201022566 六、發明說明： 【明戶斤屬々貝3 發明領域 本發明係關於一種積層結構的管狀體，關於一種用於 例如醫藥品製造設備、半導體製造設備、食品製造設備等 之配管的管狀體。 發明背景 用於醫藥品製造設備等之配管的管狀體，要求具有耐 藥品性、耐熱性、溶出性等之化學安定性和柔軟性（可撓 性、彎曲性）、耐壓性等之物理耐久性。滿足該等要求的管 狀體’在特開2001-12659號公報中已教示具有氟樹脂製的 内側層和加成聚合系矽氧橡膠製的外側層之2層結構的管 狀體。若利用該管狀體，則耐藥品性、封熱性、溶出性等 之化學安定性會因氟樹脂而獲得保證，柔軟性、耐壓性等 之物理耐久性則會因加成聚合系矽氧橡膠而得到確保。但 是’一般而言，因為氟樹脂與矽氧橡膠的接著性低，使用2 層結構的管狀體若歷經長時間會有氟樹脂製的内侧層與加 成聚合系矽氧橡膠製的外侧層之間發生剝離之虞。 因此’該管狀體在氟樹脂製的内側層之外側設有經化 學處理及石夕氧橡膠系底漆處理過的底漆處理部，使氟樹脂 製的内側層與加成聚合系矽氧橡膠製的外側層透過交聯接 著而一體化。藉此，可以提高氟樹脂製的内側層與加成聚 合系矽氧橡膠製的外側層之間的剝離強度，使2層結構的管 201022566 狀體能夠歷經長時間的使用。 -- 因為上述2層結構的管狀體中，必須將氟樹脂製的内側 . 層之外側以化學處理及矽氧橡膠系底漆施行表面處理，所 以製造程序變得繁雜，作業量增加。因此，2層結構的管狀 體有成本升高的情形。另外，將2層結構的管狀體用於例如 管式幫浦(tube pump)等之滑動用途時，氟樹脂製的内側層 與加成聚合系矽氧橡膠製的外側層之間承受強大的滑動阻 力，而該滑動阻力有時比透過底漆處理得到的剥離強度還 要大。因此’氟樹脂製的内側層與加成聚合系矽氧橡膠製 魯 的外側層之間有發生剝離之虞。 【明内 發明揭示 本發明係根據上述事實而完成者，本發明之目的在於 提供—種化學安定性及物理耐久性、柔軟性優異，而且積 層間的接著性優異之低成本積層結構的管狀體。 為達成上述目的，本發明之積層結構的管狀體係以具 有，用熱可塑性氟樹脂製成的内層和，被覆於該内層之外 參 周的用具有接著性官能基之氟樹脂製成的中間層和，被覆 於該中間層之外周的用矽氧系橡膠製成的外層為特徵。若 利用該管狀體’因為内層係由氟樹脂製成，故可確保化學 女疋性’因為外層係由矽氧系的橡膠製成，故可確保物理 耐久性。而且，由於在習知的化學處理或電漿處理之類的 物理處理後即使不對内層的外側施行底漆處理，依然可以 透過讓以具有接著性官能基的氟樹脂製成之中間層介於内 4 201022566 層和外層之_方式來提高内層與外層的剝離強度，所以 製造程序變得«且作業量降低，可抑制管狀體的成本增 加。此外，因為從後述的實驗得知，_中間層介於中間 所得到之上述剝離強度比利用習知的表面處理所得到之剝 離強度有所增大，所以即使將本發明之管狀體使用於滑動 用途上，依然可以防止施加於内層與外層之間的滑動阻力 所造成的剝離，可以歷經長時間的使用該管狀體。 具有前述接著性官能基的氟樹脂，特徵在於，其係具 有羥基或酸酐基團的四氟乙烯—全氟烷基乙烯基醚共聚物 (tetrafluoroethylene-perfluoroalkylvinylether)(變性PFA)。因 利用具有該種特定接著性官能基的材料製成中間層，在獲 得大的接著強度的同時，不需要此前繁雜的製造程序，可 以容易地製造’並可抑制管狀體的成本增加。再者，以下 將就構成具有上述羥基之變性pFA的聚合物之例作敘述。 含羥基的熱可塑性氟聚物可藉含羥基的單量體（單體) 與不含羥基的單量體(單體)之共聚合得到。含羥基的單量體 之例示意如下，含羥基的單量體並不限制於此，亦可含有 可以適用的其他羥基之單量體。 cf2=cf-r-ch2-oh， ch3=ch-r-ch2-oh， CF2=CH-R-CH2-OH， CF2=CF-〇-R-CH2-〇H， ch2=ch-o-r-ch2-oh， cf2=cfcf2-o-r-ch2-oh， 201022566 CH2=CFCF2-R-CH2-OH， ch2=cfcf2-o-r-ch2-OH， 再者* R為選自 a : -(CX2)「， b : -(OCF(CF3)CF2)m-， c : -(OCF2CF(CF3))m-， d : -(OCF(CF3))n-， e : -(OCF2CF2)n-， 之中的任意1個或2個以上之組合。 另外，X為Η(氫)或F(氟）， 1 : 0〜40，m : 0〜10，η : 0〜10。 圖式簡單說明 第1圖（Α)及(Β)為，示意本發明相關之實施態樣的管狀 體之積層結構的斜視圖以及Α-Α線斷面圖。 第2圖為實施例1、比較例1、2之各管狀體的剝離強度 等之結果示意圖。 C實施方式;3 用以實施發明之最佳形態 以下，將就本發明之實施態樣做說明。再者，以下說 明的實施態樣並不限定專利申請之範圍相關的發明，另 外，實施態樣中說明之特徵組合的全部並不限定必須為發 明的解決手段。 第1圖（A)、（B)為示意本發明之管狀體的實施態樣之積 層結構的斜視圖及A-A線斷面圖。該管狀體1為積層的管或 201022566 軟管，由具有内層11和、被覆於該内層i1之外周的中間層 12和、被覆於該中間層12之外周的外層13之3重結構製成。 内層11係以财藥品性、耐熱性、溶出性等之化學安定性優 異的熱可塑性氟樹脂製成，中間層12係以具有接著性官能 基的氟樹脂製成，外層13係以柔軟性、耐壓性等之物理耐 久性優異的矽氧系橡膠製成。 内層11的熱可塑性氟樹脂係從，四氟乙烯-全氟烷基乙 烯基醚共聚物(PFA)、乙烯-四氟乙烯共聚物(ETFE)、四氟 乙烯-六氟丙烯共聚物(FEP)、聚四氟乙烯(PTFE)、聚偏氟 乙烯(PVDF)等之中選擇使用單獨一種或其等之組合。特別 以耐品藥性和抗應力破裂性優異，容易以熔融擠壓做加工 的PFA為佳。 中間層12之具有接著性官能基的氟樹脂，可使用具有 羥基或酸酐基團的PFA(變性PFA)。 外層13之石夕氧系橡膠使用的是加熱硬化型混煉 (millable)橡膠、加熱硬化型液體橡膠等。而且，該等橡膠 的交聯機制有，有機過氧化物交聯、加成反應交聯。尤其 以對柔軟性優異的加熱硬化型混煉橡膠施行有機過氧化物 交聯者為佳。 該種結構的管狀體1係利用以下的順序製成。首先，利 用2轴擠壓機進行共擠壓製成以熱可塑性的氟樹脂為内層 11且以具有接著性官能基的氟樹脂為中間層12的2層結構 之成形體。接著，在2層結構的成形體之外周，亦即中間層 12之外周，利用單軸擠壓機進行擠壓製成以矽氧系橡膠為 201022566 外層is的3層結構之成形體。然後，將3層結糾成形體在 恒溫槽内施行熱硫化處理，固化外層13。利用以上順序完 成管狀體1。再者，2層結構的成形體之共擠壓成形，3層結 構的成形體之擠壓成形以及3層結構的成形體之熱硫化的 各處理，可以利用成批處理或連續處理。 若利用如以上結構之管狀體1，則以氟樹脂製成内層11 來確保化學安定性’以矽氧系的橡膠製成外層13來確保物 理耐久性、柔軟性。而且’即使不在内層11的外側施行習 知的底漆處理或電漿處理等之表面處理，因以具有接著性 官能基的氟樹脂製成之中間層12與内層11共同利用共擠壓 介於内層11與外層13之間，可提高内層11與外層13的剝離 強度。藉此’製造程序變得簡易，且可降低作業量，此外 因為由所謂變性PFA之具有特定接著性官能基的材料製成 中間層12 ’所以在獲得大的接著強度的同時’不需要此前 繁雜的製造程序，可以容易地製造，且可抑制管狀體1的成 本增加。 此外’利用中間層12介於中間的方式所得到之上述剝 離雜度’比利用習知的表面處理得到之剝離強度提高的情 / 為後述之本發明人等的實驗所確認。