JPH0350262A - Thermoplastic elastomer composition for refrigerant hose - Google Patents
Thermoplastic elastomer composition for refrigerant hoseInfo
- Publication number
- JPH0350262A JPH0350262A JP18578589A JP18578589A JPH0350262A JP H0350262 A JPH0350262 A JP H0350262A JP 18578589 A JP18578589 A JP 18578589A JP 18578589 A JP18578589 A JP 18578589A JP H0350262 A JPH0350262 A JP H0350262A
- Authority
- JP
- Japan
- Prior art keywords
- refrigerant
- polyamide resin
- thermoplastic elastomer
- test
- polymer blend
- 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
- 239000003507 refrigerant Substances 0.000 title claims abstract description 30
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 7
- 239000000203 mixture Substances 0.000 title claims description 10
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 229920002959 polymer blend Polymers 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
- 230000002087 whitening effect Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 238000009864 tensile test Methods 0.000 abstract description 5
- 229920001897 terpolymer Polymers 0.000 abstract description 3
- 229920002292 Nylon 6 Polymers 0.000 abstract description 2
- 229920000800 acrylic rubber Polymers 0.000 abstract 1
- 239000011859 microparticle Substances 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 7
- 238000009863 impact test Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 229920000571 Nylon 11 Polymers 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- 229920000577 Nylon 6/66 Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 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
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 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
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- -1 sodium acid Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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〕
この出願の発明は、耐冷媒透過性、耐熱性、及び低温衝
撃性に優れた冷媒ホース用熱可塑性エラストマー組成物
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The invention of this application relates to a thermoplastic elastomer composition for refrigerant hoses that has excellent refrigerant permeation resistance, heat resistance, and low-temperature impact resistance.
自動車のクーラーやエアコン等に使用される冷媒ホース
用材料には、柔軟性、耐冷媒透過性、耐熱性、及び低温
衝撃性等が要求される。Materials for refrigerant hoses used in automobile coolers, air conditioners, etc. are required to have flexibility, refrigerant permeation resistance, heat resistance, low-temperature impact resistance, etc.
従来、この種の冷媒ホース用材料としては、アクリロニ
トリル−ブタジェンゴム（ＮＢＲ）、ナイロン１１やナ
イロン６／６６等のポリアミド樹脂、及びこれら両者の
ブレンド樹脂等が使用されていた〔発明が解決しようと
する課題〕
しかしながら、上記ＮＢＲでは、柔軟性、及び低温衝撃
性に優れているが、耐冷媒透過性、及び耐熱性について
は不充分であり、またポリアミド樹脂では、耐冷媒透過
性、耐熱性、及び低温衝撃性に優れているが、柔軟性に
ついては不充分であり、さらに両者のブレンド樹脂では
、低温衝撃性に優れると共に、柔軟性、及び耐冷媒透過
性について比較的硬れているが、耐熱性については不充
分であるという課題を有していた。Conventionally, as materials for this type of refrigerant hose, acrylonitrile-butadiene rubber (NBR), polyamide resins such as nylon 11 and nylon 6/66, and blend resins of these two have been used. [Problem] However, although the above NBR has excellent flexibility and low-temperature impact resistance, it is insufficient in refrigerant permeation resistance and heat resistance, and polyamide resin has poor refrigerant permeation resistance, heat resistance, and Although it has excellent low-temperature impact resistance, its flexibility is insufficient.Furthermore, a blend resin of the two has excellent low-temperature impact resistance and is relatively hard in terms of flexibility and refrigerant permeation resistance, but it has poor heat resistance. However, there was a problem in that it was insufficient in terms of gender.
そこで、この出願の発明は、自動車のクーラーやエアコ
ン等に使用される冷媒ホース用材料に要求される上記の
性質の全てに優れたものを提供することを目的としてな
されたものである。Therefore, the invention of this application was made for the purpose of providing a material for refrigerant hoses used in automobile coolers, air conditioners, etc. that is excellent in all of the above-mentioned properties.
そのため、この出願の請求項１記載の発明では、ポリア
ミド樹脂中に官能基を有するエチレン不飽和アクリル酸
アルキルエステル共重合体が分散したポリマーブレンド
であって、常態引張物性における２０％伸長時の強度が
２０〜２００ ｋｇｆ／ｃｆｆｌの範囲内であるものと
している。Therefore, the invention according to claim 1 of this application provides a polymer blend in which an ethylenically unsaturated acrylic acid alkyl ester copolymer having a functional group is dispersed in a polyamide resin, which has strength at 20% elongation in normal tensile properties. is within the range of 20 to 200 kgf/cffl.
