JPH0753823A - Resin composition - Google Patents
Resin compositionInfo
- Publication number
- JPH0753823A JPH0753823A JP20338193A JP20338193A JPH0753823A JP H0753823 A JPH0753823 A JP H0753823A JP 20338193 A JP20338193 A JP 20338193A JP 20338193 A JP20338193 A JP 20338193A JP H0753823 A JPH0753823 A JP H0753823A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyamide
- weight
- tube
- layer
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、優れた物性と、フッ素
樹脂とポリアミド樹脂との両方に優れた接着性能を持つ
フッ素樹脂とポリアミド樹脂を含むブレンド樹脂組成物
に関するものである。また、この組成物を一層にもつ、
ガソリン、アルコール、酸等に対する耐薬品性や透過防
止性、チューブとしての柔軟性、耐衝撃性等に優れた性
質を持つ樹脂多層チューブに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blended resin composition containing a fluororesin and a polyamide resin, which has excellent physical properties and excellent adhesiveness to both the fluororesin and the polyamide resin. Also, with this composition as one layer,
The present invention relates to a resin multilayer tube having excellent properties such as chemical resistance and permeation resistance to gasoline, alcohol, acid, etc., flexibility as a tube, and impact resistance.
【０００２】[0002]
【従来技術及びその問題点】ポリアミド樹脂は諸特性の
バランスのとれた材料であり、特に高強度、靱性、耐疲
労強度、耐摩擦・磨耗性、加工性等に特徴を有し、自動
車部品、電気部品、一般機械部品等多くの用途に使用さ
れている。可塑剤を含有した柔軟ポリアミドは自動車、
自動機械、ロボット等のチューブ、ホースインナーチュ
ーブ等として広く応用されている。しかしながら通常の
一般用途のチューブより過酷な使用用途においてはその
要求特性を満たしていない。例えば、自動車用フューエ
ルチューブにおいては公害上の問題から要求されている
ガソリンまたはアルコール配合ガソリン燃料透過防止性
に対しては十分ではない。さらに、サワー化したガソリ
ンに対しても耐性が充分なものではなかった。2. Description of the Related Art Polyamide resin is a material in which various properties are well balanced, and is particularly characterized by high strength, toughness, fatigue strength, friction / wear resistance, workability, etc. It is used in many applications such as electrical parts and general mechanical parts. Flexible polyamide containing plasticizer is used for automobiles,
Widely applied as tubes for automatic machines, robots, hose inner tubes, etc. However, it does not meet the required characteristics in applications that are more demanding than ordinary tubes for general applications. For example, in a fuel tube for automobiles, it is not sufficient to prevent permeation of gasoline or alcohol-blended gasoline fuel due to pollution problems. In addition, it was not sufficiently resistant to sour gasoline.
【０００３】一方、ＥＴＦＥ共重合体は、耐薬品性・柔
軟性・耐低温衝撃性・難燃性に優れ各種用途に使用され
てきた。しかし、テトラフルオロエチレンとエチレンに
基づく単位からなる共重合体（以下ＥＴＦＥ共重合体と
いう）は、材料コストが高くまた、成形性が良くないた
めにチューブ等の成形品にした場合非常にコスト高なも
のとなり一般的に使用が制限されてきた。On the other hand, ETFE copolymers have been used for various purposes because of their excellent chemical resistance, flexibility, low temperature impact resistance and flame retardancy. However, a copolymer composed of tetrafluoroethylene and a unit based on ethylene (hereinafter referred to as ETFE copolymer) has a high material cost, and since the moldability is poor, the cost is extremely high when a molded product such as a tube is used. However, its use has been generally restricted.
【０００４】そこで、ポリアミド樹脂およびフッ素樹脂
の改良および価格改善のために、種々の樹脂とのポリマ
ーブレンドおよび積層体の製造検討もなされてきた。Therefore, in order to improve the polyamide resin and the fluororesin and to improve the price, the production of polymer blends and laminates with various resins have been studied.
【０００５】しかし、ポリアミド樹脂とフッ素樹脂の積
層体を製造するにあたっては、ポリアミド樹脂とフッ素
樹脂の間に相溶性・接着性がないためそのまま共押出成
形しても、接着力が全く無く、使用中に層剥離が生じチ
ューブ閉塞等種々の問題が発生する可能性があった。However, in the production of a laminate of a polyamide resin and a fluororesin, there is no compatibility or adhesiveness between the polyamide resin and the fluororesin, and even if it is coextruded as it is, there is no adhesive force and it is used. There is a possibility that delamination may occur inside and various problems such as tube clogging may occur.
【０００６】そこで、この問題を解決するために種々の
検討がなされ、例えば、特開平５−８３５３号公報には
フッ素樹脂とポリアミド樹脂との多層チューブを製造す
るにあたり、フッ素樹脂とポリアミド樹脂との両層の分
子間に、放射線照射し、架橋構造を導入することによっ
て接着力を高めようとする特許が提案されている。Therefore, various investigations have been made to solve this problem. For example, in Japanese Unexamined Patent Publication No. Hei 5-8353, in manufacturing a multilayer tube of a fluororesin and a polyamide resin, a fluororesin and a polyamide resin are used. Patents have been proposed which attempt to enhance the adhesive force by irradiating radiation between the molecules of both layers to introduce a crosslinked structure.
