JPH0232515B2 - PURASUCHITSUKUHOOSUNOSEIZOHOHO - Google Patents
PURASUCHITSUKUHOOSUNOSEIZOHOHOInfo
- Publication number
- JPH0232515B2 JPH0232515B2 JP20008583A JP20008583A JPH0232515B2 JP H0232515 B2 JPH0232515 B2 JP H0232515B2 JP 20008583 A JP20008583 A JP 20008583A JP 20008583 A JP20008583 A JP 20008583A JP H0232515 B2 JPH0232515 B2 JP H0232515B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- polyamide resin
- hose
- phase
- resin material
- 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.)
- Expired - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 claims description 23
- 239000005060 rubber Substances 0.000 claims description 23
- 229920006122 polyamide resin Polymers 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 229920005672 polyolefin resin Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- -1 etc. Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
- F16L11/085—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
Description
〔産業上の利用分野〕
本発明は、フレンホース、ブレーキホース等に
適用し得るプラスチツクホースの製造方法に関す
る。
〔従来技術〕
従来、一般に、ホースの材料としてゴムの替わ
りにポリアミド樹脂を用いると耐オゾン性、耐ガ
ス透過性、耐油性、耐熱性等が向上し、かつ軽量
化が期待できることは知られているが、ポリアミ
ド樹脂ホースはゴムホースに比べて非常に硬いた
め曲げにくくかつ折れやすいという欠点があり、
また、ポリアミド樹脂材料は吸水し易いためホー
ス内部に水分が溜まり、使用上有害な欠陥をもた
らすという危険性がある。後者の欠点を改良する
方法として、ポリアミド樹脂ホースの外周に官能
基を有する耐透水性の優れたオレフイン系樹脂材
料を用いて同時押出しし、両者を強固に接着せし
めることが有効である。
〔発明が解決しようとする問題点〕
前者の欠点を改良するため、ポリアミド樹脂と
可塑剤とのブレンド、ポリアミド樹脂とゴムとの
ブレンドあるいはゴムとの共重合を行なうことに
より柔難性を付与すると、従来の共押出による製
造方法では、官能基を有するオレフイン系樹脂と
の接着が著しく悪くなるという欠点があつた。
〔問題点を解決するための手段〕
本発明者は、ポリアミド樹脂材料ホースにおけ
る従来技術の欠点を解消すべく、種々研究を行つ
たところ、本発明により従来の共押出による製造
方法においても、これらの欠点を解消したプラス
チツクホースを提供することに成功した。
すなわち、本発明は、ポリアミド樹脂に未架橋
ゴムを、そのゴムの架橋用の架橋剤の存在下にブ
レンドして得られる、ポリアミド樹脂が海相で、
架橋ゴムが島相である相構造のポリアミド樹脂−
ゴムブレンド組成物の内層と、官能基を有するポ
リオレフイン系樹脂材料の外層を共押出すること
によりプラスチツクホースを製造する方法を提供
するものである。
上記のポリアミド樹脂−ゴムブレンド組成物と
上記のポリオレフイン系樹脂材料を溶融状態で共
押出すると、内層のポリアミド樹脂−ゴムブレン
ド組成物において、ポリアミド樹脂が海相となつ
ているため、通常のゴムブレンドナイロン、ゴム
共重合ナイロンあるいは可塑化ナイロンなどに比
較すると、ポリオレフイン系樹脂材料に対する接
着性が著しく優れたものとなる。
以下に本発明を詳細に説明する。
本発明により得られるプラスチツクホースは、
添付図面にその態様例の模式図が示されている
が、内層１は、ポリアミド樹脂材料、例えばナイ
ロン６、ナイロン66、ナイロン11、ナイロン12等
に、ゴム、例えば未架橋の天然ゴム（NR）、ス
チレン−ブタジエンゴム（SBR）、アクリロニト
リル−ブタジエンゴム（NBR）、イソブチレン−
イソプレンゴム（IIR）、アクリルゴム（ACM）、
エピクロルヒドリンゴム（EO、ECO）等と、そ
のゴムの架橋用の架橋剤とをポリアミド樹脂材料
の融点以上の温度においてブレンドし、ブレンド
中に未架橋ゴムの一部あるいは全部を架橋せしめ
ポリアミド樹脂材料中にゴムを分散させることに
よつて、ポリアミド樹脂が海相、架橋ゴムが島相
という相構造からなるポリアミド樹脂−ゴムブレ
ンドとした構造よりなつている。外層２はカルボ
キシル基、エポキシ基、アミノ基等の官能基を有
し、かつ耐透水性の優れたポリオレフイン系樹脂
材料からなつている。
本発明より得られるプラスチツクホースにおけ
る内層と外層（ポリオレフイン系樹脂材料）との
剥離強さを従来技術による製品と比較した試験の
結果を下記の表１に示す。
[Industrial Application Field] The present invention relates to a method for manufacturing a plastic hose that can be applied to a full hose, a brake hose, and the like. [Prior Art] It is generally known that using polyamide resin instead of rubber as a hose material can improve ozone resistance, gas permeability, oil resistance, heat resistance, etc., and can also be expected to be lighter. However, polyamide resin hoses have the disadvantage that they are much harder than rubber hoses, making them difficult to bend and easily break.
