JPH03115342A - Polypropylene resin composition - Google Patents
Polypropylene resin compositionInfo
- Publication number
- JPH03115342A JPH03115342A JP25047389A JP25047389A JPH03115342A JP H03115342 A JPH03115342 A JP H03115342A JP 25047389 A JP25047389 A JP 25047389A JP 25047389 A JP25047389 A JP 25047389A JP H03115342 A JPH03115342 A JP H03115342A
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene resin
- ethylene
- copolymer
- resin
- pref
- 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
- -1 Polypropylene Polymers 0.000 title claims abstract description 38
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 32
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 32
- 239000011342 resin composition Substances 0.000 title claims description 22
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 17
- 229920000098 polyolefin Polymers 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 11
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 31
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 3
- 101150014588 ethA gene Proteins 0.000 abstract 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 16
- 239000005977 Ethylene Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 14
- 239000004952 Polyamide Substances 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 229920001384 propylene homopolymer Polymers 0.000 description 9
- 239000008188 pellet Substances 0.000 description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N fumaric acid group Chemical group C(\C=C\C(=O)O)(=O)O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 2
- 229920000577 Nylon 6/66 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229920012753 Ethylene Ionomers Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 229920000393 Nylon 6/6T Polymers 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical group CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229920003182 Surlyn® Polymers 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
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000232 polyglycine polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001567 vinyl ester resin Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はポリプロピレン樹脂組成物に関し、詳しくはポ
リプロピレン樹脂組成物とポリアミド樹脂のそれぞれの
優れた特性を併せ有し、耐熱性、特に高温雰囲気下にお
ける耐熱剛性に優れ、自動車部品やＯＡ機器部品等に適
したポリプロピレン樹脂組成物に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polypropylene resin composition, and more specifically, it has both the excellent properties of a polypropylene resin composition and a polyamide resin, and has excellent heat resistance, especially in a high temperature atmosphere. The present invention relates to a polypropylene resin composition that has excellent heat resistance and rigidity and is suitable for automobile parts, OA equipment parts, etc.
〔従来の技術及び発明が解決しようとする課題〕−ａに
、ポリプロピレン樹脂は、比較的安価で実用上吸水性を
ほとんど示さず軟質である等の良好な特性を有するため
、広範な分野で使用されている。しかしながら、耐熱性
、特に高温雰囲気下、例えば１５０〜１８０ ’Ｃ程度
における形状保持性（耐熱剛性）は、ポリプロピレン樹
脂の融点近傍であるため一般に不充分な場合が多い。そ
のため、耐熱性が要求される分野、具体的には塗装工程
で１５０〜１７０°Ｃ程度の焼付温度の必要な自動車外
装部品等への応用が制約されていた。[Prior art and problems to be solved by the invention]-a. Polypropylene resin is relatively inexpensive and has good properties such as being soft with almost no water absorption in practical use, so it is used in a wide range of fields. has been done. However, heat resistance, particularly shape retention (heat resistance rigidity) under a high temperature atmosphere, for example, around 150 to 180'C, is generally insufficient in many cases because it is near the melting point of polypropylene resin. Therefore, its application to fields where heat resistance is required, specifically, automotive exterior parts that require a baking temperature of about 150 to 170°C during the painting process, has been restricted.
従来、このような特性を改良するため、各種フィラーの
充填、樹脂部分の架橋、高耐熱性の他の樹脂とのブレン
ド等が行われている。しかし、このようにして得られる
樹脂組成物は満足できる程度に耐熱性が改善されなかっ
たり、ある程度効果を発揮するものでも他の特性例えば
剛性、成形加工性などを著しく阻害したり、あるいは大
幅な価格の上昇を招くなどの問題があり、実用に供しえ
ない場合が多かった。Conventionally, in order to improve such properties, filling of various fillers, crosslinking of the resin portion, blending with other highly heat resistant resins, etc. have been carried out. However, the heat resistance of the resin compositions obtained in this way is not improved to a satisfactory extent, and even if they are effective to some extent, other properties such as rigidity and moldability are significantly impaired, or they are significantly impaired. There were problems such as an increase in price, and there were many cases where it could not be put into practical use.
そこで本発明者らは、ポリプロピレン樹脂の有する特性
を損なうことなく、耐熱性、特に高温雰囲気下における
耐熱剛性の優れた樹脂組成物を開発すべく鋭意研究した
結果、ポリプロピレン樹脂に該ポリプロピレン樹脂と一
定の関係にあるポリアミド樹脂及び変成ポリオレフィン
を配合するこにより、目的とする樹脂組成物が得られる
ことを見出した。本発明はかかる知見に基いて完成した
ものである。Therefore, the present inventors conducted extensive research to develop a resin composition with excellent heat resistance, especially heat-resistant rigidity under high-temperature atmospheres, without impairing the properties of polypropylene resin. It has been discovered that the desired resin composition can be obtained by blending a polyamide resin and a modified polyolefin that have the following relationship. The present invention was completed based on this knowledge.
