JPH01269536A - Multilayered polyamide resin tube - Google Patents
Multilayered polyamide resin tubeInfo
- Publication number
- JPH01269536A JPH01269536A JP9793288A JP9793288A JPH01269536A JP H01269536 A JPH01269536 A JP H01269536A JP 9793288 A JP9793288 A JP 9793288A JP 9793288 A JP9793288 A JP 9793288A JP H01269536 A JPH01269536 A JP H01269536A
- Authority
- JP
- Japan
- Prior art keywords
- nylon
- polyamide
- resin layer
- flame
- tube
- 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 18
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000003063 flame retardant Substances 0.000 claims abstract description 17
- -1 polyoxymethylene Polymers 0.000 claims abstract description 17
- 229920000571 Nylon 11 Polymers 0.000 claims abstract description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 14
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004952 Polyamide Substances 0.000 claims abstract description 14
- 229920002647 polyamide Polymers 0.000 claims abstract description 14
- 229920000299 Nylon 12 Polymers 0.000 claims abstract description 13
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 7
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims abstract description 6
- 239000000806 elastomer Substances 0.000 claims abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- NLJYVSRAICBDSH-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,15-triacontachlorocyclopentadecane Chemical compound ClC1(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C1(Cl)Cl NLJYVSRAICBDSH-UHFFFAOYSA-N 0.000 description 1
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 101150104684 UL44 gene Proteins 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZIWYFFIJXBGVMZ-UHFFFAOYSA-N dioxotin hydrate Chemical compound O.O=[Sn]=O ZIWYFFIJXBGVMZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 101150002378 gC gene Proteins 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LKOCAGKMEUHYBV-UHFFFAOYSA-N tris(3-bromo-3-chloropropyl) phosphate Chemical compound ClC(Br)CCOP(=O)(OCCC(Cl)Br)OCCC(Cl)Br LKOCAGKMEUHYBV-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はポリアミド樹脂チューブに関し、その目的はガ
ソリン、水等に対する透過性の小さい難燃性かつ柔軟性
をもったチューブを堤供することにある。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a polyamide resin tube, and its purpose is to provide a flame-retardant and flexible tube with low permeability to gasoline, water, etc. .
（従来技術および課題）
一般にナイロン１１又はナイロン１２を主体とする樹脂
よりなるナイロン系樹脂チューブは、高圧ホース用チュ
ーブ、自動車用燃料チューブ、クラッチチューブ、カー
クーラ用チューブ、エアーブレーキ配管等、特に高度な
信顆性を要求される分野に広く用いられている。これら
のうち特に自動車フューエルチューブ、クラッチチュー
ブ、カークーラホース用チューブには、ガソリン、フレ
オン等の漏洩を防ぐため、これらのチューブ壁を通して
のガソリン等の透過性が小さいこと、および外気からの
水分の侵入を防ぐため、水の透過性が小さいことが要求
されると同時に、その組立作業上柔軟であることが要求
される。(Prior Art and Problems) Generally, nylon resin tubes made of resin mainly composed of nylon 11 or nylon 12 are used for high-pressure hose tubes, automobile fuel tubes, clutch tubes, car cooler tubes, air brake piping, etc. It is widely used in fields where reliability is required. Among these, in particular, automobile fuel tubes, clutch tubes, and car cooler hose tubes are designed to have low permeability for gasoline, etc. through the walls of these tubes, and to prevent moisture from leaking from the outside air, in order to prevent leakage of gasoline, Freon, etc. In order to prevent intrusion, it is required to have low water permeability, and at the same time, it is required to be flexible in terms of assembly.
さらにこれらチューブ、ホースが例えば溶接用ロボット
のように複雑な動作を行ない、燃焼の恐れが極めて高い
環境で使用されることもあるが、このよううな場合本来
自消性のポリアミド樹脂も十分満足して使用できるもの
ではない。Furthermore, these tubes and hoses are sometimes used in environments where the risk of combustion is extremely high, such as in welding robots, where they perform complex movements, and in such cases polyamide resin, which is inherently self-extinguishing, is not sufficient. It is not something that can be used.