Furthermore, since polyamide resin materials tend to absorb water, there is a risk that moisture may accumulate inside the hose, resulting in defects that are harmful to use. As a method to improve the latter drawback, it is effective to coextrude a polyamide resin hose with an olefin resin material having excellent water permeability and having a functional group on the outer periphery of the hose, thereby firmly adhering the two. [Problems to be solved by the invention] In order to improve the former drawback, flexibility can be imparted by blending a polyamide resin with a plasticizer, blending a polyamide resin with rubber, or copolymerizing it with rubber. However, the conventional production method using coextrusion had the disadvantage that adhesion with olefinic resins having functional groups deteriorated significantly. [Means for Solving the Problems] The present inventor has conducted various studies in order to eliminate the drawbacks of the conventional technology for polyamide resin material hoses, and the present invention has found that these problems can be solved even in the conventional coextrusion manufacturing method. We have succeeded in providing a plastic hose that eliminates the disadvantages of That is, the present invention provides a polyamide resin obtained by blending an uncrosslinked rubber with a polyamide resin in the presence of a crosslinking agent for crosslinking the rubber, in which the polyamide resin is in the sea phase,
Polyamide resin with a phase structure in which the crosslinked rubber is an island phase.
A method is provided for making a plastic hose by coextruding an inner layer of a rubber blend composition and an outer layer of a functionalized polyolefin resin material. When the above-mentioned polyamide resin-rubber blend composition and the above-mentioned polyolefin resin material are coextruded in a molten state, the polyamide resin becomes a sea phase in the inner layer polyamide resin-rubber blend composition, so that the polyamide resin becomes a normal rubber blend. Compared to nylon, rubber copolymerized nylon, plasticized nylon, etc., it has significantly superior adhesion to polyolefin resin materials. The present invention will be explained in detail below. The plastic hose obtained by the present invention is
The inner layer 1 is made of a polyamide resin material such as nylon 6, nylon 66, nylon 11, nylon 12, etc., and rubber such as uncrosslinked natural rubber (NR), as shown in the accompanying drawings. , styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), isobutylene-
Isoprene rubber (IIR), acrylic rubber (ACM),
Epichlorohydrin rubber (EO, ECO), etc. and a crosslinking agent for crosslinking the rubber are blended at a temperature higher than the melting point of the polyamide resin material, and during the blending, part or all of the uncrosslinked rubber is crosslinked to form a crosslinker in the polyamide resin material. By dispersing the rubber in the rubber, the polyamide resin-rubber blend has a phase structure in which the polyamide resin is a sea phase and the crosslinked rubber is an island phase. The outer layer 2 is made of a polyolefin resin material that has functional groups such as carboxyl groups, epoxy groups, and amino groups and has excellent water permeation resistance. Table 1 below shows the results of a test in which the peel strength between the inner layer and the outer layer (polyolefin resin material) of the plastic hose obtained according to the present invention was compared with products according to the prior art.