すなわち、本発明は（Ａ）ポリプロピレン樹脂９４〜５
０重量％、（Ｂ）変性ポリオレフィン１〜４０重量％及
び（Ｃ）ポリアミド樹脂５〜４０重量％からなり、かつ
成形加工温度、せん断速度１００ｓｅｃ””における前
記（Ａ）ポリプロピレン樹脂の溶融粘度ηｒｒ（ｐｏｉ
ｓｅ）と（Ｃ）ポリアミド樹脂の溶融粘度７７ＰＡ （
ｐｏｔｓｅ）の比が、式（１）％式％（）
を満たすことを特徴とするポリプロピレン樹脂組成物を
提供するものである。That is, the present invention is based on (A) polypropylene resin 94-5.
0% by weight, (B) 1 to 40% by weight of modified polyolefin, and (C) polyamide resin 5 to 40% by weight, and the melt viscosity of the polypropylene resin (A) at a molding temperature and a shear rate of 100 seconds ηrr ( poi
se) and (C) polyamide resin melt viscosity 77PA (
The purpose of the present invention is to provide a polypropylene resin composition characterized in that the ratio of potse) satisfies the formula (1).
本発明において、（Ａ）ポリプロピレン樹脂（以下（Ａ
）成分と記す。）としては、プロピレン単独重合体およ
び／あるいはプロピレン共重合体が用いられる。ここで
プロピレン共重合体としては、プロピレン−エチレン共
重合体、プロピレン−ブテン−１共重合体などがあり、
これらのブロック共重合体やランダム共重合体が用いら
れる。In the present invention, (A) polypropylene resin (hereinafter (A)
) Ingredients. ), a propylene homopolymer and/or a propylene copolymer is used. Here, the propylene copolymer includes propylene-ethylene copolymer, propylene-butene-1 copolymer, etc.
These block copolymers and random copolymers are used.
なお、このポリプロピレン樹脂は、プロピレン単独重合
体やプロピレン共重合体を一種類で使用してもよく、あ
るいは二種類以上併用することもできる。この際プロピ
レン単独重合体、プロピレン共重合体の分子量は、特に
制限されないが、一般にはメルトフローレート（ＭＦＲ
）が０．０１〜５０ｇ／１０分のものが好適に使用され
る。In addition, for this polypropylene resin, a propylene homopolymer or a propylene copolymer may be used alone, or two or more types may be used in combination. At this time, the molecular weight of the propylene homopolymer and propylene copolymer is not particularly limited, but generally the melt flow rate (MFR
) of 0.01 to 50 g/10 min is preferably used.
次に本発明における（Ｂ）変性ポリオレフィン（以下（
Ｂ）成分と記す。）としては、カルボン酸基（酢酸基、
アクリル酸基、メタクリル酸基。Next, (B) modified polyolefin in the present invention (hereinafter ((
B) Indicated as component. ) as carboxylic acid group (acetate group,
Acrylic acid group, methacrylic acid group.
フマル酸基、イタコン酸基など） カルボン酸金属塩基
（ナトリウム塩、カルシウム塩、マグネシウム塩、亜鉛
塩など）、カルボン酸エステル基（メチルエステル基、
エチルエステル基、プロピルエステル基、ブチルエステ
ル基、ビニルエステル基など）、酸無水物基（無水マレ
イン酸基など）およびエポキシ基から選ばれた少なくと
も一種の官能基を有するポリオレフィンである。またこ
のポリオレフィンとしては、ポリエチレン、ポリプロピ
レン、ポリブテン、エチレン／プロピレン共重合体、エ
チレン／ブテン共重合体、エチレン／ヘキセン共重合体
さらにはこれらに少量のジエンを含む共重合体などをあ
げることができる。fumaric acid group, itaconic acid group, etc.), carboxylic acid metal bases (sodium salt, calcium salt, magnesium salt, zinc salt, etc.), carboxylic acid ester group (methyl ester group,
It is a polyolefin having at least one functional group selected from ethyl ester group, propyl ester group, butyl ester group, vinyl ester group, etc.), acid anhydride group (maleic anhydride group, etc.), and epoxy group. Examples of the polyolefin include polyethylene, polypropylene, polybutene, ethylene/propylene copolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and copolymers containing a small amount of diene. .