【０００７】しかし、この方法でも、放射線照射用の装
置が必要であり、また、製造工程も通常の共押出成形よ
りも２〜３以上の工程が必要であり、やはりコストの高
いものになっていた。However, this method also requires an apparatus for radiation irradiation, and the manufacturing process requires 2-3 or more steps as compared with ordinary coextrusion molding, which also results in high cost. It was
【０００８】[0008]
【発明の目的】本発明の目的は、フッ素樹脂とポリアミ
ド樹脂との双方に対して優れた接着性を持ち、しかも優
れた物性を有する組成物を提供することにある。また、
この組成物を一層にもつ、ガソリン、アルコール、酸等
に対する耐薬品性や透過防止性、チューブとしての柔軟
性、耐衝撃性等に優れた性質を持つチューブを提出する
ことにあり、具体的には、内層がフッ素樹脂、接着層が
優れた物性と、フッ素樹脂とポリアミド樹脂との双方に
対する優れた接着性能を持つフッ素樹脂とポリアミド樹
脂を含む樹脂組成物、外層がポリアミド樹脂のすくなく
とも３層からなる樹脂多層チューブを提供することにあ
る。OBJECT OF THE INVENTION It is an object of the present invention to provide a composition having excellent adhesiveness to both fluororesin and polyamide resin and having excellent physical properties. Also,
It is to submit a tube having this composition as one layer, which has excellent properties such as chemical resistance and permeation resistance to gasoline, alcohol, acid, etc., flexibility as a tube, impact resistance, etc. Is a resin composition containing a fluororesin and a polyamide resin having an inner layer made of a fluororesin, an adhesive layer having excellent physical properties, and excellent adhesion performance to both a fluororesin and a polyamide resin, and an outer layer comprising at least three layers of a polyamide resin. Another object is to provide a resin multilayer tube.
【０００９】[0009]
【問題点を解決するための手段】上記課題を解決するた
めに、本発明にあっては、ポリアミド樹脂、ＥＴＦＥ共
重合体とからなる樹脂組成物を製造し、ポリアミド樹脂
およびフッ素樹脂の双方に対する接着性を付与させるた
めのものである。In order to solve the above problems, according to the present invention, a resin composition comprising a polyamide resin and an ETFE copolymer is produced, and both polyamide resin and fluororesin are prepared. It is for imparting adhesiveness.
【００１０】本発明で用いるポリアミド樹脂の例として
は、溶融成形に優れたものが好ましく、ポリアミド−１
１、ポリアミド−１２、ポリアミド−６、ポリアミド−
６６、ポリアミド６−１０、ポリアミド６−１２、ポリ
アミド１２−１２、ポリアミドエラストマー等が例示さ
れるが、ＥＴＦＥ共重合体の成形温度の上限である３２
０℃以下に融点あるいは流動点を有するものであれば、
特にその組成を限定するものではない。また、あるいは
耐衝撃性改良のためＮＢＲ等の耐衝撃強度改良剤を添加
したものを使用することも可能である。また、耐熱剤・
耐候剤・滑剤等を添加してもよい。As an example of the polyamide resin used in the present invention, one excellent in melt molding is preferable, and polyamide-1
1, polyamide-12, polyamide-6, polyamide-
66, polyamide 6-10, polyamide 6-12, polyamide 12-12, polyamide elastomer and the like are exemplified, but the upper limit of the molding temperature of the ETFE copolymer is 32.
If it has a melting point or pour point below 0 ° C,
The composition is not particularly limited. Further, it is also possible to use those to which an impact resistance improver such as NBR is added for improving impact resistance. In addition,
A weathering agent and a lubricant may be added.
【００１１】本発明で用いるポリアミド樹脂の含有率
は、５〜５０重量％が適切であり、好ましくは、１０〜
４０重量％である。ポリアミド樹脂の含有率が、５重量
％以下になるとポリアミド樹脂との接着性が低下し好ま
しくなく、ポリアミド樹脂の含有率が、５０重量％以上
になると、フッ素樹脂との接着性が低下し好ましくな
い。The content of the polyamide resin used in the present invention is appropriately 5 to 50% by weight, preferably 10 to 50% by weight.
It is 40% by weight. When the content of the polyamide resin is 5% by weight or less, the adhesion with the polyamide resin is unfavorably decreased, and when the content of the polyamide resin is 50% by weight or more, the adhesion with the fluororesin is decreased, which is not preferable. .
【００１２】本発明で用いるＥＴＦＥ共重合体として
は、テトラフルオロエチレンに基づく単位、エチレンに
基づく単位、およびこれらと共重合可能で共重合体に側
鎖を与える含フッ素ビニルモノマーに基づく単位を含ん
でなる共重合体であり、テトラフルオロエチレンとエチ
レン単位およびエチレン単位の含有モル比が６２：３８
〜９０；１０であって、含フッ素ビニルモノマーの単位
の含有量がテトラフルオロエチレン単位およびエチレン
に基づく単位の合計モル数に対して０．１〜５モル％で
あることが好ましい。The ETFE copolymer used in the present invention includes a unit based on tetrafluoroethylene, a unit based on ethylene, and a unit based on a fluorine-containing vinyl monomer which is copolymerizable therewith and gives a side chain to the copolymer. And a molar ratio of tetrafluoroethylene to ethylene units and ethylene units is 62:38.