因此，即使將管 伏用於滑動用途上’亦可防止施加於内層11與外層13 門的潸動阻力造成之剝離，可以歷經長時間的使用該管 狀雜1 雜 换著，如下所示地製作實施例1及比較例1、2的各管狀 炎挑各自的剝離強度等進行研討。 201022566 [實施例1 ] 首先，内層選擇PFA(大金工業製，Ρ62χρ)、中間層12 選擇變性PFA(大金工業製，RAP1RC)，並將兩者以共二壓 的方式成形，製成内徑4.1mm、外徑4.4mm、内層的厚度與 中間層的厚度比落在10 : 1的2層結構之成形體。 接著’選擇外層的加熱硬化型混煉矽氧橡膠(信越化學 工業製，KE551-U)與硫化劑(信越化學工業製，c_23)，將 兩者以100: 1的質量比混煉，與2層結構之成形體共同施以 擠壓並成形’製成外徑落在6.8mm的3層結構之成形體。 然後，將3層結構之成形體以丨次硫化溫度14〇χ：加熱i 小時’進一步以2次硫化溫度200t：加熱4小時，藉此使加熱 硬化型混煉矽氧橡膠硬化，製作3層結構的管狀體。 [比較例1] 首先，將PFA(大金工業製，ρ62χρ)擠壓成形，製成内 徑落在4.1mm、外徑落在4.4mm的1層結構之成形體。 接著，作為化學處理，使用氟聚物表面處理劑（潤工社 製，Tetra-Etch(s主冊商標）’將鈉.萘錯合物溶解於溶劑中的 液體)僅對1層結構的成形體之外周面施行表面處理後，以 甲醇、水、丙酮的順序洗淨並乾燥，之後用矽氧橡膠系底 漆將1層結構的成形體之外周面施行底漆處理。 然後，選擇加熱硬化型混煉矽氧橡膠（信越化學工業 製，KE551-U)與硫化劑（信越化學工業製，c_23)，將兩者 以100: 1的質量比混煉，與經底漆處理的丨層結構之成形體 共同擠壓成形，製成外徑落在6.8mm的2層結構的成形體。 201022566 再者透過將2層結構的成开，體以【次硫化溫度加熱^ 小時’並進一步以2次硫化溫度20(TC加熱4小時的方式，使 加熱硬化型混煉錢㈣硬化，製作2層結構的管狀體。 [比較例2] 首先’擠壓並成形附(大金卫業製，ρ62χρ)，製成内 徑落在4.lmm、外徑落在4.4mm的1層結構之成形體。 接著’用石夕氧橡膠系底漆糾層結構的成形體之外周面 施行底漆處理。 然後，選擇加熱硬化型混㈣氧橡膠(信越化學工業 Θ 製，KE551—U)與硫化劑（信越化學工業製，C-23)，將兩者 以100. 1的質量比混煉，與經底漆處理的W結構之成形體 共同擠壓並成形，製成外徑落在6_8mm的2層結構之㈣ 體。 再者透過將2層結構的成形體以1次硫化溫度140°C加 熱1小時’並進一步以2次硫化溫度200。(：加熱4小時，使加 熱硬化型混煉錢橡膠硬化，製作2層結構的管狀體。 〈剝離強度的評估方法〉 © 將官狀體切斷成長度5cmx寬度lcm的窄條狀，並將其 女裝於拉伸》式驗機（島津製作所製，Aut〇graph ags-J)中， 在長度方向以拉伸逮度5〇mm/min施行拉伸，求得強度安定 的值之平均值(N=5)。 第2圖為實施例1及比較例1、2的各管狀體之剝離強 度、標準偏差、破壞斷面之結果的示意圖。實施及比較 例1、2破裂斷面都是界面，由此測定剝離強度。實施例^是 (S) 10 201022566 在内層和外層間使用變性PFA的中間層之情形，剝離強度顯 示出11.6N的高數值。另一方面，比較例1是在内層施行化 學表面處理和底漆處理的情形，剝離強度為6.76N，與實施 例1相比顯著降低；此外，比較例2是在内層僅施行底漆處 理的情形，剝離強度為0.00N，内層與外層完全未接著，並 不適合實際應用。根據這個結果，使變性PFA製的中間層介 於熱可塑性氟樹脂製的内層與矽氧系橡膠製的外層之間的 方式，積層間有優良的接著性，可謂是合適的。 產業之可利用性 本發明相關之管狀體，作為醫藥品製造設備、半導體 製造設備、食品製造設備等之配管是特別有效的，惟亦可 適用於例如内置於電子機器等之配管。 【圖式簡單說明】 第1圖（A)及(B)為，示意本發明相關之實施態樣的管狀 體之積層結構的斜視圖以及A-A線斷面圖。 第2圖為實施例1、比較例1、2之各管狀體的剝離強度 等之結果示意圖。 【主要元件符號說明】 1···管狀體 12···中間層 11…内層 13…外層 11201022566 VI. Description of the Invention: [Minger's Capsule 3] Field of the Invention The present invention relates to a tubular body of a laminated structure, relating to a tubular body for piping such as a pharmaceutical manufacturing facility, a semiconductor manufacturing facility, a food manufacturing facility, and the like . BACKGROUND OF THE INVENTION A tubular body used for piping a pharmaceutical manufacturing facility or the like is required to have physical stability such as chemical resistance, heat resistance, and dissolution properties, and physical durability such as flexibility (flexibility, flexibility) and pressure resistance. Sex. A tubular body having a two-layer structure of an inner layer made of a fluororesin and an outer layer made of an addition polymerization type xenon rubber is disclosed in Japanese Laid-Open Patent Publication No. 2001-12659. When the tubular body is used, chemical stability such as chemical resistance, heat sealing property, and elution property is ensured by the fluororesin, and physical durability such as flexibility and pressure resistance is due to addition polymerization of the silicone rubber. And get sure. However, in general, since the fluororesin and the oxime rubber have low adhesion, the tubular body having a two-layer structure may have an inner layer made of a fluororesin and an outer layer made of an addition polymerization oxime rubber over a long period of time. There is a gap between the two. Therefore, the