このような変性ポリオレフィンの具体例としては、エチ
レン／アクリル酸共重合体、エチレン／メタクリル酸共
重合体、エチレン／フマル酸共重合体、エチレン／メタ
クリル酸／メタクリル酸亜鉛共重合体、エチレン／アク
リル酸／メタクリル酸ナトリウム共重合体、エチレン／
アクリル酸イソブチル／メタクリル酸／メタクリル酸亜
鉛共重合体、エチレン／メタクリル酸メチル／メタクリ
ル酸／メタクリル酸マグネシウム共重合体、エチレン／
アクリル酸エチル共重合体、エチレン／酢酸ビニル共重
合体、エチレン／メタクリル酸グリシジル共重合体、エ
チレン／酢酸ビニル／メタクリル酸グリシジル共重合体
、無水マレイン酸グラフトポリエチレン、アクリル酸グ
ラフトポリエチレン、無水マレイン酸グラフトポリプロ
ピレン。Specific examples of such modified polyolefins include ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/fumaric acid copolymer, ethylene/methacrylic acid/zinc methacrylate copolymer, and ethylene/acrylic acid copolymer. Acid/sodium methacrylate copolymer, ethylene/
Isobutyl acrylate/methacrylic acid/zinc methacrylate copolymer, ethylene/methyl methacrylate/methacrylic acid/magnesium methacrylate copolymer, ethylene/
Ethyl acrylate copolymer, ethylene/vinyl acetate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, maleic anhydride Grafted polypropylene.
無水マレイン酸クラフトエチレン／プロピレン共重合体
、アクリル酸グラフトエチレン／プロピレン共重合体、
フマル酸グラフトエチレン／１−ブデン共重合体、エチ
レン／１−ヘキセン−イタコンＭ共重合体、エチレン／
プロピレン−エンドビシクロ（２，２，１）−５−へブ
テン−２，３−無水ジカルボン酸共重合体、エチレン／
プロピレン−メタクリル酸グラフトグリシジル共重合体
。Maleic anhydride kraft ethylene/propylene copolymer, acrylic acid grafted ethylene/propylene copolymer,
Fumaric acid grafted ethylene/1-butene copolymer, ethylene/1-hexene-itacone M copolymer, ethylene/
Propylene-endobicyclo(2,2,1)-5-hebutene-2,3-dicarboxylic anhydride copolymer, ethylene/
Propylene-grafted glycidyl methacrylate copolymer.
無水マレイン酸グラフトエチレン／プロピレン／１．４
−へキサジエン共重合体、フマル酸グラフトエチレン／
プロピレン／ジシクロペンタジェン共重合体、マレイン
酸グラフトエチレン／プロピレン／ノルボルナジェン共
重合体およびアクリル酸グラフトエチレン／酢酸ビニル
共重合体などであり、これらの変性ポリオレフィンを単
独で使用してもよく、また二種以上を併用することも可
能である。Maleic anhydride grafted ethylene/propylene/1.4
-Hexadiene copolymer, fumaric acid grafted ethylene/
These modified polyolefins include propylene/dicyclopentadiene copolymer, maleic acid grafted ethylene/propylene/norbornadiene copolymer, and acrylic acid grafted ethylene/vinyl acetate copolymer, and these modified polyolefins may be used alone, or It is also possible to use two or more types together.
上記変性ポリオレフィンの製造は公知の方法、例えば特
公昭３９−６８１０号公報、特公昭４６−２７５２７号
公報、特公昭５０−２６３０号公報、特公昭５２−４３
６７７号公報、特公昭５３−５７１６号公報、特公昭５
３−１９０３７号公報１特公昭５３−４１１７３号公報
、特公昭５６−９９２５号公報などに示された方法に従
って製造することができる。なお、エチレン系アイオノ
マーについては一般に“サーリン”、“ハイミラン°”
、“′コーポレン゛′なる商品名で市販されている各種
グレードを用いることができる。また、本発明で用いら
れる変性ポリオレフィンの重合度は特に制限はないが、
通常メルトインデックスが０．０１〜１００ｇ／１０分
の範囲内にあるものを任意に選択できる。The above-mentioned modified polyolefin can be produced by known methods, for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 46-27527, Japanese Patent Publication No. 50-2630, Japanese Patent Publication No. 52-43.
Publication No. 677, Special Publication No. 53-5716, Special Publication No. 577
It can be produced according to the methods disclosed in Japanese Patent Publication No. 3-19037, Japanese Patent Publication No. 53-41173, Japanese Patent Publication No. 56-9925, and the like. Regarding ethylene ionomers, “Surlyn” and “Himilan°” are generally used.
