1988-04-25 | 1988-04-25 | Automobile outside sheet member comprising polyolefin resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10017988A JPH01271450A (en) | 1988-04-25 | 1988-04-25 | Automobile outside sheet member comprising polyolefin resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01271450A true JPH01271450A (en) | 1989-10-30 |
Family
ID=14267083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10017988A Pending JPH01271450A (en) | 1988-04-25 | 1988-04-25 | Automobile outside sheet member comprising polyolefin resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01271450A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2246358A (en) * | 1990-06-27 | 1992-01-29 | Nissan Motor | Plastic automotive bumper |
| US5412020A (en) * | 1993-07-28 | 1995-05-02 | Mitsui Petrochemical Industries, Ltd. | Propylene polymer compositions |
| US5591795A (en) * | 1993-06-30 | 1997-01-07 | Mitsui Petrochemical Industries, Ltd. | Polypropylene composition |
| US5856400A (en) * | 1995-12-18 | 1999-01-05 | Ube Industries, Ltd. | Polypropylene resin composition |
| US6710131B2 (en) | 2001-11-07 | 2004-03-23 | Indian Petrochemicals Corporation Limited | Melt processible thermoplastic polyolefin blends for car bumpers and other articles and a process for the preparation thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58111846A (en) * | 1981-12-25 | 1983-07-04 | Ube Ind Ltd | Polypropylene composition |
| JPS61276840A (en) * | 1985-06-01 | 1986-12-06 | Mitsubishi Petrochem Co Ltd | Propylene polymer resin composition |
| JPS6284142A (en) * | 1985-10-08 | 1987-04-17 | Mitsui Toatsu Chem Inc | Polypropylene resin composition |
| JPS6343942A (en) * | 1986-08-12 | 1988-02-25 | Mitsui Petrochem Ind Ltd | Resin composition for automobile bumper |
| JPS6375054A (en) * | 1986-09-19 | 1988-04-05 | Mitsui Toatsu Chem Inc | Polypropylene resin composition |
-
1988
- 1988-04-25 JP JP10017988A patent/JPH01271450A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58111846A (en) * | 1981-12-25 | 1983-07-04 | Ube Ind Ltd | Polypropylene composition |
| JPS61276840A (en) * | 1985-06-01 | 1986-12-06 | Mitsubishi Petrochem Co Ltd | Propylene polymer resin composition |
| JPS6284142A (en) * | 1985-10-08 | 1987-04-17 | Mitsui Toatsu Chem Inc | Polypropylene resin composition |
| JPS6343942A (en) * | 1986-08-12 | 1988-02-25 | Mitsui Petrochem Ind Ltd | Resin composition for automobile bumper |
| JPS6375054A (en) * | 1986-09-19 | 1988-04-05 | Mitsui Toatsu Chem Inc | Polypropylene resin composition |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2246358A (en) * | 1990-06-27 | 1992-01-29 | Nissan Motor | Plastic automotive bumper |
| GB2246358B (en) * | 1990-06-27 | 1993-08-11 | Nissan Motor | Plastic automotive bumper |
| US5266619A (en) * | 1990-06-27 | 1993-11-30 | Nissan Motor Co., Ltd. | Plastic automotive bumper |
| US5591795A (en) * | 1993-06-30 | 1997-01-07 | Mitsui Petrochemical Industries, Ltd. | Polypropylene composition |
| US5412020A (en) * | 1993-07-28 | 1995-05-02 | Mitsui Petrochemical Industries, Ltd. | Propylene polymer compositions |
| US5856400A (en) * | 1995-12-18 | 1999-01-05 | Ube Industries, Ltd. | Polypropylene resin composition |
| US6710131B2 (en) | 2001-11-07 | 2004-03-23 | Indian Petrochemicals Corporation Limited | Melt processible thermoplastic polyolefin blends for car bumpers and other articles and a process for the preparation thereof |
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