It is preferable that the content of the fluorine-containing vinyl monomer unit is 0.1 to 5 mol% with respect to the total number of moles of the tetrafluoroethylene unit and the unit based on ethylene.
【００１３】また、本発明で用いられる含フッ素ビニル
モノマー単位は、式； ［式中、Ｘは水素またはフッ素、Ｒｆはフルオロアルキ
ル基をあらわす。］で示される。The fluorine-containing vinyl monomer unit used in the present invention has the formula: [In the formula, X represents hydrogen or fluorine, and Rf represents a fluoroalkyl group. ] Is shown.
【００１４】本発明で用いるＥＴＦＥ共重合体の含有率
は、５０〜９５重量％が適切であり、好ましくは、６０
〜９０重量％である。ＥＴＦＥ共重合体の含有率が５０
重量％以下になるとフッ素樹脂との接着性が低下し好ま
しくなく、ＥＴＦＥ共重合体の含有率が９５重量％以上
になるとポリアミド樹脂との接着性が低下し好ましくな
い。The content of the ETFE copolymer used in the present invention is suitably 50 to 95% by weight, preferably 60.
Is about 90% by weight. ETFE copolymer content is 50
If it is less than 10% by weight, the adhesiveness to the fluororesin is lowered, which is not preferable.
【００１５】本発明で用いる可塑剤の例としては、Ｎブ
チルベンゼンスルホン酸アミド、２−エチル−ｐ−ヒド
ロオキシベンゾエート等が挙げられ、幾つかの種類を併
用することも可能である。Examples of the plasticizer used in the present invention include N-butylbenzenesulfonic acid amide, 2-ethyl-p-hydroxybenzoate and the like, and it is possible to use several kinds in combination.
【００１６】本発明で用いる可塑剤の含有率としては、
０〜５０重量％が適切であり、好ましくは、０〜３０重
量％である。この可塑剤は、本発明において必須条件で
はないがこれを加えることによってポリアミド樹脂とＥ
ＴＦＥ共重合体の相溶性が向上し、低温衝撃性等の物性
が向上する。但し、この含有率が５０重量％を越える
と、ポリアミド樹脂とＥＴＦＥ共重合体双方への接着性
が低下し好ましくない。The content of the plasticizer used in the present invention is as follows.
0-50% by weight is suitable, preferably 0-30% by weight. This plasticizer is not an essential condition in the present invention, but by adding it, the polyamide resin and E
The compatibility of the TFE copolymer is improved, and physical properties such as low temperature impact resistance are improved. However, if this content exceeds 50% by weight, the adhesiveness to both the polyamide resin and the ETFE copolymer decreases, which is not preferable.
【００１７】本発明のラジカル発生剤の存在下で不飽和
カルボン酸もしくは、その無水物と共にポリアミド樹脂
とすくなくともＥＴＦＥ共重合体を単軸または、２軸混
練機にて混合することを特徴とする樹脂組成物の製造方
法に用いる、ラジカル発生剤の例としては、公知の有機
過酸化物、ジアゾ化合物が挙げられ、好ましい例として
は、ｔｅｒｔ−ブチルハイドロパーオキサイド、ジーｔ
ｅｒｔ−ブチルパーオキシド、ベンゾイルパーオキサイ
ドなどが挙げられる。ラジカル発生剤の使用量として
は、樹脂１００重量部に対して、０．０１〜２重量部で
ある。配合量が前記下限値より少ない場合には、得られ
た組成物の接着性・耐衝撃性が十分でなく、配合量が前
記上限値より多い場合には、それ以上添加しても接着性
・耐衝撃性の向上効果が顕著でなく種々の問題を生じる
場合があり好ましくない。A resin characterized by mixing a polyamide resin and at least an ETFE copolymer together with an unsaturated carboxylic acid or its anhydride in the presence of the radical generator of the present invention in a uniaxial or biaxial kneader. Examples of the radical generator used in the method for producing the composition include known organic peroxides and diazo compounds, and preferable examples include tert-butyl hydroperoxide and di-t.
Examples include ert-butyl peroxide and benzoyl peroxide. The amount of the radical generator used is 0.01 to 2 parts by weight with respect to 100 parts by weight of the resin. If the blending amount is less than the lower limit value, the adhesiveness / impact resistance of the obtained composition is not sufficient. The effect of improving the impact resistance is not remarkable and various problems may occur, which is not preferable.
【００１８】また本発明に使用される不飽和カルボン酸
もしくは、その無水物の好ましい例としては、マレイン
酸、無水マレイン酸、イタコン酸、無水イタコン酸、無
水ハイミック酸、無水グルタコン酸、フタル酸、無水フ
タル酸等を例示することができる。Further, preferred examples of the unsaturated carboxylic acid or its anhydride used in the present invention include maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, hymic acid anhydride, glutaconic anhydride, phthalic acid, Examples thereof include phthalic anhydride and the like.