, various grades commercially available under the trade name 'Corpolene' can be used.Also, there is no particular restriction on the degree of polymerization of the modified polyolefin used in the present invention, but
Generally, one having a melt index within the range of 0.01 to 100 g/10 minutes can be arbitrarily selected.
さらに 本発明に用いる（Ｃ）ポリアミド樹脂（以下（
Ｃ）成分と記す、）としては各種のものが使用可能であ
るが、具体的にはナイロン６、ナイロン１１．ナイロン
１２などのポリラクタム類；ナイロン６６、ナイロン６
１０．ナイロン６エ２゜ナイロン４６等のジカルボン酸
とジアミンとから得られるポリアミド類；ナイロン６／
６６、ナイロン６／１２．ナイロン６／６６／６１０等
の共重合体ポリアミド類；ナイロン６／６Ｔ（Ｔ：テレ
フタル酸成分）、イソフタル酸のような芳香族ジカルボ
ン酸とメタキシレンジアミンあるいは脂環族ジアミンか
ら得られる半芳香族ポリアミド類；ポリエステルアミド
、ポリエーテルアミド及びポリエステルエーテルアミド
を挙げることができる。Furthermore, (C) polyamide resin used in the present invention (hereinafter ((
Various materials can be used as component C), specifically nylon 6, nylon 11. Polylactams such as nylon 12; nylon 66, nylon 6
10. Polyamides obtained from dicarboxylic acids and diamines such as nylon 6/2゜nylon 46; nylon 6/
66, nylon 6/12. Copolymer polyamides such as nylon 6/66/610; nylon 6/6T (T: terephthalic acid component), semi-aromatics obtained from aromatic dicarboxylic acids such as isophthalic acid and metaxylene diamine or alicyclic diamine Polyamides; mention may be made of polyesteramides, polyetheramides and polyesteretheramides.
なお、（Ｃ）成分のポリアミド樹脂としては、上記各種
のポリアミドを単独で用いてもよく、また二種以上のポ
リアミドを併用することもできる。In addition, as the polyamide resin of the component (C), the above-mentioned various polyamides may be used alone, or two or more types of polyamides may be used in combination.
さらに、本発明において使用できる（Ｃ）成分のポリア
ミド樹脂は、上述のポリアミドより選択されたものであ
れば、これらのポリアミドの末端基の種類や濃度および
分子量などにより制限されることなく種々のものを使用
することができるが、とりわけ高アミノ末端ポリアミド
が好ましい。また、ポリアミドの重合時に残存または生
成する千ツマ−、オリゴマー等の低分子量物が混在して
いるポリアミドも用いることが可能である。Furthermore, the polyamide resin of component (C) that can be used in the present invention is not limited by the type, concentration, molecular weight, etc. of the terminal group of these polyamides, as long as it is selected from the above-mentioned polyamides. can be used, but highly amino-terminated polyamides are particularly preferred. Further, it is also possible to use a polyamide in which low molecular weight substances such as polymers and oligomers that remain or are generated during polymerization of the polyamide are mixed.
本発明の組成物では、（Ａ）〜（Ｃ）成分として、上記
の如き種々のものが使用可能であるが、これらのうち、
（Ａ）成分及び（Ｃ）成分の間では、成形加工温度、せ
ん断速度１００ｓｅｃ”’における（Ａ）成分の溶融粘
度７７ ｒｒ（ｐｏｉｓｅ）及び（Ｃ）成分の溶融粘度
ηｒＡ（ｐｏｉｓｅ）の比率が、式（１゛ηＰＦ／ηＰ
Ａ１１ ・・・ （Ｎ好ましくは
η、７／η２．〉２ ・・・〔ビ〕
を満たすものを組合せて選定することが必要である。こ
こでη１．／η、Ａの値が１以下であると、ポリアミド
樹脂が分散相を形成してしまうため、得られる樹脂組成
物に所望の耐熱剛性を付与することができず、好ましく
ない。なお、−ここで成形加工温度とは、本発明の組成
物を成形して各種の成形品を製造する際の温度であり、
一般には１８０〜３５０°Ｃの範囲である。In the composition of the present invention, various components as described above can be used as components (A) to (C), but among these,
Between component (A) and component (C), the ratio of the melt viscosity of component (A), 77 rr (poise), and the melt viscosity of component (C), ηrA (poise) at the molding temperature and shear rate of 100 sec'' is , formula (1゛ηPF/ηP
A11...(Npreferably η, 7/η2.>2... [B] It is necessary to select a combination of those that satisfy the following.Here, the value of η1./η, A is 1 or less. If this is the case, the polyamide resin will form a dispersed phase, making it impossible to impart the desired heat-resistant rigidity to the resulting resin composition, which is undesirable. It is the temperature when molding the composition to produce various molded products,
Generally it is in the range of 180-350°C.