ナイロン１１、ナイロン１２はガソリン、フレオン等の
無極性化合物に対しても、水のような極性化合物に対し
ても共に小さい透過性を有するが、あまりにも硬くその
チューブは組立作業に適さない。このため−船釣にはこ
のような用途に可塑化されたナイロン１１、ナイロン１
２が用いられるが、可塑化されたナイロンは透過性が大
きい欠点がある。一方、ナイロン１１又はナイロン１２
を可塑化しないで柔軟にする方法として、ナイロン１１
又はナイロン１２をポリテトラヒドロフランと共重合さ
せる方法が知られているが、この共重合体は更に透過性
が大きい欠点がある。Nylon 11 and nylon 12 have low permeability to both non-polar compounds such as gasoline and Freon, as well as to polar compounds such as water, but are too hard and the tubes are not suitable for assembly work. For this reason, for boat fishing, plasticized nylon 11 and nylon 1 are used for boat fishing.
2 is used, but plasticized nylon has the disadvantage of high permeability. On the other hand, nylon 11 or nylon 12
Nylon 11 is a method to make it flexible without plasticizing it.
Alternatively, a method is known in which nylon 12 is copolymerized with polytetrahydrofuran, but this copolymer also has the disadvantage of high permeability.
またナイロンの難燃化には臭素系、塩素系、リン系など
の難燃剤を添加することによってなされるが、これら難
燃化されたポリアミドをチューブに用いると、添加した
難燃剤が溶出するばかりでなく、チューブ中を通過する
ガソリン、フレオンまたは水などの透過性を増大させて
しまう。Additionally, nylon can be made flame retardant by adding bromine, chlorine, or phosphorus flame retardants, but if these flame retardant polyamides are used for tubes, the added flame retardants will simply leach out. Instead, it increases the permeability of gasoline, Freon, or water through the tube.
本発明者は難燃、柔軟かつ透過性の小さいポリアミド樹
脂チューブを得るべく鋭意検討した結果、本発明に至っ
たものである。The inventors of the present invention have conducted intensive studies to obtain a polyamide resin tube that is flame retardant, flexible, and has low permeability, and as a result, they have arrived at the present invention.
（課題を解決するための手段）
すなわち、本発明は内側がナイロン１１又はナイロン１
２より成る樹脂層で構成され、外側がハードセグメント
をポリアミド、ソフトセグメントをポリオキシメチレン
とするポリアミドエラストマー共重合体を主成分とする
難燃性ポリアミド樹脂層で構成されていることを特徴と
する多層ポリアミド樹脂チューブである。(Means for Solving the Problem) That is, the present invention has a structure in which the inside is made of nylon 11 or nylon 1.
The outer layer is composed of a flame-retardant polyamide resin layer whose main component is a polyamide elastomer copolymer with hard segments made of polyamide and soft segments made of polyoxymethylene. It is a multilayer polyamide resin tube.
本発明のチューブ内側に配されるナイロン１１とは、１
１−アミノウンデカン酸の重合体であり、ナイロン１２
とはラウリルラクタムまたは１２−アミノドデカン酸の
重合体であり、またはこれらのモノマーを主成分とした
共重合体である。また透過性を著しく増大させない程度
の可塑剤、滑剤、安定剤等を含んでいてもよい。The nylon 11 arranged inside the tube of the present invention is 1
A polymer of 1-aminoundecanoic acid, nylon 12
is a polymer of lauryllactam or 12-aminododecanoic acid, or a copolymer containing these monomers as a main component. Furthermore, it may contain plasticizers, lubricants, stabilizers, etc. to the extent that they do not significantly increase permeability.
本発明のチューブ外側に配される難燃性ポリアミド樹脂
は、ハードセグメントをポリアミド、ソフトセグメント
をポリオキシメチレンとするポリアミドエラストマーを
主成分とする難燃性ポリアミド樹脂である。The flame-retardant polyamide resin arranged on the outside of the tube of the present invention is a flame-retardant polyamide resin whose main component is a polyamide elastomer in which the hard segment is polyamide and the soft segment is polyoxymethylene.
ハードセグメントとしてのポリアミドには、ナイロン６
、ナイロン１１、ナイロン１２、ナイロン６６、ナイロ
ン６１０、ナイロン６１２等が例示できるが、好ましく
はナイロン１１又はナイロン１２である。Polyamide as a hard segment includes nylon 6
, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612, etc., but nylon 11 or nylon 12 is preferable.