【００１９】本発明に利用される不飽和カルボン酸もし
くは、その無水物の配合量としては、樹脂１００重量部
に対して、０．０１〜２重量部であり、好ましくは、
０．０２〜１重量部である。配合量が、前記下限値より
少ない場合には、得られた組成物の接着性・耐衝撃性が
十分でなく、配合量が前記上限値より多い場合には、そ
れ以上添加しても接着性・耐衝撃性の向上効果が顕著で
なく着色等の種々の問題を生じる場合があり好ましくな
い。The amount of the unsaturated carboxylic acid or its anhydride used in the present invention is 0.01 to 2 parts by weight, preferably 100 parts by weight of the resin.
0.02 to 1 part by weight. If the blending amount is less than the lower limit value, the adhesiveness / impact resistance of the obtained composition is not sufficient. -The effect of improving impact resistance is not remarkable and various problems such as coloring may occur, which is not preferable.
【００２０】本発明の樹脂組成物を用いてポリアミド樹
脂およびフッ素樹脂を含む各種の多層構造体の製品を製
造することができる。そのなかでも、自動車燃料用チュ
ーブとしての用途は、耐衝撃性を含めた色々な優れたチ
ューブ物性を持ちながら、ガソリン及びアルコール含有
ガソリンに対する透過防止特性を併せもった優れたチュ
ーブを提供することができ、本発明の活用分野として期
待が大きい。The resin composition of the present invention can be used to produce various multilayer structure products containing a polyamide resin and a fluororesin. Among them, the application as a tube for automobile fuel is to provide an excellent tube having various permeation-preventing properties for gasoline and alcohol-containing gasoline while having various excellent tube properties including impact resistance. It is possible and highly expected as a field of application of the present invention.
【００２１】本発明の樹脂多層チューブは、内層がフッ
素樹脂、接着層が本発明の樹脂組成物、外層がポリアミ
ド樹脂のすくなくとも３層からなる樹脂多層チューブで
ある。チューブの大きさや各層の厚みは、特に制限され
るものではないが、通常外径４ｍｍ〜１５ｍｍ、肉厚
０．５〜２．０ｍｍであり、各層の厚みとしては、フッ
素樹脂層が５０〜５００μｍ、接着層が１０〜２００μ
ｍ程度が用いられる。また該樹脂多層チューブを構成す
る樹脂に難燃性、導電性等の諸性能をもたせることがで
きる。あるいはこれら諸性能を有する他の層を加えるこ
ともできる。The resin multi-layer tube of the present invention is a resin multi-layer tube having a fluororesin as an inner layer, a resin composition of the present invention as an adhesive layer, and a polyamide resin as an outer layer, which is composed of at least three layers. Although the size of the tube and the thickness of each layer are not particularly limited, the outer diameter is usually 4 mm to 15 mm and the wall thickness is 0.5 to 2.0 mm. As the thickness of each layer, the fluororesin layer is 50 to 500 μm. , Adhesive layer is 10 ~ 200μ
m is used. Further, the resin constituting the resin multi-layer tube can have various properties such as flame retardancy and conductivity. Alternatively, other layers having these properties can be added.
【００２２】このような樹脂多層チューブを製造する方
法としては、特に限定するものではないが、層の数、も
しくは材料の数の押出機より押し出された溶融樹脂を一
つの多層チューブ用ダイスに導入し、ダイス内もしくは
ダイスを出た直後に接着し、その後通常のチューブ成形
と同様の方法で製造してもよい。The method for producing such a resin multi-layer tube is not particularly limited, but the molten resin extruded from the extruder by the number of layers or the number of materials is introduced into one multi-layer tube die. Then, they may be bonded in the die or immediately after leaving the die, and then manufactured by a method similar to ordinary tube molding.
【００２３】また一旦単層チューブを製造し、その外側
もしくは内側にその他の層をコーティングし、多層チュ
ーブを製造する方法によってもよい。Alternatively, a method for producing a multi-layer tube by once producing a single-layer tube and coating other layers on the outer side or the inner side thereof may be used.
【００２４】[0024]
【実施例】以下に実施例および比較例を示し、本発明を
さらに具体的に説明するが、本発明がそのような実施例
の記載によって何等の制約を受けるものではない。また
本発明には以下の実施例の他にも本発明の趣旨を逸脱し
ない限りにおいて種々なる変更、修正、改良が加え得る
ものであることが理解されるべきである。EXAMPLES The present invention will be described in more detail below by showing Examples and Comparative Examples, but the present invention is not limited by the description of such Examples. Further, it should be understood that various changes, modifications and improvements can be made to the present invention other than the following examples without departing from the spirit of the present invention.
