JPH0374691A - Low permeable hose - Google Patents
Low permeable hoseInfo
- Publication number
- JPH0374691A JPH0374691A JP1211145A JP21114589A JPH0374691A JP H0374691 A JPH0374691 A JP H0374691A JP 1211145 A JP1211145 A JP 1211145A JP 21114589 A JP21114589 A JP 21114589A JP H0374691 A JPH0374691 A JP H0374691A
- Authority
- JP
- Japan
- Prior art keywords
- hose
- reinforcing
- rubber
- layer
- nylon
- 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.)
- Granted
Links
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 239000005060 rubber Substances 0.000 claims abstract description 28
- 230000035699 permeability Effects 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 238000009954 braiding Methods 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 abstract description 10
- 229920001778 nylon Polymers 0.000 abstract description 9
- 239000003507 refrigerant Substances 0.000 abstract description 7
- 229910000831 Steel Inorganic materials 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 6
- 239000010959 steel Substances 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 229920000297 Rayon Polymers 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract description 2
- 239000002964 rayon Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 46
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 8
- 229920000299 Nylon 12 Polymers 0.000 description 8
- 229920002292 Nylon 6 Polymers 0.000 description 8
- 229920000571 Nylon 11 Polymers 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 6
- 229920005549 butyl rubber Polymers 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 4
- -1 polyethylene terephthalate Polymers 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 229920000577 Nylon 6/66 Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 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 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920005556 chlorobutyl Polymers 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 240000003173 Drymaria cordata Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- 241000692870 Inachis io Species 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 229920006065 Leona® Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920000305 Nylon 6,10 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
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000010088 rubber extraction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000004711 α-olefin Substances 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
Abstract
Description
く！業上の利用分野〉
本発明は、フレオンガスのような冷媒輸送用、またはガ
ソリン、軽油などの燃料輸送用ヒして、均衡のとれた実
用性能を有する、特に、低透過性に優れたホースに関す
る。
〈従来技術〉
従来、冷媒輸送用または燃料輸送用等に使用されるホー
スヒしては、耐油性＆：優れ、かつ冷媒や燃料の透過性
の低いゴム、例えばニトリルゴムで形成したホースや、
ホースの内管なゴムと樹脂の１層から形成したものが使
用されていた。
しかし、特に最近では、カーエアコン等の冷媒として用
いられているフレオンガスが、オゾン層を破壊し、皮膚
ガンを誘発することが明らかにされてきたため、フレオ
ンガスの代替品を研究する一方で、従来のホースよりも
ガス洩れの少ない、すなわち低透過性のホースの開発も
