WO2017094807A1 - Multilayer tube - Google Patents

Multilayer tube Download PDF

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Publication number
WO2017094807A1
WO2017094807A1 PCT/JP2016/085647 JP2016085647W WO2017094807A1 WO 2017094807 A1 WO2017094807 A1 WO 2017094807A1 JP 2016085647 W JP2016085647 W JP 2016085647W WO 2017094807 A1 WO2017094807 A1 WO 2017094807A1
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Prior art keywords
tube
layer
intermediate layer
outer layer
fluorine
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PCT/JP2016/085647
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French (fr)
Japanese (ja)
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晋哉 山田
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株式会社 潤工社
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Priority to JP2017554162A priority Critical patent/JPWO2017094807A1/en
Publication of WO2017094807A1 publication Critical patent/WO2017094807A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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

Definitions

  • the present invention relates to a laminated tube having high flexibility, in particular, high resilience against radial crushing, high delamination strength and long life.
  • Tubes for tube pumps must have high flexibility and high shape recovery after stress release.
  • a typical material for a tube for a tube pump is silicone rubber. Silicone rubber has excellent shape restoring properties and high heat resistance, but does not have high mechanical strength and sufficient resistance to organic solvents. Accordingly, when an organic solvent such as benzene, toluene or acetone is fed through the tube for a tube pump made of silicone rubber, the tube is broken by repeated crushing, and its life is very short.
  • Another representative material for tube pump tubes is an olefinic elastomer. Olefin-based elastomers have excellent shape recovery properties and high mechanical strength, but do not have sufficient heat resistance and resistance to organic solvents.
  • the problem to be solved by the present invention is to provide a tube having a high shape restoring property and having a long life even when an organic solvent is fed.
  • the inventor of the present invention as a result of earnest studies to solve the above problems, a laminated tube in which a specific inner layer made of a porous fluororesin and an outer layer made of an elastomer are laminated via a specific intermediate layer, The inventors have found that the above characteristics are obtained and have completed the present invention.
  • the present invention comprises an inner layer made of a porous fluororesin impregnated with a fluorine-based elastomer, an intermediate layer made of the above-mentioned fluorine-based elastomer, and an outer layer made of an elastomer, and the delamination strength between the inner layer and the outer layer is 0.48 N / mm. It is the laminated tube which is the above.
  • the present invention is a laminated tube in which the intermediate layer made of the fluorine-based elastomer has a thickness of 5 ⁇ m or more.
  • the laminated tube of the present invention has a high shape restoring property for a long time even when an organic solvent is fed.
  • FIG. 1 schematically shows a cross section of the laminated tube of the present invention.
  • the laminated tube of the present invention has a structure in which an inner layer 1 and an outer layer 3 are laminated via an intermediate layer 2.
  • the inner layer 1 is made of a porous fluororesin impregnated with a fluoroelastomer.
  • a fluorine-based elastomer having high organic solvent resistance is impregnated in a porous fluororesin having high organic solvent resistance and high flexibility, and the inner layer 1 prevents the organic solvent from penetrating into the outer layer 3.
  • the fibril structure of the porous fluororesin contributes to the improvement of the mechanical strength of the elastomer of the inner layer 1 and improves the durability.
  • the intermediate layer 2 is made of the same fluorine-based elastomer as the fluorine-based elastomer constituting the inner layer 1.
  • the intermediate layer 2 prevents the organic solvent from penetrating into the outer layer 3 and bonds the inner layer 1 and the outer layer 3 together.
  • the outer layer 3 is made of an elastomer.
  • the inner layer 1 is not suitable for uses such as a pump tube because the shape of the inner layer 1 is low.
  • the outer layer 3 is suitable to be flexible and has a good shape restoring property.
  • the outer layer 3 protects the inner layer 1 and the intermediate layer 2 and imparts the shape restoring property to the laminated tube of the present invention. Effective functions for tube pump applications.