【００２５】[0025]
【実施例１】内容積０．４ｍ3 のガラスライニング製オ
ートクレーブに脱酸素した水０．１２ｍ3 を入れて真空
にし、ジクロロテトラフルオロエタン１００ｋｇを入れ
て槽内温度を１５℃に保った。これにＣＨ2 ＝ＣＦＣ3
Ｆ6 Ｈ４．５ｋｇおよびシクロヘキサン１５ｃｃを仕込
み、攪拌下、テトラフルオロエチレン／エチレン混合ガ
ス（モル９８：２）を６ｋｇ／ｃｍ2 まで圧入した。次
いで、ジ（ωーヒドロパーフルオロヘキサノイル）パー
オキサイド２１０ｇを仕込んで重合を開始した。重合の
進行とともに圧力が低下するのでテトラフルオロエチレ
ン／エチレン／ＣＨ2 ＝ＣＦＣ3 Ｆ6 Ｈ混合ガス（モル
比７３．２：２４．４：２．４）を追加圧入して重合圧
力を６ｋｇ／ｃｍ2 に保った。２時間毎に上記パーオキ
サイド各６０ｇを仕込み、重合を１１時間行った。内容
物を回収して、７．５ｋｇの白色粉末をえた。EXAMPLE 1 was evacuated to put the contents of water 0.12 m 3 was deoxygenated in a glass-lined autoclave of volume 0.4 m 3, maintaining the chamber temperature to 15 ℃ put dichlorotetrafluoroethane 100 kg. CH 2 = CFC 3
4.5 kg of F 6 H and 15 cc of cyclohexane were charged, and a tetrafluoroethylene / ethylene mixed gas (mol 98: 2) was injected under pressure to 6 kg / cm 2 . Then, 210 g of di (ω-hydroperfluorohexanoyl) peroxide was charged to initiate polymerization. Since the pressure decreases as the polymerization progresses, a tetrafluoroethylene / ethylene / CH 2 = CFC 3 F 6 H mixed gas (molar ratio 73.2: 24.4: 2.4) is additionally injected to bring the polymerization pressure to 6 kg / It was kept at cm 2 . 60 g of each of the above peroxides was charged every 2 hours, and polymerization was carried out for 11 hours. The contents were collected to give 7.5 kg of white powder.
【００２６】得られた重合物（以下樹脂（Ｂ）とする）
７５．０重量％、相対粘度２．４５のポリアミド１２樹
脂（ＵＢＥナイロン３０２４Ｂ；宇部興産（株）製、以
下樹脂（Ａ）とする）２５．０重量％のブレンド率にて
１８ｌ缶に投入し５分間回転混合ブレンドを行った。The obtained polymer (hereinafter referred to as resin (B))
Polyamide 12 resin with 75.0% by weight and relative viscosity of 2.45 (UBE Nylon 3024B; Ube Industries, Ltd., hereinafter referred to as resin (A)) was added to an 18 l can at a blending ratio of 25.0% by weight. Roll mix blend for 5 minutes.
【００２７】得られた混合物を池貝鉄工（株）製２軸混
練機ＰＣＭ−４５にて、シリンダー設定温度２４０℃回
転数１５０ｒｐｍ吐出量１５ｋｇ／ｈｒにて混練し目的
の組成物をえた。（以下接着用組成物（Ｃ）とする）The obtained mixture was kneaded with a twin-screw kneader PCM-45 manufactured by Ikegai Tekko Co., Ltd. at a cylinder temperature of 240 ° C., a rotation speed of 150 rpm, and a discharge rate of 15 kg / hr to obtain a desired composition. (Hereinafter referred to as adhesive composition (C))
【００２８】さらに、外層に可塑剤（ベンゼンスルホン
酸ブチルアミド）を１０％、変性ポリオレフィンを１０
％添加したポリアミド１２樹脂（ＵＢＥナイロン３０３
５ＪＩ２；宇部興産（株）製、以下樹脂（Ｄ）とす
る）、接着層に接着用組成物（Ｃ）、内層に樹脂（Ａ）
として３層チューブを成形し、次の実験を行った。Further, 10% of plasticizer (benzene sulfonic acid butylamide) and 10% of modified polyolefin are used for the outer layer.
% Polyamide 12 resin (UBE Nylon 303
5JI2; Ube Industries, Ltd., hereinafter referred to as resin (D)), adhesive composition (C) for the adhesive layer, and resin (A) for the inner layer
As a result, a three-layer tube was molded and the following experiment was conducted.
【００２９】成形装置は３台の押出機を有し、この３台
の押出し機から吐出された樹脂をアダプターによって集
めチューブ状に成形するダイス、並びにチューブを冷却
・寸法制御するサイジングダイ、引取り機等からなるも
のである。３層チューブは内径６ｍｍ、外径８ｍｍで内
層、接着層、外層の厚みはそれぞれ０．２ｍｍ、０．１
ｍｍ、０．７ｍｍとした。The molding apparatus has three extruders, and a die for collecting the resin discharged from the three extruders by an adapter to form a tube, a sizing die for cooling and controlling the dimensions of the tube, and a take-up die. It consists of machines and the like. The three-layer tube has an inner diameter of 6 mm and an outer diameter of 8 mm, and the inner layer, the adhesive layer, and the outer layer have thicknesses of 0.2 mm and 0.1, respectively.
mm and 0.7 mm.