急がれている。
この種のホースとしては、ゴムおよび／＊たは樹脂層を
用いた複合構造のホースが主であり、ホース最内層は、
ホースの柔軟性を考慮して、厚さ０．１〜０．５ｍｍの
範囲内と薄い。
また、補強層を設ける場合も考えられているが、この補
強層の構成自体も従来のゴムホースの構造と何ら変りが
ないため、加圧時の外径変化（膨張）が１〜２％も生じ
てしまう。 そのためホースの内表面積増大と樹脂伸長
による薄肉化によって、ガス洩れが生じやす（なるとい
った欠点があった。
〈発明が解決しようとする課題〉
そこで本発明は、上記事情に鑑み、また、産業上の要請
に応えてなされたものであり、フレオンガス等の冷媒や
、ガソリン等の燃料の透過性が低いホースを提供するこ
とを目的とする。
く課題を解決するための手段〉
すなわち本発明は、ゴムおよび／または樹脂層および補
強糸で構成される補強層を有する複合構造のホースにお
いて、
前記補強層を構成する補強糸の一定荷重（４，５ｋｇｆ
／本）伸び率が３．５％以下であり、補強糸の編組角度
が５４．７５°超５６．０°以下の範囲であることを特
徴ヒする低透過性ホースを提供する。
また、前記ホースの加圧時において、補強糸に加わる負
荷が、補強糸破断強度の５〜１５％の範囲内となる耐圧
力を有するのが好ましい。
さらに、使用加圧時の径変化が０．５％以下であるのが
よい。
以下、本発明について、詳細に説明する。
本発明の低透過性ホースは、ゴムおよび／または樹脂層
を有し、かつ前記ゴムおよび／または樹脂層内に補強層
を有する複合構造から構成される。
本発明の補強層を構成する補強糸ヒしては、一定荷重（
４，５ｋｇｆ／本）伸び率が３．５％以下であり、補強
糸の編組角度が５４．７５°超５６．０°以下の範囲で
あるのがよい。
ここでいう一定荷重伸び率（Ｊ Ｉ ５−Ｌ１０１７）
とは、４゜５ ｋｇｆの荷重を、ホース補強層を構成す
る補強糸１本にかけた場合の補強糸の伸び率をいう、
＊たことでいう補強糸１本とは、編組して補強層ヒする
前の繕った糸をいう。
本発明に用いる補強糸の一定荷重（４，５ｋｇｆ／本）
伸び率は、３．５％以下であるのが好ましい、 ３．５
％超では補強糸が伸び過ぎ、ホースの径が広がるため透
過性が高くなり好ましくない。
補強糸に用いる材料としては、レーヨン繊維、ポリエス
テル繊維、ナイロン繊維、硬鋼線等があげられるが、前
記伸び率を満足する繊維であれば特に限定されない。
具体的には、ポリエステル繊維としては、ポリエチレン
テレフタレート（音大、東し社製；テトロン）が一般に
好適Ｃ使用される。
ナイロン繊維としては、ナイロン６、ナイロン６６、（
旭化成社製：レオナ）等が、硬鋼線としては、一般に該
硬鋼線上は防錆および接着性付与の為、真鍮メツキされ
た鋼線が使用される。
特に好ましくは、芳香族ポリアミド（アラ暑ド）繊維が
ある芳香族ボリア主ド繊維としては、ポリ（ｐ−フェニ
レンテレフタルアセト）（デュポン社；ケブラー アク
ゾ社；トワロン）、ポリバラフェニレン−３，４−ジフ
ェニルエーテル・テレフタルアくド（奇人；テクノーラ
）等があり、これらを用いる。
上述の補強糸を編組して補強層に用いるが、本発明にお
いて、その編組角度は５４．７５゜超、５６．０”以下
であるのがよい、 さらに好ましくは５５″″以上、５
５．５°以下であるのがよい。 編組角度が５４．７５
° （静止角度）以下では、ホース加圧時にホース長さ
が縮みその代わりにホースの径が膨らむため、透過可能
な面積が大きくなってしまう、 また５６．０”超では
、ホース加圧時にホース長さが長（なりすぎ、寸法安定
性が悪く好ましくない。
さらに、本発明のホースは、−殻内な使用圧力である３
０〜４０ ｋｇｆ／ｃ−の圧力をかけたとき、補強糸１
本に加わる負荷が破断強度の５〜１５％の範囲（即ち加
圧時負荷率が５〜１５％）ヒなるような耐圧力を有する
ものが好ましい。 即ち、ホースの耐圧力（破壊圧力）
が、使用圧力の６．６〜２０倍の範囲であるのがよい、
この範囲内であれば、糸の伸びが少な（、長い間借透
過性が維持され、また耐圧力に対しても優れた効果を有
する。
ざらＣ１本発明のホースは、使用加圧（４０Ｋｇｆ／ｃ
ｍ” ）時のホースの径変化は、０゜５％以下であるの
がよい、 径変化が０．５％超では、径変化が大き過ぎ
るためにガスが透過しやすくなり好ましくない。
また、本発明の低透過性ホースは、ゴムおよび／または
樹脂よりなる多層構造内に前述の補強層を有するよう構
成されている。
ホースに用いられるゴムは、天然ゴム、合成ゴム等一般
的なものであればよい。
具体的には、アクリロニトリル・ブタジェンゴム（ＮＢ
Ｒ） クロロスルホン化ポリエチレン（ＣＳＭ）
エチレン・プロピレン・ジエン三元共重合体ゴムｌ：
Ｐ ＤＭ）、ブチルゴム（ＩＩＲ） 塩素化ブチルゴ
ム（Ｃｌ３−１１ Ｒ） 、臭素化ブチルゴム（Ｂｒ−
１１Ｒ）、ヒドリンゴム（ＣＨＲ，ＣＨＣ）、アクリル
ゴム（ＡＣＭ）等のゴム組成物があげられ、ホース特性
上のバランスあるいは耐油性、水分不透過性等を考慮す
るヒ、ＮＢＲ１Ｃ３Ｍ％ＥＰＤＭ％ＣＨＲ，ＣＨＣ，Ｉ
ＩＲ。
０皿−ＩＩＲ％Ｂｒ−１１Ｒのゴム組成物が好ましい。
尚、ゴム組成物Ｃは、ゴムの他に加硫剤、充填剤、補強
剤、可塑剤、老化防止剤等が配合されており、また、加
硫促進剤、軟化剤、粘着付与剤、滑剤、しやく解剖、分
散剤、加工助剤等が配合されていてもよい。
また樹脂としては、フレオンガスの透過防止または使用
環境下で生成する金属塩化物によるストレスクラック防
止等用途に応じてナイロン系′１Ｍ脂、芳香族ボリア主
ド樹脂、ボリアKu! Field of Industrial Application> The present invention relates to a hose that has balanced practical performance, particularly excellent low permeability, for transporting refrigerants such as Freon gas, or fuels such as gasoline and diesel oil. . <Prior Art> Conventionally, hoses used for transporting refrigerant or fuel have been made of rubber that has excellent oil resistance and low permeability to refrigerant or fuel, such as nitrile rubber.