ソフトセグメントとしてのポリオキシメチレンには、テ
トラヒドロフランスは１，４−ブタンジオールの重合体
であるポリオキシテトラメチレングリコールや、その両
末端をアミノ化、カルボキシル化等の処理をしたものが
用いられる。ソフトセグメントの数平均重合度は１６０
〜３０００が好ましく、１０００前後が最も好ましい。For polyoxymethylene as the soft segment, polyoxytetramethylene glycol, which is a polymer of 1,4-butanediol (tetrahydrofuran), or polyoxytetramethylene glycol, which is treated with amination, carboxylation, etc. at both ends, is used. The number average degree of polymerization of the soft segment is 160
~3000 is preferred, and around 1000 is most preferred.
本共重合体１００重量部中のポリアミド成分は３０〜９
５重量部好ましくは４０〜７０重量部であり、ポリオキ
シメチレン成分は５〜７０重量部好ましくは２０〜５０
重量部である。The polyamide component in 100 parts by weight of this copolymer is 30 to 9
5 parts by weight, preferably 40 to 70 parts by weight, and the polyoxymethylene component is 5 to 70 parts by weight, preferably 20 to 50 parts by weight.
Parts by weight.
本共重合体には、さらにポリアミド成分と、ポリオキシ
メチレン成分を結びつける二塩基酸のようなものを含ん
でいてもよい。二塩基酸としては一般式
％式％
（×は４〜１１の値）
の脂肪族ジカルボン酸が使用され、例えばアジピン酸、
ピメリン酸、スペリン酸、アゼライン酸、セバシン酸、
デカンジカルボン酸等が挙げられる。The copolymer may further contain something such as a dibasic acid that binds the polyamide component and the polyoxymethylene component. As the dibasic acid, aliphatic dicarboxylic acids having the general formula % (x is a value of 4 to 11) are used, such as adipic acid,
pimelic acid, speric acid, azelaic acid, sebacic acid,
Examples include decanedicarboxylic acid.
更に少なくとも８の炭素原子数を有する環状脂肪族ジカ
ルボン酸及び／または芳香族ジカルボン酸、例えばヘキ
サヒドロテレフタル酸、テレフタル酸、イソフタル酸、
フタル酸またはナフタリンジカルボン酸等が挙げられる
。Furthermore, cycloaliphatic dicarboxylic acids and/or aromatic dicarboxylic acids having at least 8 carbon atoms, such as hexahydroterephthalic acid, terephthalic acid, isophthalic acid,
Examples include phthalic acid and naphthalene dicarboxylic acid.
更に特願昭６２−１４４７９７号に記載されている共重
合体１００重量部に対し、ハロゲン化ゴム３０〜１００
重量部配合してなるポリアミド樹脂も好ましく用いられ
る。Furthermore, 30 to 100 parts of halogenated rubber is added to 100 parts by weight of the copolymer described in Japanese Patent Application No. 144797/1983
A polyamide resin formed by blending in parts by weight is also preferably used.
本共重合体に添加する難燃剤はどのようなものでもよい
が、一般に用いられるトリクレジルホスフェート、クレ
ジルフェニルホスフェート、オクチルフェニルホスフェ
ート等に代表されるリン酸エステル系、トリス（２，３
−ブロモプロピル）ホスフェート、トリス（ブロモクロ
ロプロピル）ホスフェートに代表されるハロゲン化リン
酸エステル系、芳香族ポリホスフェート、デカブロモジ
フェニルエーテル、デカブロモビフェニル、ヘキサブロ
ムベンゼン、テトラブロモビスフェノールＡ、パークロ
ロシクロペンタデカン、ポリジブロムフェニレンオキサ
イド等に代表される含ハロゲン難燃剤、酸化アンチモン
、メタホウ酸バリウム、酸化スズ水和物、水酸化アルミ
ニウム等の無機系灘燃剤のいずれを使用してもよく、こ
れらの一種又は二種以上を混合して使用することができ
る。Any flame retardant may be added to the present copolymer, but phosphoric acid esters such as commonly used tricresyl phosphate, cresyl phenyl phosphate, octylphenyl phosphate, tris(2,3
- Halogenated phosphate esters represented by bromopropyl) phosphate, tris(bromochloropropyl)phosphate, aromatic polyphosphate, decabromodiphenyl ether, decabromobiphenyl, hexabromobenzene, tetrabromobisphenol A, perchlorocyclopentadecane , halogen-containing flame retardants such as polydibrophenylene oxide, and inorganic flame retardants such as antimony oxide, barium metaborate, tin oxide hydrate, and aluminum hydroxide may be used. Two or more types can be used in combination.