【表】【table】
本発明により従来の共押出による製造方法にお
いても、内層とポリオレフイン系樹脂材料の外層
とが強固に接着され、すべての利点を備えている
ので、例えばカークーラー、ルームエアコン等の
フレオン冷媒の通路として用いられるフレオン用
ホースに適用するときは、ポリアミド樹脂のフレ
オン透過量が少ないことから耐フレオン透過性、
耐透水性を同時に満足し、かつフレキシブルなフ
レオン用ホースとして極めて有用なものである。
The present invention provides strong adhesion between the inner layer and the outer layer of polyolefin resin material even in the conventional co-extrusion manufacturing method, and has all the advantages. When applied to Freon hoses, polyamide resin has low Freon permeation resistance, so
It is extremely useful as a flexible Freon hose that satisfies water permeation resistance at the same time.
第１図は、本発明のプラスチツクホースの一態
様例を模式的に示す部分切欠斜視図であり、第２
図は本発明のプラスチツクホースに補強層と外皮
層を設けた一態様例を模式的に示す部分切欠斜視
図である。
１……内層、２……外層、３……中間外層、４
……補強層、５……外皮層。
FIG. 1 is a partially cutaway perspective view schematically showing one embodiment of the plastic hose of the present invention, and FIG.
The figure is a partially cutaway perspective view schematically showing an embodiment of the plastic hose of the present invention provided with a reinforcing layer and an outer skin layer. 1...Inner layer, 2...Outer layer, 3...Middle outer layer, 4
... Reinforcement layer, 5 ... Outer skin layer.
Claims (1)
架橋用の架橋剤の存在下にブレンドして得られ
る、ポリアミド樹脂が海相で、架橋ゴムが島相で
ある相構造のポリアミド樹脂−ゴムブレンド組成
物の内層と官能基を有するポリオレフイン系樹脂
材料の外層を共押出することを特徴とするプラス
チツクホースの製造方法。1 A polyamide resin-rubber blend composition having a phase structure in which the polyamide resin is a sea phase and the crosslinked rubber is an island phase, which is obtained by blending an uncrosslinked rubber with a polyamide resin in the presence of a crosslinking agent for crosslinking the rubber. A method for producing a plastic hose, characterized by co-extruding an inner layer of the material and an outer layer of a polyolefin resin material having functional groups.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20008583A JPH0232515B2 (en) | 1983-10-27 | 1983-10-27 | PURASUCHITSUKUHOOSUNOSEIZOHOHO |
| DE19843439312 DE3439312C2 (en) | 1983-10-27 | 1984-10-26 | Double-layer flexible plastic hose, especially as a line for fluorinated hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20008583A JPH0232515B2 (en) | 1983-10-27 | 1983-10-27 | PURASUCHITSUKUHOOSUNOSEIZOHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6095294A JPS6095294A (en) | 1985-05-28 |
| JPH0232515B2 true JPH0232515B2 (en) | 1990-07-20 |
Family
ID=16418601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20008583A Expired - Lifetime JPH0232515B2 (en) | 1983-10-27 | 1983-10-27 | PURASUCHITSUKUHOOSUNOSEIZOHOHO |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0232515B2 (en) |
| DE (1) | DE3439312C2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013114689A1 (en) * | 2012-01-30 | 2013-08-08 | 東海ゴム工業株式会社 | Resin hose and method for producing same |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4633912A (en) * | 1985-05-31 | 1987-01-06 | The Goodyear Tire & Rubber Company | Hose construction |
| DE3715251A1 (en) * | 1987-05-08 | 1988-12-01 | Caprano & Brunnhofer | MOTOR VEHICLE PIPELINE FOR GUIDING AN ALCOHOLIC MEDIUM |