The inner tube of the hose was made from a single layer of rubber and resin. However, especially recently, it has been revealed that Freon gas, which is used as a refrigerant in car air conditioners, destroys the ozone layer and causes skin cancer. There is also an urgent need to develop hoses that leak less gas than other hoses, that is, have low permeability. This type of hose mainly has a composite structure using rubber and /* or resin layers, and the innermost layer of the hose is
Considering the flexibility of the hose, the thickness is within the range of 0.1 to 0.5 mm. Additionally, the provision of a reinforcing layer is being considered, but since the structure of this reinforcing layer itself is no different from the structure of conventional rubber hoses, a change in outer diameter (expansion) when pressurized occurs by as much as 1 to 2%. I end up. Therefore, the increase in the inner surface area of the hose and the thinning of the hose due to the elongation of the resin have the disadvantage of causing gas leakage. The purpose of the present invention is to provide a hose that has low permeability to refrigerants such as Freon gas and fuels such as gasoline. In a hose with a composite structure having a reinforcing layer composed of a rubber and/or resin layer and a reinforcing thread, the reinforcing thread constituting the reinforcing layer has a constant load (4.5 kgf).
Provided is a low permeability hose characterized by having an elongation rate of 3.5% or less and a braiding angle of reinforcing yarns in a range of more than 54.75° and less than 56.0°. Further, when pressurizing the hose, the reinforcing yarn preferably has a pressure resistance such that the load applied to the reinforcing yarn falls within a range of 5 to 15% of the reinforcing yarn breaking strength. Furthermore, it is preferable that the change in diameter during pressurization during use is 0.5% or less. The present invention will be explained in detail below. The low permeability hose of the present invention is constructed from a composite structure having a rubber and/or resin layer and a reinforcing layer within the rubber and/or resin layer. The reinforcing yarn constituting the reinforcing layer of the present invention can be used under a certain load (
(4.5 kgf/strand) The elongation rate is preferably 3.5% or less, and the braiding angle of the reinforcing yarn is preferably in the range of more than 54.75° and less than 56.0°. Constant load elongation rate (J I 5-L1017) here
refers to the elongation rate of the reinforcing thread when a load of 4.5 kgf is applied to one reinforcing thread constituting the hose reinforcing layer.
*One reinforcing thread refers to the mended thread before being braided and applying the reinforcing layer. Constant load of reinforcing yarn used in the present invention (4.5 kgf/strand)
The elongation rate is preferably 3.5% or less, 3.5
If it exceeds %, the reinforcing yarn will stretch too much and the diameter of the hose will expand, resulting in increased permeability, which is not preferable. Materials used for the reinforcing yarn include rayon fibers, polyester fibers, nylon fibers, hard steel wires, etc., but are not particularly limited as long as the fibers satisfy the above-mentioned elongation rate. Specifically, as the polyester fiber, polyethylene terephthalate (manufactured by Music University, Toshisha Co., Ltd.; Tetron) is generally preferably used. Nylon fibers include nylon 6, nylon 66, (
Leona (manufactured by Asahi Kasei Co., Ltd.), etc. As the hard steel wire, generally, a brass-plated steel wire is used for rust prevention and adhesion on the hard steel wire. Particularly preferably, the aromatic boria-based fibers having aromatic polyamide (Araratto) fibers include poly(p-phenylene terephthalaceto) (DuPont; Kevlar; Akzo; Twaron); poly(paraphenylene-3,4); - There are diphenyl ether and terephthalate (technora), etc., and these are used. The above-mentioned reinforcing threads are braided and used for the reinforcing layer. In the present invention, the braiding angle is preferably more than 54.75° and less than 56.0", more preferably more than 55"", and less than 56.0".
It is preferable that the angle is 5.5° or less. Braid angle is 54.75
° Below (resting angle), the length of the hose will shrink when the hose is pressurized and the diameter of the hose will expand instead, increasing the permeable area. The length is too long, which is undesirable due to poor dimensional stability.Furthermore, the hose of the present invention has - an internal working pressure of 3.
When applying a pressure of 0 to 40 kgf/c-, reinforcing yarn 1
It is preferable that the book has a pressure resistance such that the load applied to the book is within a range of 5 to 15% of the breaking strength (that is, the load rate during pressurization is 5 to 15%). In other words, the withstand pressure (rupture pressure) of the hose
is preferably in the range of 6.6 to 20 times the working pressure.
Within this range, the elongation of the yarn is small (the permeability is maintained for a long time, and the hose of the present invention has an excellent effect on pressure resistance).