tubular body is provided with a primer treatment portion which has been subjected to chemical treatment and a Nisshin rubber primer for the outer side of the inner layer made of a fluororesin, and the inner layer of the fluororesin and the addition polymerization type oxirane rubber are provided. The outer layers of the system are integrated by cross-linking. Thereby, the peeling strength between the inner layer made of the fluororesin and the outer layer made of the addition-polymerized silicone rubber can be improved, and the tube of the two-layer structure 201022566 can be used for a long period of time. - In the tubular body of the two-layer structure, it is necessary to subject the inner side of the fluororesin to the outer side of the layer to be subjected to surface treatment with a chemical treatment and a silicone rubber primer, so that the manufacturing process becomes complicated and the amount of work increases. Therefore, the tubular body having a two-layer structure has a situation in which the cost is increased. Further, when the tubular body having a two-layer structure is used for sliding applications such as a tube pump, the inner layer of the fluororesin and the outer layer made of the addition polymerization type silicone rubber are strongly slid. Resistance, which is sometimes greater than the peel strength obtained by the primer treatment. Therefore, there is a problem that peeling occurs between the inner layer of the fluororesin and the outer layer of the addition polymerization type oxy-rubber rubber. In the present invention, it is an object of the present invention to provide a tubular body having a low-cost laminated structure excellent in chemical stability, physical durability, flexibility, and excellent adhesion between layers. . In order to achieve the above object, the tubular structure of the laminated structure of the present invention has an inner layer made of a thermoplastic fluororesin and an intermediate layer made of a fluororesin having an adhesive functional group which is coated on the outer periphery of the inner layer. And an outer layer made of a neodymium-based rubber coated on the outer periphery of the intermediate layer. When the tubular body is used, since the inner layer is made of a fluororesin, the chemical nature can be ensured. Since the outer layer is made of a neodymium-based rubber, physical durability can be ensured. Moreover, since the outer layer of the inner layer is not subjected to the primer treatment after the physical treatment such as the conventional chemical treatment or the plasma treatment, the intermediate layer made of the fluororesin having the adhesive functional group can be penetrated. 4 201022566 The layer and the outer layer are used to increase the peel strength of the inner layer and the outer layer, so the manufacturing process becomes «and the amount of work is reduced, and the cost increase of the tubular body can be suppressed. Further, since it is known from the experiment described later that the peel strength obtained by the middle layer is increased in comparison with the peel strength obtained by the conventional surface treatment, even if the tubular body of the present invention is used for sliding In use, it is possible