難燃剤の量は、用いる難燃剤によって異なるがナイロン
１００重量部に対して５〜７０重量部であり、好ましく
は１０〜３０重量部である。The amount of flame retardant varies depending on the flame retardant used, but is 5 to 70 parts by weight, preferably 10 to 30 parts by weight, per 100 parts by weight of nylon.
本発明のチューブは多層構造を有するポリアミド樹脂チ
ューブである。内外二層構造を有し、その内層がナイロ
ン１１又はナイロン１２より成る樹脂層で、外層が難燃
性ポリアミド共重合体より成る樹脂層で構成されるチュ
ーブが代表的なものであるが、この内外層の中間に、こ
れらのポリアミド樹脂又はその他の樹脂からなる−又は
二以上の中間樹脂層を有する多層ポリアミド樹脂チュー
ブも含まれる。The tube of the present invention is a polyamide resin tube having a multilayer structure. A typical tube has a two-layered structure, the inner layer being a resin layer made of nylon 11 or nylon 12, and the outer layer being a resin layer made of a flame-retardant polyamide copolymer. Also included are multilayer polyamide resin tubes having one or more intermediate resin layers made of these polyamide resins or other resins between the inner and outer layers.
本発明のチューブにあってその効果を発揮するにあたり
内側の樹脂の肉厚はチューブ全体の肉厚の１／１００以
上が望ましい。In order for the tube of the present invention to exhibit its effects, the thickness of the inner resin is preferably 1/100 or more of the thickness of the entire tube.
本発明のチューブは共押出の方法によって作られる。こ
れは２つ以上の押出機を用いて、同心円状に配された２
つのチューブダイから異種樹脂を吐出させて２層チュー
ブを作る方法であり、その特徴とするところは、ナイロ
ン１１又はナイロン１２と難燃性ポリアミド樹脂が溶融
状態で接触することにある。溶融状態での接触によって
両樹脂は良好に接着するのが特徴である。The tube of the present invention is made by the method of coextrusion. This uses two or more extruders, two or more extruders arranged concentrically.
This is a method of making a two-layer tube by discharging different resins from two tube dies, and its feature is that nylon 11 or nylon 12 and flame-retardant polyamide resin come into contact in a molten state. The two resins are characterized by good adhesion by contact in the molten state.
（発明の効果）
従来の多層チューブは屈曲に伴い界面剥離を生じ、チュ
ーブとしての諸性質が著しく低下することが多いが、本
発明のチューブはいかなる屈曲を与えても界面剥離が起
らず、柔軟で単一層チューブと同様に容易に取扱うこと
ができ１．かつ難燃性及び低い透過性が得られる。(Effects of the Invention) Conventional multilayer tubes often suffer from interfacial delamination when bent, resulting in a significant deterioration of various properties as a tube, but the tube of the present invention does not suffer from interfacial delamination no matter how bent it is. It is flexible and can be easily handled like a single layer tube.1. Moreover, flame retardancy and low permeability can be obtained.
（実施例） 以下に本発明の実施例を示す。(Example) Examples of the present invention are shown below.
実施例１〜９
内側樹脂層及び外側樹脂層に表１に示した樹脂を使用し
、内側樹脂用に３０止φ押出機、外側樹脂用に４０止φ
押出機を用いて共押出を行い、バキュームボックスサイ
ジング法により内径６鴎φ、外径８ｆｉφのチューブを
作った。チューブを屈曲させ界面での剥離を観察した後
、２０ａｍのチューブを用意し、これにガソリンを封入
し５０°Ｃの熱風乾燥炉中に５日間放置して重量減少を
測定した。Examples 1 to 9 The resins shown in Table 1 were used for the inner resin layer and the outer resin layer, and a 30-stop φ extruder was used for the inner resin and a 40-stop φ extruder was used for the outer resin.
Coextrusion was performed using an extruder, and a tube with an inner diameter of 6 mm and an outer diameter of 8 fi was produced by a vacuum box sizing method. After bending the tube and observing peeling at the interface, a 20 am tube was prepared, filled with gasoline, and left in a hot air drying oven at 50° C. for 5 days to measure weight loss.
減少量がチューブを透過したガソリン量と考えられる。The amount of decrease is considered to be the amount of gasoline that permeated through the tube.
燃焼試験はＵＬ４４の水平燃焼試験に準処して行なった
。結果を表１に示す。The combustion test was conducted in accordance with the UL44 horizontal combustion test. The results are shown in Table 1.