The change in diameter of the hose at the time of 100 m" is preferably 0°5% or less. If the change in diameter exceeds 0.5%, the change in diameter will be too large and gas will easily permeate, which is undesirable. The low permeability hose of the present invention is configured to have the above-mentioned reinforcing layer within a multilayer structure made of rubber and/or resin. The rubber used for the hose may be a general rubber such as natural rubber or synthetic rubber. Specifically, acrylonitrile butadiene rubber (NB
R) Chlorosulfonated polyethylene (CSM)
Ethylene-propylene-diene terpolymer rubber:
P DM), butyl rubber (IIR), chlorinated butyl rubber (Cl3-11 R), brominated butyl rubber (Br-
11R), hydrin rubber (CHR, CHC), acrylic rubber (ACM), etc. Considering the balance of hose properties, oil resistance, water impermeability, etc., NBR1C3M%EPDM%CHR,CHC ,I
IR. A rubber composition of 0 plate-IIR% Br-11R is preferred. The rubber composition C contains, in addition to rubber, a vulcanizing agent, a filler, a reinforcing agent, a plasticizer, an anti-aging agent, etc., and also a vulcanization accelerator, a softener, a tackifier, a lubricant, etc. , a quick dissection agent, a dispersant, a processing aid, etc. may be blended. In addition, as resins, nylon-based 1M resin, aromatic boria-based resin, boria
【ド・ポリエーテル共重合体等が使用さ
れる。
ナイロン系樹脂としては、ナイロン６、ナイロン８、ナ
イロン１０５ナイロン１１、ナイロン１２、ナイロン６
６、ナイロン６１０等およびこれらの共重合体、ならび
にこれらを含有するポリアミド系樹脂などが挙げられる
。
特にフレオンガスの透過防止と耐ストレスクラック性を
同時に考慮した場合は、ナイロン１１Ｊ５よび／＊には
ナイロン１２を必須成分として含有するポリアミド系樹
脂とすることが好１バ、あるいは、４０〜８０重量部の
ナイロン６および／またはナイロン６・６６共重合体、
５〜３０重量部のナイロン１１および／またはナイロン
１２、および１０〜４０重量部のポリオレフィン系樹脂
からなる樹脂組成物とすることが好ましい。
ナイロン１１および／またはナイロン１２を必須成分と
して含有するポリアミド系樹脂の具体例ヒしては、ナイ
ロン１１、ナイロン１２のそれぞれ単独または混合樹脂
、６０重量％以上のナイロン１１および／３Ｉ！たはナ
イロン１２と、４０重量％未溝のそれ以外のポリアミド
系樹脂、例えばナイロン６等とのブレンドポリマー等が
あげられる。
また、４０〜８０重量部のナイロン６および／またはナ
イロン６・６６共重合体、５〜３０重量部のナイロン１
１および／またはナイロン１２、および１０〜４０重量
部のポリオレフィン系ｓｉｎからなる樹脂組成物では、
ポリオレフインはα−オレフィン共重合体であってもよ
く、また、ポリオレフィンの具体例としては、ポリエチ
レン、ポリプロピレン、エチレン・プロピレン共重合体
および／またはこれら重合体のマレイン酸付加物等があ
げられる。
該樹脂組成物には、必要に応じて老化防止剤等の他の添
加剤を加えてもよい（例えば、耐熱剤０．０３〜０．５
重量％および可塑剤３〜１０重量％添加）。
なお、上記の配合割合は、該樹脂組成物に耐ストレス・
クラック性と柔軟性とをあわせ持たせるために限定され
たものである。
芳香族ボリアミド樹脂としては、メタキシリレンシア主
ンとアジピン酸とから合成され、一般式（１）
で示され、具体例としては、ＭＸＤ６ （東洋紡（株）
製〉等があげられる。
また、ポリアミド・ポリエーテル共重合体は、ポリアミ
ドセグメントとポリエーテルセグメントとからなるブロ
ック共重合体であり、ボリアミドセグメントは、ナイロ
ン６、ナイロン１１、ナイロン１２、ナイロン６・６６
共重合体、ナイロン６１２共重合体等から、ポリエーテ
ルセグメントは、ポリテトラメチレングリコール、ポリ
プロピレングリコール、ポリエチレングリコール等から
なる。
ボリア９ドセグメントとポリエーテルセグメントの成分
の組み合せ社より、様々な程度の柔軟性、融点、耐油性
を示す共重合体が得られている。
具体例としては、ＰＥＢＡＸ ５５３３ＳＴＯ１，Ｐ
ＥＢＡＸ５Ｓ６２ＭＡＯＯ％ＰＨＢＡＸ ５５１２ＭＮ
０Ｏ（以上、アトケム（株）製）、ダイアミド−ＰＡＥ
Ｅ４７ （ダイセル・ヒエルス■製）等があげられ
る。
本発明の低透過性ホースは、前述のゴムおよび／または
樹脂を何層かに重ね、前記補強層とともに多層化した複
合構造のものがよい。
たとえば、内管、補強層および外管を有するホースであ
って、そのホースの使用目的、使用条件等によって、内
管な古らに多層化したり、ストレス・クジャク防止層を
設けたりしてもよい。
本発明の低透過性ホースの製造法としては、公知の手段
を適用することができるが、ｋとえば内管を樹脂層とゴ
ム層の多層構造とし、その上に補強層および外管を有す
る場合の例を示す。
樹脂の種類社応じて用意した複数の押出機を使用し、予
め離型剤を付与したマンドレル上に、各押出機を結合し
た共通の複層押出ヘッドからホースの内管を形成する樹
脂をそれぞれ押出し、複層構造の樹脂チェーンを形成す
る。 この樹脂チェーンを形成されたマンドレルをゴム
抽出機に通し、樹脂チ具−ブ上にゴムを押出し、ゴム製
の内管外層を形成する。 なお、必要に応じ、樹脂チュ
ーブ表面に塩化ゴム系、フェノール樹脂系、ＨＲ）（系
等の接着剤を重布、スプレーなどにより付与した後、ゴ
ム層を形成することができる。
上記のように形成された内管上Ｃ１縞組機を使用して、
本発明に示す条件の補強糸を編組し、その上社、ゴム押
出機を用いてゴム製外管を形成する。 このようにして
内管、補強層および外管の形成されたマンドレルを、１
３０〜１７０℃、好ましくは１４０〜１６０℃の温度範