to prevent peeling due to sliding resistance applied between the inner layer and the outer layer, and the tubular body can be used for a long period of time. A fluororesin having the above-mentioned adhesive functional group is characterized in that it is a tetrafluoroethylene-perfluoroalkylvinylether (denatured PFA) having a hydroxyl group or an acid anhydride group. Since the intermediate layer is formed by using a material having such a specific adhesive functional group, a large bonding strength can be obtained, and the complicated manufacturing procedure can be eliminated, and the manufacturing cost can be easily made and the cost of the tubular body can be suppressed. Further, an example of a polymer constituting the denatured pFA having the above hydroxyl group will be described below. The hydroxyl group-containing thermoplastic fluoropolymer can be obtained by copolymerization of a hydroxyl group-containing monomer (monomer) and a hydroxyl group-free monomer (monomer). Examples of the hydroxyl group-containing monomer are as follows. The hydroxyl group-containing monomer is not limited thereto, and may contain a monovalent body of another hydroxyl group which can be used. Cf2=cf-r-ch2-oh, ch3=ch-r-ch2-oh, CF2=CH-R-CH2-OH, CF2=CF-〇-R-CH2-〇H, ch2=ch-or-ch2 -oh, cf2=cfcf2-or-ch2-oh, 201022566 CH2=CFCF2-R-CH2-OH, ch2=cfcf2-or-ch2-OH, and then *R is selected from a: -(CX2)", b : -(OCF(CF3)CF2)m-, c : -(OCF2CF(CF3))m-, d : -(OCF(CF3))n-, e : -(OCF2CF2)n-, any one of In addition, X is hydrazine (hydrogen) or F (fluorine), 1: 0 to 40, m: 0 to 10, η: 0 to 10. The simple description of the figure is shown in Fig. 1 (Α) And (Β) is a perspective view showing a laminated structure of a tubular body according to an embodiment of the present invention, and a cross-sectional view of a Α-Α line. Fig. 2 is a view showing the tubular bodies of the first embodiment and the comparative examples 1 and 2. A schematic diagram of the results of the peeling strength, etc. C. Embodiments 3: Best Mode for Carrying Out the Invention Hereinafter, an embodiment of the present invention will be described. Further, the embodiments described below are not limited to the scope of the patent application. In addition, all of the combinations of features described in the embodiments are not necessarily limited to the solution of the invention. FIGS. 1(A) and (B) are schematic diagrams of the present invention. An oblique view and a cross-sectional view of the AA line of the embodiment of the tubular body. The tubular body 1 is a laminated tube or a 201022566 hose, having an inner layer 11 and an intermediate layer 12 covering the outer periphery of the inner layer i1 and A three-fold structure of the outer layer 13 covering the outer periphery of the intermediate layer 12. The inner layer 11 is made of a thermoplastic fluororesin having excellent chemical stability such as chemical properties, heat resistance, and dissolution properties, and the intermediate layer 12 is formed. The outer layer 13 is made of a fluororesin having an adhesive functional group and is excellent in physical durability such as flexibility and pressure resistance. The thermoplastic fluororesin of the inner layer 11 is made of