  • the peel strength between the inner layer 1 and the outer layer 3 is 0.48 N / mm or more.
  • the fluororesin or fluoroelastomer of the inner layer 1 and the elastomer of the outer layer 3 are not bonded as they are.
  • the sufficiently high peel strength of the inner layer 1 and the outer layer 3 contributes to the maintenance of the strength and shape restoration of the tube against repeated radial collapse when the laminated tube of the present invention is used as a tube for a tube pump. Contributes to longer tube life.
  • the tube peel strength is 0.48 N / mm or more, so that the outer layer receives from the roller pump in the longitudinal direction.
  • the manufacturing method of the laminated tube of the present invention is not limited to a specific manufacturing method. Specific examples of the production method are as follows. First, a porous fluororesin tube is impregnated with a liquid fluoroelastomer composition that is a precursor of a fluoroelastomer to form the inner layer 1. At the same time as or after impregnation with the liquid fluorine-based elastomer composition, a liquid fluorine-based elastomer composition layer serving as an intermediate layer is formed on the surface of the porous fluororesin tube. After forming the intermediate layer, it is allowed to stand for a certain time.
  • the liquid fluorine-based elastomer composition of the intermediate layer is primarily crosslinked.
  • the hardness of the fluoroelastomer surface of the intermediate layer is lower than the hardness before crosslinking of the elastomer used for the outer layer, but if it is too low, the shape is difficult to maintain and a problem arises in the tube forming accuracy.
  • an elastomer layer to be an outer layer is formed on the outer side of the primary cross-linked fluorinated elastomer by extrusion molding.
  • the obtained tube is heated, and the fluoroelastomer of the intermediate layer and the elastomer of the outer layer are secondarily crosslinked at the same time to obtain the laminated tube of the present invention.
  • the liquid fluoroelastomer composition of the intermediate layer is cross-linked while entering the pores of the porous fluororesin tube. Since the liquid fluorine-based elastomer composition of the inner layer and the fluorine-based elastomer of the intermediate layer are the same, the liquid fluorine-based elastomer composition in the pores on the outer surface of the inner layer and the fluorine-based elastomer of the intermediate layer are integrated.
  • the interface between the inner layer and the intermediate layer is firmly bonded by the anchor effect of the integrated fluorine-based elastomer.
  • fluororesins and elastomers and elastomers of other materials are not bonded as they are, but are bonded by surface treatment, primer treatment, electron beam irradiation, etc.
  • Such processing is not required. Since the inner layer fluoroelastomer and the outer layer elastomer are simultaneously cross-linked while forming a laminated structure of tubes, the interface between the intermediate layer fluoroelastomer and the outer layer elastomer is also chemically bonded by a cross-linking reaction. Inferred.
  • the adhesive strength is not sufficient only by crosslinking at the same time, and before the intermediate layer and the outer layer are laminated, the hardness of the fluoroelastomer in the intermediate layer is slightly lower than the hardness of the outer layer elastomer before the cross-linking. It is important that In other words, the primary cross-linking reaction on the surface of the fluoroelastomer after forming the inner layer and the intermediate layer is stopped within an appropriate range, so that when the outer layer elastomer is coated, the fine irregularities of the outer layer elastomer are formed on the intermediate layer. The area where the fluoroelastomer enters and the two come into contact with each other increases, and the reaction between the two can proceed sufficiently.
  • the inner layer porous fluororesin tube of the multilayer tube and the outer layer elastomer are firmly bonded via the intermediate layer fluorine-based elastomer.
  • fluororesin and elastomer of other materials are bonded by pretreatment such as surface treatment and primer treatment, but the porous fluororesin constituting the inner layer and the elastomer constituting the outer layer of the laminated tube of the present invention are It can be bonded via a fluorine-based elastomer constituting the intermediate layer without being pretreated.
  • the fluororesin that constitutes the porous fluororesin tube is not limited to a specific fluororesin.