本発明において、上記（Ａ）、（Ｂ）及び（Ｃ）の三成
分の配合割合は、（Ａ）成分９４〜５０重景％、好まし
くは９０〜５５重量％、（Ｂ）成分１〜４０重量％、好
ましくは３〜３０重量％、（Ｃ）成分５〜４０重量％、
好ましくは１０〜４０重景％である。In the present invention, the blending ratio of the three components (A), (B), and (C) is 94 to 50% by weight of component (A), preferably 90 to 55% by weight, and 1 to 40% by weight of component (B). % by weight, preferably 3 to 30% by weight, component (C) 5 to 40% by weight,
Preferably it is 10 to 40%.
ここで、（Ａ）成分の配合割合が５０重量％未満では、
得られる樹脂組成物が、ポリプロピレン樹脂本来のＱ、
ｐ）を有しないものとなり、９４重盪％を超えて配合
すると、耐熱剛性の改善効果が得られず好ましくない。Here, if the blending ratio of component (A) is less than 50% by weight,
The resulting resin composition has the original Q of polypropylene resin,
p), and if it is blended in an amount exceeding 94% by weight, the effect of improving heat resistance stiffness cannot be obtained, which is not preferable.
また、（Ｂ）成分の配合割合が１重量％未満では、（Ａ
）成分と（Ｃ）成分との相溶性を改善することが不充分
であり、４０重量％を超えて配合しても、配合割合に相
当する効果は小さく、むしろ得られる樹脂組成物の他の
諸物性を低下させてしまう。さらに、（Ｃ）−成分の配
合割合が５重量％未満では、耐熱剛性の改善効果が不充
分であり、また４０重量％を超えて配合すると、（Ａ）
成分の配合割合が低下して、ポリプロピレン樹脂の本来
の特性が見られなくなり好ましくない。Furthermore, if the blending ratio of component (B) is less than 1% by weight, (A
It is insufficient to improve the compatibility between component ) and component (C), and even if the amount exceeds 40% by weight, the effect corresponding to the blending ratio is small, and rather the other components of the resulting resin composition This results in deterioration of various physical properties. Furthermore, if the blending ratio of (C)-component is less than 5% by weight, the effect of improving heat resistance stiffness is insufficient, and if the blending ratio exceeds 40% by weight, (A)
This is not preferable because the blending ratio of the components decreases and the original properties of the polypropylene resin are lost.
本発明の樹脂組成物は、上記の（Ａ）、（Ｂ）及び（Ｃ
）の三成分を主成分とするものであるが、必要により他
の添加剤を上記成分の特性を阻害しない範囲で添加して
もよい。ここで配合できる添加剤としては、染料、Ｒ料
、充填剤、核剤、繊維状物、可塑剤、滑剤、離型剤、カ
ップリング剤発泡剤、耐熱剤、耐候剤、難燃剤、帯電防
止剤。The resin composition of the present invention includes the above (A), (B) and (C).
), but if necessary, other additives may be added as long as they do not impede the properties of the above components. Additives that can be added here include dyes, R materials, fillers, nucleating agents, fibrous materials, plasticizers, lubricants, mold release agents, coupling agents, foaming agents, heat resistant agents, weathering agents, flame retardants, and antistatic agents. agent.
摺動剤等が挙げられる。Examples include sliding agents.
本発明の樹脂組成物は、上記三成分及び必要により添加
する添加剤を所定量配合してなる樹脂組成物である。配
合の順序について特に制限はなく、各成分を順次あるい
は同時に配合してもよい。また重合反応終了後の粉末状
あるいはペレット状の（Ａ）成分に（Ｂ）及び（Ｃ）成
分を配合してもよい。The resin composition of the present invention is a resin composition formed by blending the above three components and additives added as necessary in predetermined amounts. There is no particular restriction on the order of blending, and each component may be blended sequentially or simultaneously. Further, components (B) and (C) may be blended with component (A) in powder or pellet form after the polymerization reaction is completed.
