JPS62283151A - Molded article of polyamide resin - Google Patents
Molded article of polyamide resinInfo
- Publication number
- JPS62283151A JPS62283151A JP12669686A JP12669686A JPS62283151A JP S62283151 A JPS62283151 A JP S62283151A JP 12669686 A JP12669686 A JP 12669686A JP 12669686 A JP12669686 A JP 12669686A JP S62283151 A JPS62283151 A JP S62283151A
- Authority
- JP
- Japan
- Prior art keywords
- nylon
- halide
- polyamide resin
- molded article
- plasticizer
- 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
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 150000004820 halides Chemical class 0.000 claims abstract description 10
- 229920000299 Nylon 12 Polymers 0.000 claims abstract description 9
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229920000571 Nylon 11 Polymers 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims 1
- 230000006353 environmental stress Effects 0.000 abstract description 7
- 229920001778 nylon Polymers 0.000 abstract description 5
- 239000004677 Nylon Substances 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 4
- -1 gold halide Chemical class 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- VTIMKVIDORQQFA-UHFFFAOYSA-N 2-Ethylhexyl-4-hydroxybenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(O)C=C1 VTIMKVIDORQQFA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 210000004798 organs belonging to the digestive system Anatomy 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は柔軟性を有するポリアミド樹脂成形品に関し、
更に詳しくは特定のポリアミド樹脂と、特定の構造式を
有する可塑剤を混合してなる樹脂組成物より成形され、
金属ハロゲン化物と接触して使用しても物性劣化を生じ
ない成形品に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a flexible polyamide resin molded product,
More specifically, it is molded from a resin composition made by mixing a specific polyamide resin and a plasticizer having a specific structural formula,
This invention relates to a molded article that does not cause deterioration of physical properties even when used in contact with metal halides.
（従来の技術と問題点）
従来ポリアミド樹脂は、機械的、化学的性質に優れてい
るため、エンジニアリングプラスチックとして種々の成
形品に使用されているっ中でもナイロン１１、ナイロン
１２、ナイロン６・１２は、種々の可塑剤を混合するこ
とにより任意の柔軟性を付与することができ、射出成形
、押出成形により成形された成形品は、電気、自動車、
灘械等広範囲な産業分野で利用されている。(Conventional technology and problems) Conventional polyamide resins have excellent mechanical and chemical properties, so among those used in various molded products as engineering plastics, nylon 11, nylon 12, and nylon 6/12 are Any flexibility can be imparted by mixing various plasticizers, and molded products molded by injection molding and extrusion molding can be used for electrical, automobile,
It is used in a wide range of industrial fields such as Nada machinery.
しかしながら、可塑剤を混合することにより柔軟化され
た成形品の中には、本来ナイロン１１、ナイロン１２、
ナイロン６・１２が有する金尼ハロゲン化物による環境
応力亀裂に対する抵抗性が損なわれ、短時間で成形品に
亀裂を生じ、成形品の破Ｗ′Ｊにつながるという問題点
を右する。However, some molded products softened by mixing plasticizers originally contain nylon 11, nylon 12,
This causes the problem that the resistance to environmental stress cracking due to the gold halide of nylon 6/12 is impaired, causing cracks in the molded product in a short period of time, leading to molded product failure W'J.
本発明者はかかる問題点を解決し、柔軟性を有し、なお
かつ］Ｉａ又は■ｂ届金屈元素のハロゲン化物による環
境応力亀裂が少ない成形品を提供する事を目的に、鋭意
検討を行なった結果、特定のポリアミド樹脂と特定の構
造式を有する可塑剤を混合してなる樹脂組成物から成形
された成形品が、該金属ハロゲン化物による環境応力亀
裂の発生が少ない事を発見し、本発明に到達した。The inventors of the present invention have conducted extensive studies with the aim of solving these problems and providing a molded product that is flexible and has fewer environmental stress cracks caused by halides of the metallurgical elements Ia or B. As a result, they discovered that molded products made from resin compositions made by mixing a specific polyamide resin and a plasticizer with a specific structural formula were less likely to develop environmental stress cracks due to the metal halide. The invention has been achieved.