【００３０】得られた多層チューブに対して次の評価を
行った。 チューブ低温衝撃（−４０℃）；ＳＡＥ Ｊ８４４に
準ずる ガソリン透過性 ３０ｃｍにカットしたチューブの片端を密栓し、内部に
市販ガソリンとメチルアルコールを８５対１５に混合し
たアルコールガソリンを入れ、残りの片端も密栓した。
その後に全体の重量を測定し、試験チューブを６０℃の
オーブンの中に入れ、重量変化によりアルコールガソリ
ン透過性を測定した。 接着強度 作成した多層チューブより長手方向に２００ｍｍ×５ｍ
ｍのテストピースを作成し、剥離強度を測定した。The following evaluation was performed on the obtained multilayer tube. Tube low temperature impact (-40 ° C); SAE J844 conforming gasoline permeability One end of a tube cut into 30 cm is sealed with an alcohol gasoline mixture of commercial gasoline and methyl alcohol in a ratio of 85:15, and the remaining one end. It was sealed.
After that, the whole weight was measured, the test tube was put in an oven at 60 ° C., and the alcohol gasoline permeability was measured by the weight change. Adhesive strength 200 mm x 5 m in the longitudinal direction from the created multilayer tube
A test piece of m was prepared and the peel strength was measured.
【００３１】[0031]
【実施例２】実施例１において樹脂（Ｂ）のブレンド率
を５５．０重量％とし、ＵＢＥナイロン３０２４Ｂのブ
レンド率を４５．０重量％とした以外は、実施例１と同
様にして３層チューブを成形した。Example 2 Three layers were prepared in the same manner as in Example 1 except that the blending ratio of the resin (B) was 55.0% by weight and the blending ratio of UBE Nylon 3024B was 45.0% by weight. The tube was molded.
【００３２】[0032]
【実施例３】実施例１において樹脂（Ｂ）のブレンド率
を７０．０重量％とし、ＵＢＥナイロン３０２４Ｂ７
５．０重量％の代わりに可塑剤（ベンゼンスルホン酸ブ
チルアミド）を１３％添加した相対粘度３．２のポリア
ミド１２樹脂（ＵＢＥナイロン３０３５ＪＵ；宇部興産
（株）製）３０．０重量％を用いた以外は、実施例１と
同様にして３層チューブを成形した。可塑剤量は、３．
９重量％となる。Example 3 The blend ratio of resin (B) in Example 1 was set to 70.0% by weight, and UBE nylon 3024B7 was used.
Instead of 5.0% by weight, 30.0% by weight of a polyamide 12 resin (UBE nylon 3035JU; manufactured by Ube Industries, Ltd.) having a relative viscosity of 3.2 added with 13% of a plasticizer (benzenesulfonic acid butylamide) was used. A three-layer tube was molded in the same manner as in Example 1 except for the above. The amount of plasticizer is 3.
It becomes 9% by weight.
【００３３】[0033]
【実施例４】実施例１において樹脂（Ｂ）のブレンド率
を６４．５重量％とし、ポリアミド樹脂のブレンド率を
３５．０重量％とし、無水マレイン酸０．４５重量％、
ｔｅｒｔ−ブチルハイドロパーオキサイド０．０５重量
％を加え、１８ｌ缶に投入し５分間回転混合ブレンドを
行った以外は、実施例１と同様にして３層チューブを成
形した。Example 4 In Example 1, the blending ratio of the resin (B) was 64.5% by weight, the blending ratio of the polyamide resin was 35.0% by weight, and the maleic anhydride was 0.45% by weight.
A three-layer tube was molded in the same manner as in Example 1 except that 0.05% by weight of tert-butyl hydroperoxide was added, and the mixture was placed in an 18-liter can and rotationally blended for 5 minutes.
【００３４】[0034]
【実施例５】実施例３において樹脂（Ｂ）のブレンド率
を６９．５重量％とし、可塑剤１３％添加相対粘度３．
２のポリアミド１２樹脂のブレンド率を３０．０重量％
のままとし、さらに、無水マレイン酸０．４５重量％、
ｔｅｒｔ−ブチルハイドロパーオキサイド０．０５重量
％を加え、１８ｌ缶に投入し５分間回転混合ブレンドを
行った以外は、実施例３と同様にして３層チューブを成
形した。[Example 5] In Example 3, the blending ratio of the resin (B) was set to 69.5% by weight, and a plasticizer 13% was added.
Blend ratio of polyamide 12 resin of 2 is 30.0% by weight
0.45% by weight of maleic anhydride,
A three-layer tube was molded in the same manner as in Example 3 except that 0.05% by weight of tert-butyl hydroperoxide was added, and the mixture was placed in an 18-liter can and subjected to rotary mixing blending for 5 minutes.
【００３５】[0035]
【比較例１】実施例１において樹脂（Ｂ）のブレンド率
を４０．０重量％とし、樹脂（Ａ）のブレンド率を６
０．０重量％とした以外は実施例１と同様にして３層チ
ューブを成形した。Comparative Example 1 In Example 1, the blend ratio of the resin (B) was 40.0% by weight, and the blend ratio of the resin (A) was 6%.
A three-layer tube was molded in the same manner as in Example 1 except that the content was 0.0% by weight.