さらに、この出願の請求項２記載の発明では、ポリアミ
ド樹脂中に官能基を有するエチレン不飽和アクリル酸ア
ルキルエステル共重合体が架橋して分散したポリマーブ
レンドであって、常態引張物性における２０％伸長時の
強度が２０〜２００ｋｇ ｆ ／ ｃｕｔの範囲内であ
るものとしている。Furthermore, the invention according to claim 2 of this application is a polymer blend in which an ethylenically unsaturated acrylic acid alkyl ester copolymer having a functional group is crosslinked and dispersed in a polyamide resin, and the polymer blend has a 20% elongation in normal tensile properties. The strength at the time is within the range of 20 to 200 kgf/cut.
この出願の発明において使用されるポリアミド樹脂は、
主鎖中にアミド結合−Ｃｏ−ＮＨ−を有する熱可塑性樹
脂であり、ナイロン６、ナイロン１２、ナイロン６．６
、ナイロン１１、ナイロン６．９、ナイロン６．１０、
ナイロン６７６６、ナイロン６６／６１０等を例示する
ことができるが、これらに限定されるものではない。The polyamide resin used in the invention of this application is
A thermoplastic resin with an amide bond -Co-NH- in the main chain, including nylon 6, nylon 12, and nylon 6.6.
, nylon 11, nylon 6.9, nylon 6.10,
Examples include nylon 6766, nylon 66/610, etc., but are not limited to these.
この出願の発明におけるエチレン不飽和アクリル酸アル
キルエステル共重合体としては、エーチレン・アクリル
酸アルキルエステル・無水マレイン酸三元共重合体（Ｅ
ＡＲ） 、エチレン・メタクリル酸アルキルエステル・
無水マレイン酸三元共重合体等を例示することができる
が、これらに限定されるものではない。The ethylene unsaturated acrylic acid alkyl ester copolymer in the invention of this application is an ethylene/acrylic acid alkyl ester/maleic anhydride terpolymer (E
AR), ethylene/methacrylic acid alkyl ester/
Examples include maleic anhydride terpolymer, but are not limited thereto.
この出願の発明における架橋は、熱可塑性樹脂のマトリ
ックス中に他のゴムをブレンドし、混練しながらゴムを
高度に架橋させ、かつその架橋ゴムはマトリックス中に
ミクロに分散させる動的架橋を行うのが好ましい。そし
て、この動的架橋により熱可塑性樹脂のマトリックスは
熱可塑性を示す。Crosslinking in the invention of this application involves dynamic crosslinking in which other rubber is blended into a thermoplastic resin matrix and the rubber is highly crosslinked while being kneaded, and the crosslinked rubber is microdispersed in the matrix. is preferred. Due to this dynamic crosslinking, the thermoplastic resin matrix exhibits thermoplasticity.
この出願の発明において使用される架橋剤としては、亜
鉛華、酸化マグネシウム等の金属酸化物、ステアリン酸
、オレイン酸等の脂肪酸、ジェタノールアミン、ヘキサ
メチレンジアミン等のアミン類、ステアリン酸亜鉛、ス
テアリン酸ナトリウム等の金属塩等を例示することがで
きるが、これらに限定されるものではない。Examples of crosslinking agents used in the invention of this application include metal oxides such as zinc white and magnesium oxide, fatty acids such as stearic acid and oleic acid, amines such as jetanolamine and hexamethylene diamine, zinc stearate, and stearin. Examples include metal salts such as sodium acid, but are not limited thereto.
さらに、この出願の発明におけるポリアミド樹脂と官能
基を存するエチレン不飽和アクリル酸アルキルエステル
共重合体の割合は、柔軟性、耐冷媒透過性、耐熱性の均
衡を取るにはポリアミド樹脂２５〜６５重量部、官能基
を有するエチレン不飽和アクリル酸アルキルエステル共
重合体３５〜７５重量部とするのが好ましい。Furthermore, in the invention of this application, the ratio of the polyamide resin and the ethylenically unsaturated acrylic acid alkyl ester copolymer having a functional group is 25 to 65% by weight in order to balance flexibility, refrigerant permeation resistance, and heat resistance. 35 to 75 parts by weight of the ethylenically unsaturated acrylic acid alkyl ester copolymer having a functional group.
以下、この出願の発明を、実施例及び比較例に基づき、
さらに詳細に説明する。The invention of this application will be described below based on Examples and Comparative Examples.
This will be explained in more detail.