tetrafluoroethylene- Perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polytetrafluoroethylene (PTFE), polyvinylidene fluoride ( Among the PVDF) and the like, a single one or a combination thereof is selected, and in particular, PFA which is excellent in resistance to chemical resistance and stress crack resistance and which is easily processed by melt extrusion is preferred. Fluorine having an intermediate functional group 12 of an intermediate functional group Resin, PF with hydroxyl or anhydride groups can be used A (denatured PFA). The outer layer 13 is made of a heat-hardening type of millable rubber, a heat-curing type liquid rubber, etc. Moreover, the crosslinking mechanism of the rubbers is organic peroxide peroxide. The association and addition reactions crosslink. In particular, it is preferred to carry out organic peroxide crosslinking for a heat-curing type kneading rubber having excellent flexibility. The tubular body 1 of this structure is produced in the following order. First, a two-layer structure molded body in which a thermoplastic fluororesin is used as the inner layer 11 and a fluororesin having an adhesive functional group as the intermediate layer 12 is formed by co-extrusion using a 2-axis extruder. Next, on the outer circumference of the two-layer molded body, that is, the outer periphery of the intermediate layer 12, a single-axis extruder was used to extrude a molded body having a three-layer structure in which the niobium-based rubber was 201022566 outer layer is. Then, the three-layered shape-corrected body was subjected to a heat vulcanization treatment in a thermostatic chamber to cure the outer layer 13. The tubular body 1 is completed in the above order. Further, the co-extrusion molding of the two-layered molded body, the extrusion molding of the three-layered molded body, and the heat-vulcanization treatment of the three-layered molded body can be carried out by batch processing or continuous treatment. When the tubular body 1 having the above structure is used, the inner layer 11 is made of a fluororesin to ensure chemical stability. The outer layer 13 is made of a ruthenium-based rubber to ensure physical durability and flexibility. Further, 'even if the surface treatment such as the primer treatment or the plasma treatment is not performed on the outer side of the inner layer 11, the intermediate layer 12 made of a fluororesin having an adhesive functional group and the inner layer 11 are co-extruded. Between the inner layer 11 and the outer layer 13, the peel strength of the inner layer 11 and the outer layer 13 can be improved. Thereby, the manufacturing process becomes simple and the amount of work can be reduced, and in addition, since the intermediate layer 12' is made of a material having a specific adhesive functional group of the so-called denatured PFA, it is not necessary to be complicated before obtaining a large adhesive strength. The manufacturing process can be easily manufactured, and the cost increase of the tubular body 1 can be suppressed. Further, the above-mentioned peeling offness obtained by the intermediate layer 12 in the middle is improved as compared with the case of the inventors of the present invention, which is improved by the conventional surface treatment. Therefore, even if the tube is used for sliding use, it is possible to prevent the peeling caused by the turbulent resistance applied to the inner layer 11 and the outer layer 13, and it is possible to use the tubular impurity for a long period of time, as shown below. The peel strength and the like of each of the tubular inflammations of Example 1 and Comparative Examples 1 and 2 were examined. 