【００３６】[0036]
【比較例２】実施例１において樹脂（Ｂ）のブレンド率
を１０．０重量％とし、樹脂（Ａ）のブレンド率を９
０．０重量％とした以外は実施例１と同様にして３層チ
ューブを成形した。Comparative Example 2 In Example 1, the blending ratio of the resin (B) was 10.0% by weight, and the blending ratio of the resin (A) was 9%.
A three-layer tube was molded in the same manner as in Example 1 except that the content was 0.0% by weight.
【００３７】[0037]
【比較例３】樹脂（Ｄ）のみを用い単層チューブを成形
し実施例１と同様の評価をおこなった。Comparative Example 3 A single-layer tube was molded using only the resin (D), and the same evaluation as in Example 1 was performed.
【００３８】[0038]
【比較例４】外層に樹脂（Ｄ）を内層に樹脂（Ｂ）を用
い、接着層無しに外層厚み０．８ｍｍ内層厚み０．２ｍ
ｍとし、２層チューブを成形し実施例１と同様の評価を
行った。評価結果を表１・２に示す。[Comparative Example 4] Resin (D) was used as the outer layer and resin (B) was used as the inner layer, and the outer layer thickness was 0.8 mm without the adhesive layer, and the inner layer thickness was 0.2 m.
m, a two-layer tube was molded, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Tables 1 and 2.
【００３９】[0039]
【表１】 [Table 1]
【００４０】[0040]
【表２】 [Table 2]
【００４１】[0041]
【発明の効果】本発明は、ポリアミド樹脂およびフッ素
樹脂の双方に対する接着性を有する樹脂組成物を提供
し、内層、接着層、外層の少なくとも３層からなる樹脂
多層チューブであって、内層がフッ素樹脂、接着層が本
発明の接着性を有する樹脂組成物、外層がポリアミド樹
脂からなる、ガソリン、アルコール、酸等に対する耐薬
品性や透過防止性、チューブとしての柔軟性、低温衝撃
性に優れた性能を有する樹脂多層チューブを提供するこ
とができる。The present invention provides a resin composition having adhesiveness to both a polyamide resin and a fluororesin, which is a resin multi-layer tube comprising at least three layers of an inner layer, an adhesive layer and an outer layer, the inner layer being fluorine. Resin, adhesive layer having a resin composition having adhesiveness of the present invention, outer layer made of polyamide resin, excellent in chemical resistance and permeation resistance to gasoline, alcohol, acid, etc., flexibility as a tube, low temperature impact resistance A resin multi-layer tube having performance can be provided.
【手続補正書】[Procedure amendment]
【提出日】平成５年１１月１２日[Submission date] November 12, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２８[Correction target item name] 0028
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２８】さらに、外層に可塑剤（ベンゼンスルホン
酸ブチルアミド）を１０％、変性ポリオレフィンを１０
％添加したポリアミド１２樹脂（ＵＢＥナイロン３０３
５ＪＩ２；宇部興産（株）製、以下樹脂（Ｄ）とす
る）、接着層に接着用組成物（Ｃ）、内層に樹脂（Ｂ）
として３層チューブを成形し、次の実験を行った。Further, 10% of plasticizer (benzene sulfonic acid butylamide) and 10% of modified polyolefin are used for the outer layer.
% Polyamide 12 resin (UBE Nylon 303
5JI2; Ube Industries, Ltd., hereinafter referred to as resin (D)), adhesive composition (C) for the adhesive layer, and resin (B) for the inner layer
As a result, a three-layer tube was molded and the following experiment was conducted.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３９[Correction target item name] 0039
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３９】[0039]
【表１】 [Table 1]
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４０[Correction target item name] 0040
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４０】[0040]
【表２】 [Table 2]
Claims (4)
と、（Ｂ）テトラフルオロエチレンとエチレンに基づく
単位からなる共重合体９５〜５０重量％とからなる、ポ
リアミド樹脂およびフッ素樹脂に接着性を有する樹脂組
成物。1. (A) Polyamide resin 5 to 50% by weight
And (B) tetrafluoroethylene and a copolymer composed of ethylene-based units in an amount of 95 to 50% by weight, and a resin composition having adhesiveness to a polyamide resin and a fluororesin.
ミド１２およびポリアミド１２・１２からなる群から選
ばれたポリアミド樹脂であることを特徴とする請求項第
１項の樹脂組成物。2. The resin composition according to claim 1, wherein the component (A) is a polyamide resin selected from the group consisting of polyamide 11, polyamide 12, and polyamide 12 · 12.
酸アミド、２−エチル−ｐ−ヒドロオキシベンゾエート
等の可塑剤を含むことを特徴とする請求項第１項の樹脂
組成物。3. The resin composition according to claim 1, wherein the component (B) contains a plasticizer such as N-butylbenzenesulfonic acid amide or 2-ethyl-p-hydroxybenzoate.
らなる樹脂多層チューブであって、内層がフッ素樹脂、
外層がポリアミド樹脂、接着層が請求項１〜３項の樹脂
組成物である多層チューブ。4. A resin multi-layer tube comprising at least three layers of an inner layer, an adhesive layer and an outer layer, the inner layer being a fluororesin.