（実施例１１、比較例５．１０）
実施例１１、比較例５．１０の冷媒ホース用材料は、表
１に示す配合組成で、以下の方法により製造した。(Example 11, Comparative Example 5.10) The materials for refrigerant hoses of Example 11 and Comparative Example 5.10 had the composition shown in Table 1 and were manufactured by the following method.
ポリアミド樹脂の融点近傍に温度設定した混練機（ハー
ケ社製レオコード）に、ポリアミド樹脂とゴムを仕込み
、混練機のローター回転数を８Ｏｒ、ｐ、ｍとして混練
した。さらに、ステアリン酸を添加し約１５分間混練し
た後、ブレンド樹脂として取り出した。The polyamide resin and rubber were charged into a kneader (Rheocord, manufactured by Haake Co., Ltd.) whose temperature was set near the melting point of the polyamide resin, and kneaded with the rotor rotation speed of the kneader set to 8 Or, p, m. Further, stearic acid was added and kneaded for about 15 minutes, and then taken out as a blended resin.
このようにして得られたブレンド樹脂は、熱可塑性樹脂
としてプレス成形ができ、１ｍｍ厚のシートが得られた
。このシートからＪＩＳ Ｋ ７１１３の２号ダンベル
試験片を打ち抜き、この試験片を用いて引張試験を行っ
た。結果を表２に示す。The thus obtained blended resin could be press-molded as a thermoplastic resin, and a sheet with a thickness of 1 mm was obtained. A JIS K 7113 No. 2 dumbbell test piece was punched out from this sheet, and a tensile test was conducted using this test piece. The results are shown in Table 2.
尚、柔軟性を表す尺度として、常態引張物性における２
０％伸長時の強度を用いた。この強度が、２００ｋｇｆ
／ｃ−ｆｆｌを越すとチューブ・ホース材料としての柔
軟性に欠け、また２ ０ ｋｇｆ／ｃｉ以下になると、
チューブ・ホースに継手を取り付ける際充分に圧着する
ことができず、繰り返し変形によりその箇所から冷媒が
漏れてしまう。In addition, as a measure of flexibility, 2 in normal tensile properties
The strength at 0% elongation was used. This strength is 200kgf
/c-ffl, it lacks flexibility as a tube/hose material, and when it is less than 20 kgf/ci,
When attaching a joint to a tube or hose, it cannot be crimped sufficiently, and refrigerant leaks from that part due to repeated deformation.
次に、上記ブレンド樹脂を、連続混練押出機により混練
造粒してから熱可塑性樹脂用押出機によりチューブ（肉
厚約２． Ｏｍｍ）を成形した。これを用いて耐熱性
試験、低温衝撃試験、応力白化性評価試験を行った。結
果を表２に示す。Next, the blended resin was kneaded and granulated using a continuous kneading extruder and then molded into a tube (wall thickness: about 2.0 mm) using an extruder for thermoplastic resins. Using this, a heat resistance test, a low temperature impact test, and a stress whitening property evaluation test were conducted. The results are shown in Table 2.
さらに、前記チューブに、編組機により補強層（ポリエ
ステル繊維）を形成した後、最外層に熱可塑性エラスト
マー（ポリオレフィン樹脂）を押出被覆し、ホースを作
成した。このホースを用いて耐冷媒透過試験を行った。Further, a reinforcing layer (polyester fiber) was formed on the tube using a braiding machine, and then a thermoplastic elastomer (polyolefin resin) was extrusion coated on the outermost layer to prepare a hose. A refrigerant permeation resistance test was conducted using this hose.
尚、上記耐熱性試験、低温衝撃試験、応力白化性評価試
験、耐冷媒透過試験は、それぞれ以下に示す測定法によ
って行った。The heat resistance test, low-temperature impact test, stress whitening evaluation test, and refrigerant permeation resistance test were each performed using the measurement methods shown below.
耐熱性試験（ＪＡＳＯＭ ３２１−７７準拠）：チュー
ブを１２０°Ｃ，１６８時間で老化させ、その後の折り
曲げ時の亀裂の有無を測定した。亀裂の入ったものを×
で示し、亀裂の入らないものをＯで示した。Heat resistance test (based on JASOM 321-77): The tube was aged at 120°C for 168 hours, and the presence or absence of cracks during subsequent bending was measured. Something with cracks ×
Those with no cracks are shown as O.
低温衝撃試験（ＳＩＤＥ Ｊ ８４４準拠）：チューブ
を任意の温度に設定した低温恒温層に４時間保ち、耐衝
撃試験を行い、亀裂を生じたり、破壊する前の温度を示
した。Low-temperature impact test (according to SIDE J 844): The tube was kept in a low-temperature constant temperature layer set at an arbitrary temperature for 4 hours, and an impact test was performed, and the temperature before cracking or destruction was shown.