| US4987017A (en) * | 1987-06-26 | 1991-01-22 | Japan Synthetic Rubber Co., Ltd. | Thermoplastic elastomer composition and Freon gas hose made thereof |
| DE4000434C2 (en) * | 1990-01-09 | 1997-07-24 | Inventa Ag | Multi-layer flexible coolant line |
| JPH0826948B2 (en) * | 1990-10-01 | 1996-03-21 | 東海ゴム工業株式会社 | Resin tube for fuel piping |
| FR2700292B1 (en) * | 1993-01-13 | 1995-02-24 | Atochem Elf Sa | Composite tubular article formed from a vulcanized elastomer associated with a thermoplastic elastomer having polyamide sequences, in particular gasoline pipe and process for preparing such an article. |
| FR2712370B1 (en) * | 1993-11-09 | 1996-01-19 | Nobel Plastiques | Pipe for refrigeration fluid. |
| AU687956B2 (en) * | 1993-12-13 | 1998-03-05 | Elf Atochem S.A. | Multilayer article including a vulcanised elastomer directly combined with a thermoplastic |
| FR2719520A1 (en) * | 1994-05-06 | 1995-11-10 | Atochem Elf Sa | Material comprising a vulcanized elastomer associated with a thermoplastic elastomer. |
| FR2726345B1 (en) * | 1994-11-02 | 1996-12-27 | Atochem Elf Sa | POLYAMIDE AND POLYETHYLENE TUBES FOR DOMESTIC GAS DISTRIBUTION |
| FR2733294B1 (en) * | 1995-04-19 | 1997-06-06 | Nobel Plastiques | PIPING FOR HIGH PRESSURE AND HIGH TEMPERATURE FLUID |
| US5622210A (en) * | 1995-06-12 | 1997-04-22 | Lsp Products Group, Inc. | Flexible hose with composite core |
| EP1652887B1 (en) | 2002-03-04 | 2012-10-31 | Arkema France | Polyamide-based composition for the making of flexible hoses containing oil or gas |
| US20080017266A1 (en) * | 2006-07-24 | 2008-01-24 | Doshi Shailesh R | High pressure barrier hose and method of manufacture |
| ITTO20080404A1 (en) * | 2008-05-27 | 2009-11-28 | Dayco Fluid Technologies Spa | CABLE ELEMENT FOR THE TRANSPORT OF A REFRIGERANT FLUID IN A MOTOR VEHICLE |
| JP5360714B2 (en) * | 2009-06-05 | 2013-12-04 | 中村物産有限会社 | Moisture absorption and desorption functional pipe, pipe inner wall condensation prevention method using the same, and geothermal exchanger using the same |
| CN109109351A (en) * | 2018-09-14 | 2019-01-01 | 常州腾龙汽车零部件股份有限公司 | The preparation method of air-conditioning tubing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1650138A1 (en) * | 1967-08-18 | 1970-09-24 | Phoenix Gummiwerke Ag | Hose for fuel or propellants |
| DE2555017A1 (en) * | 1975-12-06 | 1977-06-08 | Kabel Metallwerke Ghh | TUBE-SHAPED STRUCTURE FOR TRANSPORTING LIQUID OR GAS-SHAPED MEDIA, ESPECIALLY AT HIGH TEMPERATURES AND HIGH PRESSURE |
-
1983
- 1983-10-27 JP JP20008583A patent/JPH0232515B2/en not_active Expired - Lifetime
-
1984
- 1984-10-26 DE DE19843439312 patent/DE3439312C2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013114689A1 (en) * | 2012-01-30 | 2013-08-08 | 東海ゴム工業株式会社 | Resin hose and method for producing same |
| JP2013155793A (en) * | 2012-01-30 | 2013-08-15 | Tokai Rubber Ind Ltd | Resin hose, and method of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3439312A1 (en) | 1985-05-15 |
| JPS6095294A (en) | 1985-05-28 |
| DE3439312C2 (en) | 1986-10-30 |
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