（問題点を解決するための手段）
すなわち、本発明はナイロン１１、ナイロン１２、ナイ
ロン６・１２から選ばれた少なくとも一種以上のポリア
ミド樹脂１００重Ｗ部と、下記一般式よりなる可塑剤５
〜５０ｍｎ部をａ合してなる樹脂組成物より成形され、
かつ周期律表Ｕａ又はＩｂ属の金属元素のハロゲン化物
又は該ハロゲン化物の水溶液と接触して用いられること
を特徴とする柔軟なポリアミド樹脂成形品である。(Means for Solving the Problems) That is, the present invention comprises 100 parts by weight of at least one polyamide resin selected from nylon 11, nylon 12, and nylon 6/12, and a plasticizer 5 having the following general formula.
Molded from a resin composition formed by combining ~50mm part,
The flexible polyamide resin molded article is characterized in that it is used in contact with a halide of a metal element belonging to group Ua or Ib of the periodic table or an aqueous solution of the halide.
Ｒ：ｒＡ素数４〜１０のアルキル基
本発明で用いるポリアミド樹脂は、ナイロン１１、ナイ
ロン１２、ナイロン６・１２であり、それらの一種又は
二種類以上を混合して用いることが出来るが、好ましく
はナイロン１２を使用するのが良い。R: rA Alkyl having a prime number of 4 to 10 Basic polyamide resins used in the invention are nylon 11, nylon 12, and nylon 6/12, and one or more of them can be used as a mixture, but nylon is preferable. It is better to use 12.
本発明で用いる可塑剤は下記の一般式で表わされるもの
で、アルキル基としては、ブチル基、イソブチル基、ヘ
プチル基、オクチル基、２−エチルヘキシル基、イソデ
シル基等を例示する事が出来るが、経済性、可塑化効果
の面から、２−エチルヘキシル基をアルキル基とする可
塑剤２−エチルへキシル−ｐ−とドロキシベンゾエート
が好適に用いられる。The plasticizer used in the present invention is represented by the following general formula, and examples of the alkyl group include butyl group, isobutyl group, heptyl group, octyl group, 2-ethylhexyl group, isodecyl group, etc. From the viewpoint of economy and plasticizing effect, the plasticizers 2-ethylhexyl-p- and droxybenzoate, in which 2-ethylhexyl group is an alkyl group, are preferably used.
○
Ｒ：炭素数４〜１０のアルキル基
該可塑剤の配合ωは、ナイロン１００重量部に対して５
〜５０重口部であるが、好ましくは１０〜２０重恒部で
ある。可塑剤量が５重量部以下であれば充分な柔軟性が
得られず、５０重量部以上であれば金属ハロゲン化物に
よる環境応力亀裂に対する抵抗性が著しく損なわれる。○ R: Alkyl group having 4 to 10 carbon atoms The blending ratio ω of the plasticizer is 5 parts by weight per 100 parts by weight of nylon.
~50 parts, preferably 10 to 20 parts. If the amount of plasticizer is less than 5 parts by weight, sufficient flexibility will not be obtained, and if it is more than 50 parts by weight, resistance to environmental stress cracking caused by metal halides will be significantly impaired.
本発明における周期律表［ａ又はＩＩｂ属の金属元素と
は、Ｃａ、ｌｎに代表される金属であり、これら金属の
ハロゲン化物としてはＣａＣＩ２、ｚｎｃ ｌ 、Ｚ
ｎＢｒ 、Ｚｎ １２等を例示することが出来る。The metal elements in group a or IIb of the periodic table in the present invention are metals represented by Ca and ln, and halides of these metals include CaCI2, zncl, and Z
Examples include nBr, Zn 12, etc.