  • Specific examples of the fluororesin include tetrafluoroethylene resin (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), four Fluorinated ethylene-propylene hexafluoride-perfluoroalkyl vinyl ether copolymer resin (EPE), ethylene-tetrafluoroethylene copolymer resin (ETFE), trifluorochloroethylene resin (PCTFE), ethylene-trifluoroethylene chloride These are copolymer resin (ECTFE), vinylidene fluoride resin (PVdF), and vinyl fluoride resin (PVF).
  • PTFE tetrafluoroethylene resin
  • FEP tetrafluoroethylene-hexafluor
  • the porous fluororesin tube is obtained by forming the fluororesin into a porous structure by a stretching method, a salt extraction method, a solvent extraction method, an emulsion method, a radiation irradiation method, a sintering method, or the like.
  • the liquid fluorine-based elastomer composition is a liquid composition containing a fluorine-based elastomer precursor that is crosslinked by a curing reaction to form a fluorine-based elastomer and a curing catalyst.
  • a commercially available liquid fluorine-based elastomer composition can be used.
  • a specific example of a commercially available liquid fluorine-based elastomer composition is SIFEL2618 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the liquid fluorine-based elastomer composition is a liquid composition containing a fluorine-based elastomer precursor that is crosslinked by a curing reaction to form a fluorine-based elastomer and a curing catalyst, and preferably has a hardness of Shore A 25 to 70.
  • a commercially available liquid fluorine-based elastomer composition can be used.
  • a specific example of a commercially available liquid fluorine-based elastomer composition is SIFEL2618 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the wall thickness of the intermediate layer is preferably 5 ⁇ m or more.
  • the inner layer and the outer layer of the laminated tube are made of materials having different physical properties, so that the amount of deformation is different.
  • peeling between layers tends to occur.
  • a flexible intermediate layer is disposed even after cross-linking, and the thickness thereof is set to 5 ⁇ m or more, so that the difference in deformation between the inner layer and the outer layer is mitigated with respect to the collapse in the radial direction of the tube, and the layers are separated. That can be suppressed.
  • the outer layer elastomer is not specified as a specific elastomer but is suitable for its flexibility and shape recovery.
  • silicone rubber and olefin-based elastomer can be used.
  • silicone rubber is particularly preferable because it has heat resistance, low friction, and high shape recovery.
  • Specific examples of the silicone rubber are silicone rubber formed from heat curable millable rubber and silicone rubber formed from heat curable liquid rubber, and the hardness thereof is preferably Shore A 40-70.
  • a commercially available silicone rubber can be used.
  • a specific example of a commercially available silicone rubber is KE561 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 1 A liquid fluoroelastomer composition (SIFEL2618 manufactured by Shin-Etsu Chemical Co., Ltd.) is impregnated into a porous polytetrafluoroethylene (ePTFE) tube having an outer diameter of 4.4 mm and an inner diameter of 3.2 mm, and has a thickness of about 50 ⁇ m. The elastomer layer was formed on the surface of the tube. After the elastomer layer has reached an appropriate hardness, a layer of 1.0 mm thick silicone rubber (KE561-U manufactured by Shin-Etsu Chemical Co., Ltd.) It was formed outside the elastomer layer.
  • ePTFE porous polytetrafluoroethylene
  • FIG. 2 is a micrograph of a part of the cross section of the tube.
  • the ePTFE constituting the inner layer and the silicone rubber constituting the outer layer are bonded via a fluorine-based elastomer (SIFEL) as the intermediate layer.
  • SIFEL fluorine-based elastomer
  • Comparative Example 1 A laminated tube was obtained in the same manner as in Example 1 except that the liquid fluoroelastomer intermediate layer was not formed. The physical properties of the laminated tubes obtained in Example 1 and Comparative Example 1 were measured, and the results are shown in Table 1.