囲内で加圧子加熱を行い、ゴム層を加硫し、冷却し、最
後にマンドレルを引き抜くこヒにより、本発明のホース
が得られる。
〈実施例〉
以下、本発明を実施例に基づいて、さらに具体的に説明
する。
（実施例）
すでに説明した方法で、ナイロン６
（５８，２皿量％）、ナイロン１１（１４，５重量％）
エチレン−プロピレン共重合体（２７，３重量％）か
らなる材料を用いて、内径１１ｍｍ、肉厚ｏ、ｔｓｍｍ
の最内層、ブチルゴム（ＩＩＲ）の材料を用いて肉厚１
．５ｍｍの内層、塩素化ブチルゴム（ＣＸ−ＩＩＲ）の
材料を用いて肉厚１．５ｍｍの外層、および内層と外層
の間に表１に示す各種補強層を有するホース（発明例１
〜４、比較例１〜４）を製造した。 これらのホースを
用いて、フレオンガス透過量およびこの透過量に影響を
与える加圧時のホース径変化を調べた。 結果を表１中
に示す。
（フレオンガス透過量の測定方法〉
ＪＡＲ規格（日本冷凍空調工業会規格）のＪＲＡ２００
１に準する。
ホースの長さ（自由長０．５ｍ）の前記各種ホースに冷
媒をホース内容積１ｃｍ”当りＯ，Ｓ±０．１グラム封
入する。 温度Ｗｏ。
℃に９６時間放置し、２４時間後と９６時間後の間の減
量（ガス透過量）を測定し、ｇ／ｍ／７２時間に数値を
換算した。
また、加圧時の径変化についての測定は、４０ Ｋｇｆ
／ｃｔｓ２で加圧した時のホース外径と、無加圧時のホ
ース外径をノギス（て測定し、下記式［１］に代入して
求めた。
加圧時径変化
・・・・・・【１】
表１から明らかなように、補強層の補強糸としてポリエ
ステルを用い、そのポリエステルの一定荷重（４，５Ｋ
ｇｆ／本）時の伸び率が４％のものは、３％のものより
糸の撚りが少ないため、伸びが大きくなり好ましくない
。
また、アク哉ドおよび硬鋼線は糸の伸びが極めて小さい
ため、加圧時の径変化は角度の要素が、ガスの透過性に
大きく影響を与える。
方、ポリエステルは糸の伸びが大きいので、編組角度を
５４．７５° （静止角度）より大きくすることで、加
圧時に静止角度方向に編組角度変化させ、ホースの長さ
方向（ホースを伸ばすことで、ホース径方向の膨らみを
防止することができる。
さらに、加圧時の負荷率（■１／安全率）を小さくする
ことにより、補強糸１本当たりの荷重（伸び）を抑制す
ることができる。
（発明の効果〉
本発明の補強層を、ホースの複合構造中に含むことによ
って、従来の複合構造のホースに比べ、さらにガス透過
量を３０〜５０％削減でき、低透過性のホースを得るこ
とができる。
また本発明のホースは、高温下での樹脂変形をも抑え、
樹脂層の劣化を防止することもできる。
手続ネ甫正書（自発）
平ｔ７．０２年１０月１２日
１、事件の表示
平Ｆ！ｉ０１年特許願第２１１１４５号２、発明の名称
低透過性ホース
３、補正をする者
事件ヒの関係 特許出願人
名 称 （６７１）横浜ゴム株式会社４、代理人
住 所
〒１０１ 電話８６４−４４９８
東京都千代田区岩本町３丁目２番２号
６、補正の内容
（１）明細書第３頁第７行中の「ホースの柔軟性」を、
「樹脂層を使用した場合のホースの柔軟性」に補正する
。
（２）同書第４頁第２行中の「ホースを提供する」を、
「ゴム／樹脂複合構造の内管な有するホースを提供する
」に補正する。
（３）同書第５頁第２行中の「樹脂層を有し」を「樹脂
層を有する内管な有し」に、および第３行中の「樹脂層
内に」を「樹脂層を有する白雪上に」にそれぞれ補正す
る。
（４）同書第５頁第１３行中の「緩った」を、「撚った
」に補正する。
（５）同書第６頁第１３行中の「繊維がある」を「繊維
がある。」に補正する。
（６）同書第８頁第６行中の「多層構造内に」を、「多
層構造の白雪上に」に補正する。
（７）同−書第１５頁第１行中の「最内層」をｒ内管内
層」に、第３行中の「内層」を「内管外層」に、第４〜
５行中の「外層」を「外管」に、および第５行中の「内
層と外層」を「内管外層と外管」に、それぞれ補正する
。
（８）ｆ！］書第１５頁第１２行中のｒＪＡＲ規格」を
ｒＪＲＡ規格」に、および第１８〜１９行中のｒ ｇ
／ ｍ ７７２時間」をｒｇｆ／ｍ／７２時間」にそれ
ぞれ補正する。
（９）同書第１７頁中の表１を別紙の通り差し換える。[Polyether copolymers, etc. are used. Nylon resins include nylon 6, nylon 8, nylon 105, nylon 11, nylon 12, and nylon 6.
6, nylon 610, copolymers thereof, and polyamide resins containing these. Particularly when considering Freon gas permeation prevention and stress crack resistance at the same time, it is preferable to use polyamide resin containing nylon 12 as an essential component for nylon 11J5 and /*, or 40 to 80 parts by weight. nylon 6 and/or nylon 6/66 copolymer,
The resin composition preferably includes 5 to 30 parts by weight of nylon 11 and/or nylon 12 and 10 to 40 parts by weight of a polyolefin resin. Specific examples of polyamide resins containing nylon 11 and/or nylon 12 as essential components include nylon 11 and nylon 12 alone or in combination, 60% by weight or more of nylon 11 and /3I! Alternatively, a blend polymer of nylon 12 and 40% by weight of ungrooved other polyamide resins, such as nylon 6, etc. may be mentioned. In addition, 40 to 80 parts by weight of nylon 6 and/or nylon 6/66 copolymer, 5 to 30 parts by weight of nylon 1
In a resin composition consisting of 1 and/or nylon 12 and 10 to 40 parts by weight of polyolefin sin,
The polyolefin may be an α-olefin copolymer, and specific examples of the polyolefin include polyethylene, polypropylene, ethylene-propylene copolymers, and/or maleic acid adducts of these polymers. Other additives such as an anti-aging agent may be added to the resin composition as necessary (for example, a heat resistant agent of 0.03 to 0.5