比較例１〜７
単一樹脂層のチューブ及び内側樹脂層と外側樹脂層に表
２に示した樹脂を使用して実施例１と同様の方法で作っ
た多層チューブについて、実施例１と同様の試験を行な
った。結果を表２に示す。Comparative Examples 1 to 7 A tube with a single resin layer and a multilayer tube made in the same manner as in Example 1 using the resins shown in Table 2 for the inner resin layer and outer resin layer were treated in the same manner as in Example 1. I conducted a test. The results are shown in Table 2.
手 続 補 正 書 （自発）昭和６３年５月
３０日
１、事件の表示
昭和６３年特許願第９７９３２号
２、発明の名称
多層ポリアミド樹脂チューブ
３、補正をする者
事件との関係 特許出願人
邦便番号 １００
住 所 東京都千代田区霞が関三丁目８番１号代表
者氏名 紫垣明典 ・１、二・□ｊ＼＼
−
６、補正の内容
（１）明細書第６頁第１１行〜第１４行の「更に特願昭
６２−１４４７９７号に・・・・・・・・・・・・・好
ましく用いられる。」を削除する。Procedural Amendment (Spontaneous) May 30, 1988 1. Indication of the case Patent Application No. 97932 of 1988 2. Name of the invention Multilayer polyamide resin tube 3. Person making the amendment Relationship to the case Patent applicant Japanese mail number 100 Address 3-8-1 Kasumigaseki, Chiyoda-ku, Tokyo Representative name Akinori Shigaki ・1, 2・□j\\
- 6. Contents of the amendment (1) "Furthermore preferably used in Japanese Patent Application No. 144797/1983" on page 6, lines 11 to 14 of the specification. Delete.
（２）明細書７頁１３行と１４行の間に次の文を加入す
る。(2) Add the following sentence between lines 13 and 14 on page 7 of the specification.
［更に特願昭６２−１４４７９７号に記載されている共
重合体１００重量部に対し、ハロゲン化ゴム３０〜１０
０重量部を配合してなるポリアミド樹脂も好ましく用い
られる。Ｊ以上[Additionally, 30 to 10 parts by weight of halogenated rubber is added to 100 parts by weight of the copolymer described in Japanese Patent Application No. 144797/1982
A polyamide resin containing 0 parts by weight is also preferably used. J or above
Claims (1)
構成され、外側がハードセグメントをポリアミド、ソフ
トセグメントをポリオキシメチレンとするポリアミドエ
ラストマー共重合体を主成分とする難燃性ポリアミド樹
脂層で構成されていることを特徴とする多層ポリアミド
樹脂チューブ。The inner layer is composed of a resin layer made of nylon 11 or nylon 12, and the outer layer is composed of a flame-retardant polyamide resin layer whose main component is a polyamide elastomer copolymer with hard segments made of polyamide and soft segments made of polyoxymethylene. A multilayer polyamide resin tube characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9793288A JPH01269536A (en) | 1988-04-20 | 1988-04-20 | Multilayered polyamide resin tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9793288A JPH01269536A (en) | 1988-04-20 | 1988-04-20 | Multilayered polyamide resin tube |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01269536A true JPH01269536A (en) | 1989-10-27 |
Family
ID=14205447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9793288A Pending JPH01269536A (en) | 1988-04-20 | 1988-04-20 | Multilayered polyamide resin tube |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01269536A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010520827A (en) * | 2007-03-13 | 2010-06-17 | ディーエスエム アイピー アセッツ ビー．ブイ． | Plastic tubes for use in automotive air brake systems |
| EP3670184A1 (en) | 2018-12-20 | 2020-06-24 | EMS-Patent AG | Fluid transport line and its use |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5736657A (en) * | 1980-08-13 | 1982-02-27 | Daicel Chem | HORIAMIDOKEIJUSHICHUUBU |
-
1988
- 1988-04-20 JP JP9793288A patent/JPH01269536A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5736657A (en) * | 1980-08-13 | 1982-02-27 | Daicel Chem | HORIAMIDOKEIJUSHICHUUBU |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010520827A (en) * | 2007-03-13 | 2010-06-17 | ディーエスエム アイピー アセッツ ビー．ブイ． | Plastic tubes for use in automotive air brake systems |
| EP3670184A1 (en) | 2018-12-20 | 2020-06-24 | EMS-Patent AG | Fluid transport line and its use |
| US11254083B2 (en) | 2018-12-20 | 2022-02-22 | Ems-Patent Ag | Fluid transport pipe and use thereof |
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