  • Inner layer and outer layer delamination strength The delamination strength was measured by a T-type delamination test using an automatic tensile testing machine. The laminated tube cut out to a length of 50 mm was vertically divided into two parts, and 15 mm at one end of one of the two divided tubes was peeled off by hand. Thereafter, both ends of the peeled layer were fixed to a chuck of a tensile tester, a tensile test was performed at a speed of 1 m / min, and the stress when peeled was measured. The number of samples n was 5, and measurement was performed twice per sample. The measured stress was divided by the measured sample width length to calculate the stress per unit length.
  • the peel strength of the inner layer and the outer layer of the laminated tube of Example 1 was high, and was 0.7 N / mm. Even when acetone was fed, the life of the laminated tube was 350 hours, and sufficient durability was confirmed. The peel strength of the inner layer and the outer layer of the laminated tube of Comparative Example 1 in which no intermediate layer was provided was low, and when acetone was fed, the laminated tube did not function as a pump tube in 1 hour.
  • the pump tube life when a conventional olefin-based elastomer tube was used as a pump tube was 90 hours, which was considerably shorter than the pump tube life of the laminated tube of Example 1.
  • Example 2 A laminated tube was obtained in the same manner as in Example 1 except that the thickness of the liquid fluoroelastomer intermediate layer was about 5 ⁇ m.
  • Example 3 A laminated tube was obtained in the same manner as in Example 1 except that the thickness of the liquid fluoroelastomer intermediate layer was about 10 ⁇ m.
  • Comparative Example 2 A laminated tube was obtained in the same manner as in Example 1 except that the thickness of the liquid fluoroelastomer intermediate layer was about 1 ⁇ m.
  • the physical properties of the laminated tubes obtained in Examples 1 to 3 and Comparative Example 2 were measured, and the results are shown in Table 2.
  • the intermediate layer has a sufficient thickness of 5 ⁇ m or more, even when acetone is fed, the life of the laminated tube is 300 hours or more, Sufficient durability was confirmed.
  • the tube of Comparative Example 2 since the intermediate layer has a thickness of 5 ⁇ m or less and does not have a sufficient thickness, peeling of the inner layer and the outer layer of the laminated tube cannot be suppressed, and acetone is fed. The laminated tube stopped functioning as a pump tube in 50 hours.
  • the laminated tube of the present invention is suitably used as a pump tube.

Abstract

Provided is a tube having high flexibility and having a long lifetime even when an organic solvent is delivered through the tube. The tube is provided with an inner layer comprising a porous fluororesin impregnated with a fluorine-based elastomer, an intermediate layer comprising the fluorine-based elastomer, and an outer layer comprising a silicone rubber, the interlayer peel strength of the inner layer and the outer layer being 0.48 N/mm or more. In particular, the tube has high durability and a long lifetime when the thickness of the intermediate layer is 5 µm or more.

Description

積層チューブLaminated tube
　本発明は、高い可撓性、特に径方向のつぶれに対する高い復元性、高い層間剥離強度及び長い寿命を有する積層チューブに関する。 The present invention relates to a laminated tube having high flexibility, in particular, high resilience against radial crushing, high delamination strength and long life.