% by weight and 3-10% by weight plasticizer addition). The above blending ratio provides the resin composition with stress resistance and
It is limited in order to have both crackability and flexibility. The aromatic polyamide resin is synthesized from metaxylylene cyanide and adipic acid, and is represented by the general formula (1).Specific examples include MXD6 (Toyobo Co., Ltd.)
Manufactured〉 etc. In addition, polyamide polyether copolymer is a block copolymer consisting of polyamide segments and polyether segments, and polyamide segments include nylon 6, nylon 11, nylon 12, nylon 6/66.
The polyether segment is made of polytetramethylene glycol, polypropylene glycol, polyethylene glycol and the like. Combining the components of boria 9-dosegments and polyether segments has resulted in copolymers exhibiting varying degrees of flexibility, melting point, and oil resistance. As a specific example, PEBAX 5533STO1,P
EBAX5S62MAOO%PHBAX 5512MN
0O (manufactured by Atochem Co., Ltd.), Diamid-PAE
Examples include E47 (manufactured by Daicel Hiels ■). The low permeability hose of the present invention preferably has a composite structure in which the above-mentioned rubber and/or resin are stacked in several layers together with the reinforcing layer. For example, it is a hose that has an inner pipe, a reinforcing layer, and an outer pipe, and depending on the purpose of use of the hose, usage conditions, etc., the inner pipe may have multiple layers, or a stress/peacock prevention layer may be provided. . As a method for manufacturing the low permeability hose of the present invention, known means can be applied. An example of a case is shown below. Using multiple extruders prepared according to the type of resin, the resin used to form the inner tube of the hose is placed on a mandrel pre-applied with a mold release agent and from a common multilayer extrusion head that connects each extruder. Extrusion to form a multilayer resin chain. The mandrel on which the resin chain has been formed is passed through a rubber extraction machine, and the rubber is extruded onto the resin tube to form a rubber inner tube outer layer. In addition, if necessary, a rubber layer can be formed after applying a chlorinated rubber-based, phenolic resin-based, HR) (based adhesive, etc.) to the surface of the resin tube using a heavy cloth, spray, etc. As described above. Using a C1 stripe assembling machine on the inner tube formed,
The reinforcing yarns under the conditions shown in the present invention are braided, and then a rubber outer tube is formed using a rubber extruder. The mandrel on which the inner tube, reinforcing layer and outer tube have been formed in this way is
The hose of the present invention is obtained by heating the pressurizer within a temperature range of 30 to 170°C, preferably 140 to 160°C, vulcanizing the rubber layer, cooling, and finally pulling out the mandrel. <Examples> The present invention will now be described in more detail based on Examples. (Example) Nylon 6 (58.2% by weight) and nylon 11 (14.5% by weight) were prepared by the method already described.