応力白化性評価試験：
チューブを１８０度折り曲げて、折り曲げた部分が白化
するかどうかを目視で評価した。白化したものを×、白
化しないものをＯで示した。応力白化の発生した部分は
、無数のクランクが発生しているため、その箇所のガス
バリヤ−性が著しく損なわれる。Stress whitening property evaluation test: The tube was bent 180 degrees and visually evaluated to see if the bent part would whiten. Whitening was indicated by ×, and non-whitening was indicated by O. In the area where stress whitening has occurred, countless cranks have occurred, so the gas barrier properties of that area are significantly impaired.
耐冷媒透過試験（ＪＡＳＯＭ ３２１−７７準拠）二金
具アセンブリホースに冷媒（フレオン１２）をホース内
容積１ｃＩｊ１当たり０．６±０．１ｇ充填し、測定温
度１００°Ｃで約１ケ月放置し、その間の減量を定期的
に測定した。Refrigerant permeation resistance test (based on JASOM 321-77) A two-metal assembly hose was filled with 0.6 ± 0.1 g of refrigerant (Freon 12) per 1 cIj of hose internal volume, and left at a measuring temperature of 100°C for about 1 month, during which time The weight loss was measured periodically.
（実施例１〜１０．１２〜１５、比較例４．６〜９）実
施例１〜１０．１２〜１５、比較例４．６〜９の各冷媒
ホース用材料も、表１に示す配合組成で、以下の方法に
より製造した。(Examples 1 to 10.12 to 15, Comparative Examples 4.6 to 9) Each refrigerant hose material of Examples 1 to 10.12 to 15 and Comparative Examples 4.6 to 9 also had the composition shown in Table 1. It was manufactured by the following method.
上記実施例１１、比較例５．１０と同様に、混練機用い
ポリアミド樹脂とゴムを混練した後、さらにローターを
回転させながらゴム用の架橋促進剤、充填剤、架橋剤を
添加した。そして、トルクメーターにより架橋によるト
ルク上昇を観察し、架橋終了を確認してからブレンド樹
脂を取り出した。Similarly to Example 11 and Comparative Example 5.10, after kneading the polyamide resin and rubber using a kneader, a crosslinking accelerator for rubber, a filler, and a crosslinking agent were added while rotating the rotor. Then, the increase in torque due to crosslinking was observed using a torque meter, and after confirming the completion of crosslinking, the blended resin was taken out.
尚、老化防止剤は、架橋剤を添加した後に加えたこのよ
うに作成したブレンド樹脂も熱可塑性樹脂として成形で
きるため、上記と同様にチューブ、ホースを作成し、引
張試験、耐熱性試験、低温衝撃試験、応力白化性評価試
験、耐冷媒透過試験を行った。結果を表２に示す。尚、
比較例７は、ゴム成分が多く熱可塑性が損なわれて成形
不能であった。The anti-aging agent is added after the cross-linking agent is added.The blended resin created in this way can also be molded as a thermoplastic resin, so tubes and hoses were created in the same manner as above, and subjected to tensile tests, heat resistance tests, and low temperature tests. An impact test, stress whitening property evaluation test, and refrigerant permeation resistance test were conducted. The results are shown in Table 2. still,
Comparative Example 7 contained a large amount of rubber components, impaired thermoplasticity, and could not be molded.
（比較例１〜３）
比較例１〜３の各冷媒ホース用材料は、表１に示す配合
組成のＮＢＲ、ナイロン１１、及びナイロン６／６６と
した。(Comparative Examples 1 to 3) The refrigerant hose materials of Comparative Examples 1 to 3 were NBR, nylon 11, and nylon 6/66 having the composition shown in Table 1.
そして、上記と同様にチューブ、ホースを作成し、引張
試験、耐熱性試験、低温衝撃試験、応力白化性評価試験
、耐冷媒透過試験を行った。結果を表２に示す。Then, tubes and hoses were prepared in the same manner as above, and subjected to a tensile test, a heat resistance test, a low-temperature impact test, a stress whitening property evaluation test, and a refrigerant permeation resistance test. The results are shown in Table 2.