本発明における成形品とは、熱可塑性樹脂に対して通常
一般に用いられる成形手法、例えば射出成形、押出成形
、プレス成形、ブロー成形等の方法で得られる成形品又
は該成形品を切削又は接着等を行なうことにより得られ
る二次加工品を言う。The molded product in the present invention refers to a molded product obtained by a molding method commonly used for thermoplastic resins, such as injection molding, extrusion molding, press molding, blow molding, etc., or a molded product obtained by cutting or gluing the molded product. Refers to secondary processed products obtained by performing
又本発明で用いる樹脂組成物に、酸化防止剤、紫外線吸
収剤等の安定剤、ざらにカーボン、芯先チタン等の着色
剤などを必要に応じて添加混合することができることは
いうまでもない。It goes without saying that stabilizers such as antioxidants and ultraviolet absorbers, and colorants such as carbon and titanium can be added to the resin composition used in the present invention as necessary. .
（発明の効果）
この様にして得られるポリアミド樹脂成形品は、柔軟で
かつ周期律表［ａ又は［ｂ属の金瓜元素の金属ハロゲン
化物と接触する用途においても環境応力亀裂を生じる事
が無いので、ＣａＣｌ２又はＺｎＣｌ２と接触する可能
性を有し、柔軟性が要求される自動車用ブレーキチュー
ブ、ヒュエルチューブ、バ４ニュームチューブ又はケー
ブルクランプ等の用途や、内部をＺｎＢｒ２粉末が流通
する消化器用ホース等に好適に用いることが出来る。(Effect of the invention) The polyamide resin molded product obtained in this way is flexible and does not cause environmental stress cracks even when used in contact with metal halides of metal melon elements in group a or group b of the periodic table. Therefore, it is suitable for applications such as automotive brake tubes, fuel tubes, vanium tubes, cable clamps, etc. that have the possibility of coming into contact with CaCl2 or ZnCl2 and require flexibility, and for digestive organs where ZnBr2 powder flows inside. It can be suitably used for hoses, etc.
（実施例） 以下実施例をもって本発明を説明する。(Example) The present invention will be explained below with reference to Examples.
実施例１〜５
ダイセルヒュルス社製ナイロン１２ Ｌ−２１４０と
可塑剤２−エチルへキシル−ｐ−ヒドロキシベンゾエー
トを、中央機械製ＡＳ３０ａ＋ｍφ二軸押出殿で況合し
、均一なベレットを１ｑた。得られたポリアミド組成物
を割出成形践を用い、物性より定用試哉片に成形し、諸
物性をｉＪ、！Ｉ定した。Examples 1 to 5 Nylon 12 L-2140 manufactured by Daicel Huls and plasticizer 2-ethylhexyl-p-hydroxybenzoate were combined in an AS30a+mφ twin-screw extrusion chamber manufactured by Chuo Kikai to form 1 q of uniform pellets. The obtained polyamide composition was molded into regular test pieces using index molding technique, and the physical properties were determined as iJ,! I decided.
環境応力亀裂の評価は、Ａ Ｓ Ｔ ＨＤタイプＩ引張
グンベル（厚み１７８インチ）の平行部分を半径３Ｍの
半円状に折り曲げ、各今風ハロゲン化物の飽和溶液８０
℃中に浸漬し、クラックの発生時間を１１定することに
より行なった。結果を表−１に示す。Environmental stress cracking was evaluated by bending the parallel parts of A S T HD Type I tensile Gumbel (178 inches thick) into a semicircular shape with a radius of 3M and applying a saturated solution of each modern halide at 80%
The test was carried out by immersing the sample in a temperature of 11° C. and setting the crack generation time for 11 days. The results are shown in Table-1.
実施例６
実施例１において、ポリアミド樹脂ダイアミドＬ−２１
４０にかえて、東し■販売ナイロン１１ ＢＥＳＮＯ
ＴＬを使用すること以外は実施例１と同様に試験を行な
った。結果を表−１に示す。Example 6 In Example 1, polyamide resin Diamide L-21
Instead of 40, east ■Sale nylon 11 BESNO
The test was conducted in the same manner as in Example 1 except that TL was used. The results are shown in Table-1.