Using a material made of ethylene-propylene copolymer (27.3% by weight), the inner diameter is 11 mm, the wall thickness is o, ts mm.
The innermost layer is made of butyl rubber (IIR) material with a wall thickness of 1
．． A hose having a 5 mm inner layer, a 1.5 mm thick outer layer made of chlorinated butyl rubber (CX-IIR), and various reinforcing layers shown in Table 1 between the inner layer and the outer layer (Invention Example 1)
-4, Comparative Examples 1-4) were manufactured. Using these hoses, we investigated the amount of Freon gas permeated and the change in hose diameter during pressurization that affects this amount of permeation. The results are shown in Table 1. (Measurement method of Freon gas permeation amount) JAR standard (Japan Refrigeration and Air Conditioning Industry Association standard) JRA200
Conforms to 1. A refrigerant of O, S ± 0.1 g per 1 cm of inner volume of the hose is sealed in each of the above-mentioned hoses having a length of hose (free length 0.5 m). Temperature: Wo. The weight loss (gas permeation amount) was measured after hours and the value was converted to g/m/72 hours.In addition, the diameter change during pressurization was measured at 40 Kgf.
/cts2 The outside diameter of the hose when pressurized and the outside diameter of the hose when no pressure is applied were measured with a caliper and calculated by substituting it into the following formula [1]. Change in diameter when pressurized...・[1] As is clear from Table 1, polyester is used as the reinforcing thread of the reinforcing layer, and the polyester is subjected to a constant load (4,5K).
Threads with an elongation rate of 4% (gf/strand) have less yarn twist than those with an elongation rate of 3%, so the elongation increases, which is not preferable. Furthermore, since the elongation of the threads of acrylic and hard steel wires is extremely small, the change in diameter upon pressurization is caused by the angle factor, which greatly affects gas permeability. On the other hand, polyester yarn has a large elongation, so by making the braid angle larger than 54.75° (rest angle), the braid angle changes in the direction of the rest angle when pressure is applied, and the length of the hose (stretching the hose) is increased. This can prevent bulge in the radial direction of the hose.Furthermore, by reducing the load ratio (■1/safety factor) during pressurization, the load (elongation) per reinforcing thread can be suppressed. (Effects of the Invention) By including the reinforcing layer of the present invention in the composite structure of the hose, the amount of gas permeation can be further reduced by 30 to 50% compared to hoses with conventional composite structures, resulting in a hose with low permeability. The hose of the present invention also suppresses resin deformation under high temperatures,
It is also possible to prevent deterioration of the resin layer. Procedure Nefu Seisho (self-motivated) October 12, 2002 1, Incident display HeiF! i01 Patent Application No. 211145 2, Title of the invention: Low permeability hose 3, Relationship between the person making the amendment and the case: Patent applicant name (671) Yokohama Rubber Co., Ltd. 4, Agent address: 101 Telephone: 864-4498 Tokyo 3-2-2-6, Iwamoto-cho, Chiyoda-ku, Tokyo Contents of the amendment (1) "Hose flexibility" in line 7, page 3 of the specification.
Correct for "flexibility of the hose when using a resin layer". (2) “Provide a hose” in the second line of page 4 of the same book,
Amended to ``Provide a hose having an inner tube of rubber/resin composite structure.'' (3) In the second line of page 5 of the same book, “having a resin layer” has been changed to “having a resin layer”, and in the third line, “inside the resin layer” has been changed to “having a resin layer”. Correct each to ``On Snow White''. (4) "Loose" in line 13 of page 5 of the same book is corrected to "twisted." (5) In the same book, page 6, line 13, "There are fibers" is corrected to "There are fibers." (6) "Inside the multilayer structure" in line 6 of page 8 of the same book is amended to "on the white snow of the multilayer structure." (7) "Innermost layer" in the first line of page 15 of the same book is changed to "r inner tube inner layer", "inner layer" in the third line is changed to "inner tube outer layer", and fourth to
Correct "outer layer" in the 5th row to "outer tube" and correct "inner layer and outer layer" in the 5th row to "inner tube outer layer and outer tube". (8) f! ], page 15, line 12, rJAR standard” to rJRA standard”, and r g in lines 18-19.