表１
表１
（続きＩ）
表１
（続き■）
本ｚ 実Ｒ竜上・デュポン製 ベイマ・ンクし寧３
内新興化学工業製 ツクラックＣＤ（以下余白）
表１
（続き■）
表１
（続きＶ）
（以下余白）
表２
（以下余白）
表２（続きＩ）
＊：亀裂生じない
（以下余白）
表２（続き旧
［発明の効果］
この出願の発明の冷媒ホース用熱可塑性エストマー組成
物は、上記実施例と比較例との対比における、引張試験
、耐熱性試験、低温衝撃試験、応力白化性評価試験、耐
冷媒透過試験の結果からも明らかな通り、柔軟性、耐熱
性、低温衝撃性、応力白化性及び耐冷媒透過性の全てに
ついて優れた性質を有するので、自動車のクーラーやエ
アコン等に使用される冷媒ホース用材料に非常に適した
ものとなる。Table 1 Table 1 (Continued I) Table 1 (Continued ■) Book z Real Ryujo DuPont Bayma Nkushinei 3
Cracks CD manufactured by Uchishin Kagaku Kogyo Co., Ltd. (blank below) Table 1 (continued ■) Table 1 (Continued V) (blank below) Table 2 (blank below) Table 2 (continued I) *: No cracks (blank below) Table 2 (Continued Old [Effects of the Invention] The thermoplastic elastomer composition for refrigerant hoses of the invention of this application was tested in a tensile test, a heat resistance test, a low-temperature impact test, and a stress whitening property evaluation test in comparison with the above examples and comparative examples. As is clear from the results of the refrigerant permeation test, it has excellent properties in terms of flexibility, heat resistance, low-temperature impact resistance, stress whitening resistance, and refrigerant permeation resistance, so it is used in automobile coolers and air conditioners. This material is extremely suitable for refrigerant hoses.
Claims (1)
アクリル酸アルキルエステル共重合体が分散したポリマ
ーブレンドであって、常態引張物性における２０％伸長
時の強度が２０〜２００ｋｇｆ／ｃｍ＾２の範囲内であ
る冷媒ホース用熱可塑性エラストマー組成物。 ２、ポリアミド樹脂中に官能基を有するエチレン不飽和
アクリル酸アルキルエステル共重合体が架橋して分散し
たポリマーブレンドであって、常態引張物性における２
０％伸長時の強度が２０〜２００ｋｇｆ／ｃｍ＾２の範
囲内である冷媒ホース用熱可塑性エラストマー組成物。[Claims] 1. A polymer blend in which an ethylenically unsaturated acrylic acid alkyl ester copolymer having a functional group is dispersed in a polyamide resin, which has a strength at 20% elongation in normal tensile properties of 20 to 200 kgf/ Thermoplastic elastomer composition for refrigerant hoses within the range of cm^2. 2. A polymer blend in which an ethylenically unsaturated acrylic acid alkyl ester copolymer having a functional group is cross-linked and dispersed in a polyamide resin, and the normal tensile properties are 2.
A thermoplastic elastomer composition for a refrigerant hose having a strength at 0% elongation of 20 to 200 kgf/cm^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18578589A JPH0350262A (en) | 1989-07-18 | 1989-07-18 | Thermoplastic elastomer composition for refrigerant hose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18578589A JPH0350262A (en) | 1989-07-18 | 1989-07-18 | Thermoplastic elastomer composition for refrigerant hose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0350262A true JPH0350262A (en) | 1991-03-04 |
Family
ID=16176856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18578589A Pending JPH0350262A (en) | 1989-07-18 | 1989-07-18 | Thermoplastic elastomer composition for refrigerant hose |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0350262A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2781720A1 (en) * | 1998-07-31 | 2000-02-04 | Hutchinson | THERMOPLASTIC-ELASTOMER COMPOSITE PRODUCT, SUCH AS A REFRIGERANT PIPE FOR AIR CONDITIONING CIRCUIT |
| US8936583B2 (en) | 2007-09-28 | 2015-01-20 | Hollister Incorporated | Multi-layer catheter tubes with odor barrier |
-
1989
- 1989-07-18 JP JP18578589A patent/JPH0350262A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2781720A1 (en) * | 1998-07-31 | 2000-02-04 | Hutchinson | THERMOPLASTIC-ELASTOMER COMPOSITE PRODUCT, SUCH AS A REFRIGERANT PIPE FOR AIR CONDITIONING CIRCUIT |
| WO2000007810A1 (en) * | 1998-07-31 | 2000-02-17 | Hutchinson | Composite thermoplastic-elastomer product |
| US6652937B1 (en) * | 1998-07-31 | 2003-11-25 | Hutchinson | Composite thermoplastic-elastomer product |
| US8936583B2 (en) | 2007-09-28 | 2015-01-20 | Hollister Incorporated | Multi-layer catheter tubes with odor barrier |
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