比較例１
ダイセルヒュルス製Ｌ−２１４０と東し＠Ｉ製製型塑剤
ベンゼンスルホンブチルアミド混合し、実施例１と同様
の試験を行なった。結果を表−１に示す。Comparative Example 1 The same test as in Example 1 was conducted by mixing L-2140 manufactured by Daicel Huels and benzenesulfone butyramide, a mold-making plastic manufactured by Toshi@I. The results are shown in Table-1.
比較例２
比較例１において、ポリアミド樹脂をナイロン１２
Ｌ−２１４０にかえて、東し四販売ナイロン１１８ＥＳ
ＮＯ丁りを使用すること以外、比較例１と同様の試υを
行なった。結果を表−１に示す。Comparative Example 2 In Comparative Example 1, the polyamide resin was replaced with nylon 12
Instead of L-2140, use Azuma Shishi nylon 118ES
A test similar to that of Comparative Example 1 was conducted except that NO-grip was used. The results are shown in Table-1.
Claims (1)
ばれた少なくとも一種以上のポリアミド樹脂１００重量
部と下記一般式よりなる可塑剤５〜５０重量部を混合し
てなる樹脂組成物より成形され、かつ周期律表IIａ又は
IIｂ属の金属元素のハロゲン化物又は該ハロゲン化物の
水溶液と接触して用いられることを特徴とする柔軟なポ
リアミド樹脂成形品。 ▲数式、化学式、表等があります▼ Ｒ：炭素数４〜１０のアルキル基[Claims] A resin composition obtained by mixing 100 parts by weight of at least one polyamide resin selected from nylon 11, nylon 12, and nylon 6 and 12 with 5 to 50 parts by weight of a plasticizer having the following general formula. and periodic table IIa or
A flexible polyamide resin molded article, characterized in that it is used in contact with a halide of a metal element of group IIb or an aqueous solution of the halide. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R: Alkyl group with 4 to 10 carbon atoms
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12669686A JPS62283151A (en) | 1986-05-31 | 1986-05-31 | Molded article of polyamide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12669686A JPS62283151A (en) | 1986-05-31 | 1986-05-31 | Molded article of polyamide resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62283151A true JPS62283151A (en) | 1987-12-09 |
Family
ID=14941583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12669686A Pending JPS62283151A (en) | 1986-05-31 | 1986-05-31 | Molded article of polyamide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62283151A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789529A (en) * | 1995-06-13 | 1998-08-04 | Ube Industries, Ltd. | Polyamide resin composition and tubular molding comprising the same |
| WO2009087984A1 (en) | 2008-01-10 | 2009-07-16 | Ube Industries, Ltd. | Polyamide resin molding material and laminate using the same |
| JPWO2017010389A1 (en) * | 2015-07-16 | 2017-07-13 | 三菱瓦斯化学株式会社 | Polyamide resin fiber, method for producing polyamide resin fiber, polyamide resin composition, woven fabric and knitted fabric |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5254748A (en) * | 1975-10-30 | 1977-05-04 | Toray Ind Inc | Melt molded products of polyamide |
| JPS57168940A (en) * | 1981-04-13 | 1982-10-18 | Toray Ind Inc | Underhood component for automobile use |
-
1986
- 1986-05-31 JP JP12669686A patent/JPS62283151A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5254748A (en) * | 1975-10-30 | 1977-05-04 | Toray Ind Inc | Melt molded products of polyamide |
| JPS57168940A (en) * | 1981-04-13 | 1982-10-18 | Toray Ind Inc | Underhood component for automobile use |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789529A (en) * | 1995-06-13 | 1998-08-04 | Ube Industries, Ltd. | Polyamide resin composition and tubular molding comprising the same |
| WO2009087984A1 (en) | 2008-01-10 | 2009-07-16 | Ube Industries, Ltd. | Polyamide resin molding material and laminate using the same |
| EP2581414A1 (en) | 2008-01-10 | 2013-04-17 | Ube Industries, Ltd. | Polyamide resin molding material and laminate using the same |
| JPWO2017010389A1 (en) * | 2015-07-16 | 2017-07-13 | 三菱瓦斯化学株式会社 | Polyamide resin fiber, method for producing polyamide resin fiber, polyamide resin composition, woven fabric and knitted fabric |
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