/ m 772 hours" is corrected to "rgf/m/72 hours". (9) Replace Table 1 on page 17 of the same book as shown in the attached sheet.
Claims (3)
れる補強層を有する複合構造のホースにおいて、 前記補強層を構成する補強糸の一定荷重（４．５ｋｇｆ
／本）伸び率が３．５％以下であり、補強糸の編組角度
が５４．７５°超５６．０°以下の範囲であることを特
徴とする低透過性ホース。(1) In a hose with a composite structure having a reinforcing layer composed of a rubber and/or resin layer and a reinforcing thread, the reinforcing thread constituting the reinforcing layer has a constant load (4.5 kgf
/piece) A low permeability hose, characterized in that the elongation rate is 3.5% or less and the braiding angle of the reinforcing yarn is in the range of more than 54.75° and 56.0° or less.
荷が、補強糸破断強度の５〜１５％の範囲内となる耐圧
力を有する請求項１に記載の低透過性ホース。(2) The low permeability hose according to claim 1, which has a pressure resistance such that the load applied to the reinforcing yarn is within a range of 5 to 15% of the breaking strength of the reinforcing yarn when the hose is pressurized.
１または２に記載の低透過性ホース。(3) The low permeability hose according to claim 1 or 2, which has a diameter change of 0.5% or less when pressurized during use.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1211145A JPH0374691A (en) | 1989-08-16 | 1989-08-16 | Low permeable hose |
| KR1019900012262A KR0174261B1 (en) | 1989-08-16 | 1990-08-10 | Hose with low permeability |
| DE4026161A DE4026161C2 (en) | 1989-08-16 | 1990-08-15 | tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1211145A JPH0374691A (en) | 1989-08-16 | 1989-08-16 | Low permeable hose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0374691A true JPH0374691A (en) | 1991-03-29 |
| JPH0477194B2 JPH0477194B2 (en) | 1992-12-07 |
Family
ID=16601128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1211145A Granted JPH0374691A (en) | 1989-08-16 | 1989-08-16 | Low permeable hose |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH0374691A (en) |
| KR (1) | KR0174261B1 (en) |
| DE (1) | DE4026161C2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4962080A (en) * | 1988-03-08 | 1990-10-09 | Kanzaki Paper Mfg. Co., Ltd. | Image-receiving sheet for thermal dye-transfer recording |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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. |
| EP0609946A1 (en) * | 1993-02-05 | 1994-08-10 | Akzo Nobel N.V. | Product comprising reinforcing fibres of aromatic polyamide |
| KR20020047936A (en) * | 2000-12-14 | 2002-06-22 | 이계안 | Hose for auto transmission oil cooler |
| JP2007502726A (en) | 2003-08-19 | 2007-02-15 | ソルヴェイ アドバンスド ポリマーズ リミテッド ライアビリティ カンパニー | Polyamide hollow body with improved impact resistance |
| FR2909433B1 (en) | 2006-11-30 | 2014-01-10 | Arkema France | USE OF A MULTILAYER STRUCTURE FOR THE MANUFACTURE OF GAS PIPES, IN PARTICULAR METHANE. |
| CN102563236B (en) * | 2010-12-16 | 2014-09-17 | 杜邦公司 | Hose reinforcing composite rope made of contraposition aromatic polyamide fibers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50139426A (en) * | 1974-04-23 | 1975-11-07 | ||
| JPS6229242U (en) * | 1985-08-07 | 1987-02-21 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH064267B2 (en) * | 1985-06-27 | 1994-01-19 | 横浜ゴム株式会社 | Method for manufacturing hose provided with thin inner tube made of polyamide resin |
| JPS63125885A (en) * | 1986-11-13 | 1988-05-30 | 横浜ゴム株式会社 | Hose for transporting refrigerant |
| JPH0697076B2 (en) * | 1986-12-16 | 1994-11-30 | 横浜ゴム株式会社 | Low permeability hose |
-
1989
- 1989-08-16 JP JP1211145A patent/JPH0374691A/en active Granted
-
1990
- 1990-08-10 KR KR1019900012262A patent/KR0174261B1/en not_active IP Right Cessation
- 1990-08-15 DE DE4026161A patent/DE4026161C2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50139426A (en) * | 1974-04-23 | 1975-11-07 | ||
| JPS6229242U (en) * | 1985-08-07 | 1987-02-21 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4962080A (en) * | 1988-03-08 | 1990-10-09 | Kanzaki Paper Mfg. Co., Ltd. | Image-receiving sheet for thermal dye-transfer recording |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4026161C2 (en) | 1999-04-08 |
| DE4026161A1 (en) | 1991-02-21 |
| KR910004975A (en) | 1991-03-29 |
| JPH0477194B2 (en) | 1992-12-07 |
| KR0174261B1 (en) | 1999-02-18 |
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