本発明の樹脂組成物は、各成分を前述の配合割合で混合
乃至混練することによって調製するが、その方法として
は、従来知られている溶融混練法が好ましい。混合はバ
ンバリーミキサ−、ヘンシェルミキサー等を用いて行わ
れ、混練機としては一般に単軸または二輪の押出機が用
いられる。溶融混練する際の温度は、成分、配合量等に
より、各成分の溶融が充分進行しかつ分解しない温度を
適宜選定すればよい。通常は１８０〜３５０°Ｃ１好ま
しくは２００〜３００°Ｃの範囲で選定される。The resin composition of the present invention is prepared by mixing or kneading each component in the above-mentioned proportions, and a conventionally known melt-kneading method is preferred. Mixing is carried out using a Banbury mixer, a Henschel mixer, etc., and a single-screw or two-wheel extruder is generally used as the kneader. The temperature during melt-kneading may be appropriately selected depending on the components, blending amounts, etc., at a temperature at which the melting of each component progresses sufficiently and does not decompose. It is usually selected in the range of 180 to 350°C, preferably 200 to 300°C.
得られた樹脂組成物は押出成形、圧縮成形、射出成形等
により任意の形状に成形してパイプ、チューブ等の所望
の樹脂製品とすればよい。さらにその後メツキ、塗装な
どの加工を施すこともできる。The obtained resin composition may be molded into any desired shape by extrusion molding, compression molding, injection molding, etc. to produce desired resin products such as pipes and tubes. Furthermore, processing such as plating and painting can be applied afterwards.
次に、本発明を実施例および比較例に基いてさらに詳し
く説明する。Next, the present invention will be explained in more detail based on Examples and Comparative Examples.
なお、以下の各側において得られたポリアミド樹脂組成
物の各種物性は、次の如き試験方法に基いて測定したも
のである。The various physical properties of the polyamide resin compositions obtained on each side below were measured based on the following test methods.
試眉男Ｊ刈ｐえ汰
試験片は、組成物をスクリューインライン式射出成形機
で成形して作成した。このときのシリンダー温度は２８
０°Ｃ１また、金型温度は６０°Ｃとした。Test pieces were prepared by molding the composition using a screw in-line injection molding machine. The cylinder temperature at this time is 28
0°C1 Also, the mold temperature was 60°C.
耐力１辻目利」友人
ＡＳＴＭ−Ｄ−６４８に準拠し、曲げ応力４．６ｋｇｆ
／ＣＴＡにて、熱変形温度を測定した。According to ASTM-D-648, bending stress 4.6 kgf
The heat distortion temperature was measured at /CTA.
箪敵権度
東洋精器（株）製キャビログラフを用い、設定温度２８
０°Ｃ１せん断速度１００５ｅｃ−’におけるポリプロ
ピレン樹脂の溶融粘度（η１．）及びポリアミド樹脂の
溶融粘度（ηＰＡ）を測定した。Using a cavilograph manufactured by Toyo Seiki Co., Ltd., the temperature was set at 28.
The melt viscosity (η1.) of the polypropylene resin and the melt viscosity (ηPA) of the polyamide resin at a shear rate of 1005 ec-' at 0°C1 were measured.
実施例１〜１１及び比較例１〜４
第１表に示す、ポリプロピレン樹脂、変性ポリオレフィ
ン及びポリアミド樹脂の各々のペレットを第１表に示す
所定量配合し、ヘンシェルミキサーにより５分間乾式混
合した後、得られた混合物をベント付同方向二軸押出機
（内径３０ｍｍ、Ｌ／Ｄ＝１７）にて溶融混練し、ペレ
ットを製造した。Examples 1 to 11 and Comparative Examples 1 to 4 Pellets of each of polypropylene resin, modified polyolefin, and polyamide resin shown in Table 1 were blended in the prescribed amounts shown in Table 1, and after dry mixing for 5 minutes with a Henschel mixer, The resulting mixture was melt-kneaded in a vented co-directional twin-screw extruder (inner diameter 30 mm, L/D=17) to produce pellets.
なお、このペレット作成時の加熱温度は２８０ ’Ｃと
した。Note that the heating temperature at the time of making this pellet was 280'C.
得られたペレットを、減圧下に加熱乾燥した後、射出成
形機を使用して試験片とし、熱変形温度を測定した。結
果を第１表に示す。なお、この第１表には２８０°Ｃ１
せん断速度１００ｓｅｃ伺における上記ポリプロピレン
樹脂とポリアミド樹脂の溶融粘度の比率（η２．／ηＰ
Ａ）を併せて示す。The obtained pellets were heated and dried under reduced pressure, and then made into test pieces using an injection molding machine, and the heat distortion temperature was measured. The results are shown in Table 1. In addition, this Table 1 shows 280°C1
The ratio of melt viscosity of the polypropylene resin and polyamide resin at a shear rate of 100 sec (η2./ηP
A) is also shown.