201022566 [Example 1] First, the inner layer was selected from PFA (manufactured by Daikin Industries, Ltd., Ρ62χρ), and the intermediate layer 12 was selected as denatured PFA (manufactured by Daikin Industries, RAP1RC), and the two were formed by a total of two pressures. A molded body having a two-layer structure having a diameter of 4.1 mm, an outer diameter of 4.4 mm, a thickness of the inner layer, and a thickness ratio of the intermediate layer of 10:1. Then, 'the outer layer of the heat-curing type kneading niobium rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KE551-U) and the vulcanizing agent (manufactured by Shin-Etsu Chemical Co., Ltd., c_23) were selected, and the two were kneaded at a mass ratio of 100:1, and 2 The formed bodies of the layer structure were collectively pressed and formed into a molded body of a three-layer structure having an outer diameter of 6.8 mm. Then, the molded body having a three-layer structure was subjected to a secondary vulcanization temperature of 14 Torr: heating for 1 hour, and further heated at a secondary vulcanization temperature of 200 t: for 4 hours, thereby hardening the heat-curing kneaded rubber rubber to produce 3 layers. The tubular body of the structure. [Comparative Example 1] First, a PFA (manufactured by Daikin Industries, Ltd., ρ62 χρ) was extrusion-molded to obtain a molded body having a one-layer structure having an inner diameter of 4.1 mm and an outer diameter of 4.4 mm. Next, as a chemical treatment, a fluoropolymer surface treatment agent (a liquid in which a sodium naphthalene complex is dissolved in a solvent, manufactured by Weaver Co., Ltd., Tetra-Etch (sib.)) is used only for a molded body having a one-layer structure. After the outer peripheral surface was subjected to surface treatment, it was washed and dried in the order of methanol, water, and acetone, and then the outer peripheral surface of the molded body of the one-layer structure was subjected to a primer treatment with a silicone rubber primer. Then, heat-hardening type kneading rubber (KESU-NE, manufactured by Shin-Etsu Chemical Co., Ltd.) and a vulcanizing agent (manufactured by Shin-Etsu Chemical Co., Ltd., c_23) were selected, and the two were kneaded at a mass ratio of 100:1, and the primer was mixed. The molded body of the treated ruthenium structure was co-extruded to form a molded body having a two-layer structure having an outer diameter of 6.8 mm. 201022566 By making the two-layer structure open, the body is heated at [sub-vulcanization temperature for 2 hours] and further heated at a secondary vulcanization temperature of 20 (TC is heated for 4 hours to harden the heat-curing type kneading money (4). [Comparative Example 2] First, a molded body having a one-layer structure having an inner diameter of 4.1 mm and an outer diameter of 4.4 mm was prepared by extrusion and molding (manufactured by Daikin Seiki Co., Ltd., ρ62χρ). Then, the primer is treated with the outer peripheral surface of the molded body of the refractory structure of the Shixi Oxygen Rubber Primer. Then, the heat-hardened mixed (tetra) oxyethylene rubber (Shin-Etsu Chemical Industry Co., Ltd., KE551-U) and the vulcanizing agent are selected (Shin-Etsu Chemical industry, C-23), the two are kneaded at a mass ratio of 100.1, and co-extruded and formed with the molded body of the W structure treated with the primer to form a two-layer structure having an outer diameter of 6_8 mm. Further, the body of the two-layer structure is heated at a primary vulcanization temperature of 140 ° C for 1 hour and further at a secondary vulcanization temperature of 200. (: heating for 4 hours, hardening the heat-curing type kneading rubber , making a tubular structure with a two-layer structure. <Method for Evaluating Peel Strength> © Official The shape is cut into a narrow strip of 5 cm x width and 1 cm in length, and the women's wear is in a tensile test machine (Aut〇graph ags-J, manufactured by Shimadzu Corporation), and the stretch is 5 in the longitudinal direction. The mm/min was subjected to stretching, and the average value of the strength stability was determined (N=5). Fig. 2 is the peel strength, standard deviation, and fracture cross section of each of the tubular bodies of Example 1 and Comparative Examples 1 and 2. A schematic diagram of the results. The peeling strength was measured by the interface of the implementation and Comparative Examples 1 and 2, and the peel strength was measured. Example ^ is (S) 10 201022566 In the case where an intermediate layer of denatured PFA is used between the inner layer and the outer layer, the peel strength is shown. On the other hand, Comparative Example 1 was a case where the chemical surface treatment and the primer treatment were performed on the inner layer, and the peel strength was 6.76 N, which was remarkably lowered as compared with Example 1. Further, Comparative Example 2 was In the case where the inner layer is only subjected to the primer treatment, the peel strength is 0.00 N, and the inner layer and the outer layer are not completely followed, which is not suitable for practical use. According to this result, the intermediate layer made of denatured PFA is interposed between the inner layer of the thermoplastic fluororesin and the inner layer of oxygen. The way between the rubber outer layers Industrial Applicability The tubular body according to the present invention is particularly effective as a piping for pharmaceutical manufacturing equipment, semiconductor manufacturing equipment, food manufacturing equipment, etc., but is also applicable. For example, a pipe built in an electronic device or the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (A) and (B) are a perspective view showing a laminated structure of a tubular body according to an embodiment of the present invention, and an AA line section. Fig. 2 is a view showing the results of peeling strength and the like of each of the tubular bodies of Example 1 and Comparative Examples 1 and 2. [Description of main component symbols] 1··· tubular body 12···intermediate layer 11...inner layer 13... Outer layer 11