A multilayer tube in which the outer layer is a polyamide resin and the adhesive layer is the resin composition according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20338193A JP3166433B2 (en) | 1993-08-17 | 1993-08-17 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20338193A JP3166433B2 (en) | 1993-08-17 | 1993-08-17 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0753823A true JPH0753823A (en) | 1995-02-28 |
| JP3166433B2 JP3166433B2 (en) | 2001-05-14 |
Family
ID=16473099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20338193A Expired - Fee Related JP3166433B2 (en) | 1993-08-17 | 1993-08-17 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3166433B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1192658A (en) * | 1997-07-25 | 1999-04-06 | E I Du Pont De Nemours & Co | Blend of grafted fluorine-containing polymer and polyamide or polyester |
| JP2000034382A (en) * | 1998-06-29 | 2000-02-02 | E I Du Pont De Nemours & Co | Thermally cross-linkable fluoropolymer, cross-linking of thermoplastic fluoropolymer, and thermoformable fluoropolymer composition |
| US6680093B1 (en) | 1997-05-15 | 2004-01-20 | Degussa Ag | Multilayer composites |
| US6703465B2 (en) | 2002-02-22 | 2004-03-09 | Asahi Glass Company, Limited | Fluorocopolymer |
| US6753393B2 (en) | 2002-02-13 | 2004-06-22 | Asahi Glass Company, Limited | Fluorocopolymer |
| US6855787B2 (en) | 2003-03-31 | 2005-02-15 | Asahi Glass Company, Limited | Multi-layer hose |
| US6881460B2 (en) | 2000-02-10 | 2005-04-19 | Daikin Industries, Ltd. | Laminated resin |
| US6893729B2 (en) | 2000-02-18 | 2005-05-17 | Daikin Industries, Ltd. | Layered resin molding and multilayered molded article |
| JP2006169399A (en) * | 2004-12-16 | 2006-06-29 | Asahi Glass Co Ltd | Fluorine-containing copolymer composition and molded article composed of the same |
| US7132073B2 (en) | 2000-03-23 | 2006-11-07 | Daikin Industries, Ltd. | Process for producing multilayered product |
| JP2010158890A (en) * | 1997-06-27 | 2010-07-22 | Dyneon Llc | Composite article containing fluoropolymer and non-fluorinated polymer, and method for making the same |
| US8137812B2 (en) | 2002-12-25 | 2012-03-20 | Daikin Industries, Ltd. | Fluoropolymer and composition thereof |
-
1993
- 1993-08-17 JP JP20338193A patent/JP3166433B2/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6680093B1 (en) | 1997-05-15 | 2004-01-20 | Degussa Ag | Multilayer composites |
| JP2010158890A (en) * | 1997-06-27 | 2010-07-22 | Dyneon Llc | Composite article containing fluoropolymer and non-fluorinated polymer, and method for making the same |
| JPH1192658A (en) * | 1997-07-25 | 1999-04-06 | E I Du Pont De Nemours & Co | Blend of grafted fluorine-containing polymer and polyamide or polyester |
| JP2000034382A (en) * | 1998-06-29 | 2000-02-02 | E I Du Pont De Nemours & Co | Thermally cross-linkable fluoropolymer, cross-linking of thermoplastic fluoropolymer, and thermoformable fluoropolymer composition |
| EP2617562A2 (en) | 2000-02-10 | 2013-07-24 | Daikin Industries, Ltd. | Laminated resin |
| US6881460B2 (en) | 2000-02-10 | 2005-04-19 | Daikin Industries, Ltd. | Laminated resin |
| US6893729B2 (en) | 2000-02-18 | 2005-05-17 | Daikin Industries, Ltd. | Layered resin molding and multilayered molded article |
| KR100830071B1 (en) * | 2000-02-18 | 2008-05-16 | 다이낑 고오교 가부시키가이샤 | Layered resin molding and multilayered molded article |
| US7132073B2 (en) | 2000-03-23 | 2006-11-07 | Daikin Industries, Ltd. | Process for producing multilayered product |
| US6753393B2 (en) | 2002-02-13 | 2004-06-22 | Asahi Glass Company, Limited | Fluorocopolymer |
| US7273645B2 (en) | 2002-02-22 | 2007-09-25 | Asahi Glass Company, Limited | Fluorocopolymer |
| US6703465B2 (en) | 2002-02-22 | 2004-03-09 | Asahi Glass Company, Limited | Fluorocopolymer |
| US8137812B2 (en) | 2002-12-25 | 2012-03-20 | Daikin Industries, Ltd. | Fluoropolymer and composition thereof |
| US8202617B2 (en) | 2002-12-25 | 2012-06-19 | Daikin Industries, Ltd. | Fluoropolymer and composition thereof |
| US6855787B2 (en) | 2003-03-31 | 2005-02-15 | Asahi Glass Company, Limited | Multi-layer hose |
| JP2006169399A (en) * | 2004-12-16 | 2006-06-29 | Asahi Glass Co Ltd | Fluorine-containing copolymer composition and molded article composed of the same |
| JP4661205B2 (en) * | 2004-12-16 | 2011-03-30 | 旭硝子株式会社 | Fluorine-containing copolymer composition and molded article comprising the same |
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| Publication number | Publication date |
|---|---|
| JP3166433B2 (en) | 2001-05-14 |
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