（以下余白）
１：プロピレン単独重合体、ＪＩＳ Ｋ ６７５Ｂ
でのＭＦＲが０．５ｇ／１０分のプロピレン単独重合体
＊２：プロピレン単独重合体、ＪＩＳ Ｋ ６７５
８でのＭＦＲが３ｇ／１０分のプロピレン単独重合体
＊３：プロピレンブロック共重合体、 ＪＩＳ Ｋ
６７５８でのＭＦＲが０．８ｇ／ＩＯ分のプロピレンブ
ロック共重合体
＊４：プロピレン単独重合体、ＪＩＳ Ｋ ６７５
８でのＭＦＲが３０ｇ／１０分のプロピレン単独重合体
＊５：プロピレンブロック共重合体、 ＪＩＳ Ｋ
６７５８でのＭＦＲが３０ｇ／１０分のプロピレンブロ
ック共重合体
＊６；グラフト変性ポリプロピレン、２３０°ＣのＭＦ
Ｒが１．０ｇ／１０分を有するアイツタクチイックポリ
プロピレンに、無水マレイン酸を０．３５重量％付加し
たグラフト変性ポリプロピレン
＊７：グリシジルメタクリレートグラフト化エチレン−
酢酸ビニル共重合体、特公昭５５−１２４４９号公報記
載の方法を参考にして製造した。即ち、エチレン−酢酸
ビニル共重合体ペレットに、予めジクミルパーオキサイ
ドを溶解したグリシジルメタクリレートを混合し、室温
で浸透させた。次いで、このグリシジルメタクリレート
含浸ペレットを、内径３０ｍｍのベント付同方向二軸押
出機を用いて、先端温度１７０°Ｃで押出し、グラフト
重合したエポキシ基含有共重合体ペレットを得た（グリ
シジルメタクリレート含量２ｗＬ％）。(Left below) 1: Propylene homopolymer, JIS K 675B
Propylene homopolymer with MFR of 0.5 g/10 min *2: Propylene homopolymer, JIS K 675
Propylene homopolymer with MFR of 3 g/10 min at 8 *3: Propylene block copolymer, JIS K
Propylene block copolymer with MFR of 0.8 g/IO at 6758 *4: Propylene homopolymer, JIS K 675
Propylene homopolymer with MFR at 8 of 30 g/10 min *5: Propylene block copolymer, JIS K
Propylene block copolymer with MFR of 30 g/10 min at 6758 *6; graft modified polypropylene, MF at 230°C
Graft-modified polypropylene obtained by adding 0.35% by weight of maleic anhydride to tactical polypropylene having R of 1.0 g/10 minutes *7: Glycidyl methacrylate grafted ethylene-
Vinyl acetate copolymer was produced with reference to the method described in Japanese Patent Publication No. 12449/1983. That is, glycidyl methacrylate in which dicumyl peroxide had been dissolved in advance was mixed with ethylene-vinyl acetate copolymer pellets, and the mixture was allowed to penetrate at room temperature. Next, the glycidyl methacrylate-impregnated pellets were extruded using a co-directional twin-screw extruder with an inner diameter of 30 mm and a vent at a tip temperature of 170°C to obtain graft-polymerized epoxy group-containing copolymer pellets (glycidyl methacrylate content: 2 wL). %).
＊８：ナイロン６６．相対粘度２．８５．アミノ末端基
濃度 ５．２Ｘ１０−’当量／ｇ＊９：ナイロン６６．
相対粘度２．３０．アミノ末端基濃度 ５．１Ｘ１０−
’当量／ｇ＊１０：ナイロン６．相対粘度２．５２．ア
ミノ末端基濃度 ４．９Ｘ１０−’当量／ｇ
〔発明の効果〕
以上説明したように、本発明のポリプロピレン樹脂組成
物は、ポリプロピレン樹脂の優れた特性を維持しつつ、
優れた耐熱性、特に高い耐熱剛性を有するとともに、配
合したポリアミド樹脂の優れた特性を併せ有する樹脂組
成物である。このような本発明の樹脂組成物は、耐熱性
、耐熱剛性等を要求される部品などの素材として特に好
適である。*8: Nylon 66. Relative viscosity 2.85. Amino end group concentration 5.2×10-' equivalent/g*9: Nylon 66.
Relative viscosity 2.30. Amino end group concentration 5.1X10-
'Equivalent weight/g*10: Nylon 6. Relative viscosity 2.52. Amino terminal group concentration 4.9X10-' equivalent/g [Effects of the invention] As explained above, the polypropylene resin composition of the present invention maintains the excellent properties of polypropylene resin, while
This resin composition has excellent heat resistance, particularly high heat-resistant rigidity, and also has the excellent properties of the polyamide resin blended with it. Such a resin composition of the present invention is particularly suitable as a material for parts and the like that require heat resistance, heat-resistant rigidity, and the like.
したがって、本発明のポリプロピレン樹脂組成物は、耐
熱性、耐熱剛性等を要求される部品、例えは自動車部品
、電機器具９機械部品、工業部品などの素材として、幅
広く有効に利用することができる。Therefore, the polypropylene resin composition of the present invention can be widely and effectively used as a material for parts that require heat resistance, heat-resistant rigidity, etc., such as automobile parts, electrical appliances, mechanical parts, and industrial parts.
Claims (1)
Ｂ）変性ポリオレフィン１〜４０重量％及び（Ｃ）ポリ
アミド樹脂５〜４０重量％からなり、かつ成形加工温度
、せん断速度１００ｓｅｃ＾−＾１における前記（Ａ）
ポリプロピレン樹脂の溶融粘度η＿Ｐ＿Ｐ（ｐｏｉｓｅ
）と（Ｃ）ポリアミド樹脂の溶融粘度η＿Ｐ＿Ａ（ｐｏ
ｉｓｅ）の比が、式〔 I 〕 η＿Ｐ＿Ｐ／η＿Ｐ＿Ａ＞１・・・〔 I 〕 を満たすことを特徴とするポリプロピレン樹脂組成物。(1) (A) Polypropylene resin 94-50% by weight, (
B) consisting of 1 to 40% by weight of modified polyolefin and (C) 5 to 40% by weight of polyamide resin, and the above (A) at a molding temperature and a shear rate of 100 sec^-^1
Melt viscosity of polypropylene resin η_P_P (poise
) and (C) the melt viscosity η_P_A(po
A polypropylene resin composition characterized in that the ratio of .ise) satisfies the formula [I] η_P_P/η_P_A>1...[I].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25047389A JPH03115342A (en) | 1989-09-28 | 1989-09-28 | Polypropylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25047389A JPH03115342A (en) | 1989-09-28 | 1989-09-28 | Polypropylene resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03115342A true JPH03115342A (en) | 1991-05-16 |
Family
ID=17208384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25047389A Pending JPH03115342A (en) | 1989-09-28 | 1989-09-28 | Polypropylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03115342A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0753790A (en) * | 1993-08-12 | 1995-02-28 | Tosoh Corp | Resin composition for metallization |
| JPH07179751A (en) * | 1993-10-12 | 1995-07-18 | Elf Atochem Sa | Molding having weld line based on mixture of polyamide and polyolefin |
| US5874176A (en) * | 1994-05-20 | 1999-02-23 | Ube Industries, Ltd. | Resin composite containing polyamide matrix and polyolefine grains dispersed therein |
| US6305691B1 (en) | 1995-04-10 | 2001-10-23 | Nippon Pillar Packing Co., Ltd. | Shaft sealing apparatus |
| KR100422733B1 (en) * | 2001-05-21 | 2004-03-12 | 현대자동차주식회사 | A polypropylene resin composition for a interior the skin material of automobile |
| JP2007177208A (en) * | 2005-08-08 | 2007-07-12 | Mitsubishi Gas Chem Co Inc | Thermoplastic resin composition-molded article excellent in barrier property |
| CN108291085A (en) * | 2015-12-01 | 2018-07-17 | 三井化学株式会社 | High-fluidity polyamide resin combination |
-
1989
- 1989-09-28 JP JP25047389A patent/JPH03115342A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0753790A (en) * | 1993-08-12 | 1995-02-28 | Tosoh Corp | Resin composition for metallization |
| JPH07179751A (en) * | 1993-10-12 | 1995-07-18 | Elf Atochem Sa | Molding having weld line based on mixture of polyamide and polyolefin |
| US5874176A (en) * | 1994-05-20 | 1999-02-23 | Ube Industries, Ltd. | Resin composite containing polyamide matrix and polyolefine grains dispersed therein |
| US6305691B1 (en) | 1995-04-10 | 2001-10-23 | Nippon Pillar Packing Co., Ltd. | Shaft sealing apparatus |
| KR100422733B1 (en) * | 2001-05-21 | 2004-03-12 | 현대자동차주식회사 | A polypropylene resin composition for a interior the skin material of automobile |
| JP2007177208A (en) * | 2005-08-08 | 2007-07-12 | Mitsubishi Gas Chem Co Inc | Thermoplastic resin composition-molded article excellent in barrier property |
| CN108291085A (en) * | 2015-12-01 | 2018-07-17 | 三井化学株式会社 | High-fluidity polyamide resin combination |
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