　チューブポンプ用チューブは、高い柔軟性と応力解放後の高い形状復元性を有していなければならない。チューブポンプ用チューブの代表的材質はシリコーンゴムである。シリコーンゴムは、優れた形状復元性と高い耐熱性を有しているが、高い機械的強度と、有機溶剤に対する十分な耐性を有していない。従って、ベンゼン、トルエン、アセトン等の有機溶剤が、シリコーンゴム製チューブポンプ用チューブ中を送液されると、繰り返しのつぶれによって当該チューブが破壊され、その寿命は非常に短い。チューブポンプ用チューブの別の代表的材質はオレフィン系エラストマーである。オレフィン系エラストマーは優れた形状復元性と、高い機械的強度を有しているが、十分な耐熱性と、有機溶剤に対する耐性を有していない。有機溶剤が、オレフィン系エラストマー製チューブポンプ用チューブ中を送液されると、当該チューブは有機溶剤で膨潤し、繰り返しのつぶれによって当該チューブが短期間で破壊される。
　一方、チューブポンプ用チューブとは別に、架橋構造のシリコーンゴムが微細多孔質構造を有するポリテトラフルオロエチレンからなる基体チューブの微細空孔内に充填された、シリコーンゴムの機械的強度を補った可撓性チューブが検討された（例えば、特許文献１参照）。 Tubes for tube pumps must have high flexibility and high shape recovery after stress release. A typical material for a tube for a tube pump is silicone rubber. Silicone rubber has excellent shape restoring properties and high heat resistance, but does not have high mechanical strength and sufficient resistance to organic solvents. Accordingly, when an organic solvent such as benzene, toluene or acetone is fed through the tube for a tube pump made of silicone rubber, the tube is broken by repeated crushing, and its life is very short. Another representative material for tube pump tubes is an olefinic elastomer. Olefin-based elastomers have excellent shape recovery properties and high mechanical strength, but do not have sufficient heat resistance and resistance to organic solvents. When the organic solvent is fed through the tube for the olefin elastomer tube pump, the tube swells with the organic solvent, and the tube is broken in a short period of time due to repeated crushing.
On the other hand, it is possible to compensate for the mechanical strength of the silicone rubber, which is filled in the micropores of the base tube made of polytetrafluoroethylene having a microporous structure separately from the tube pump tube. A flexible tube has been studied (for example, see Patent Document 1).
特開平６－２７０３０１号公報JP-A-6-270301
　先述の特許文献１のチューブは高い形状復元性を有しているが、当該チューブの有機溶剤に対する耐久性と形状復元性は十分ではない。そこで、有機溶剤が送液されても長い寿命を有するチューブが望まれていたが、このようなチューブは実現されていなかった。
　本発明が解決しようとする課題は、高い形状復元性を有し、有機溶剤が送液されても長い寿命を有するチューブの提供である。 Although the tube of the above-mentioned patent document 1 has high shape restoration property, the durability and shape restoration property with respect to the organic solvent of the said tube are not enough. Therefore, there has been a demand for a tube having a long life even when an organic solvent is fed, but such a tube has not been realized.
The problem to be solved by the present invention is to provide a tube having a high shape restoring property and having a long life even when an organic solvent is fed.
　本発明の発明者は、上記課題を解決するために鋭意検討した結果、多孔質フッ素樹脂からなる特定の内層とエラストマーとからなる外層が特定の中間層を介して積層されている積層チューブが、上記特性を有することを見出し本発明を完成させるに至った。 The inventor of the present invention, as a result of earnest studies to solve the above problems, a laminated tube in which a specific inner layer made of a porous fluororesin and an outer layer made of an elastomer are laminated via a specific intermediate layer, The inventors have found that the above characteristics are obtained and have completed the present invention.
　本発明は、フッ素系エラストマーが含浸された多孔質フッ素樹脂からなる内層と、上記フッ素系エラストマーからなる中間層と、エラストマーからなる外層を備え、内層と外層の層間剥離強度が０．４８Ｎ/ｍｍ以上である積層チューブである。 The present invention comprises an inner layer made of a porous fluororesin impregnated with a fluorine-based elastomer, an intermediate layer made of the above-mentioned fluorine-based elastomer, and an outer layer made of an elastomer, and the delamination strength between the inner layer and the outer layer is 0.48 N / mm. It is the laminated tube which is the above.
　本発明は、さらに、前記フッ素系エラストマーからなる中間層の厚さが、５μｍ以上である積層チューブである。 The present invention is a laminated tube in which the intermediate layer made of the fluorine-based elastomer has a thickness of 5 μm or more.
　本発明の積層チューブは、有機溶剤が送液されても、高い形状復元性を長期間有する。 The laminated tube of the present invention has a high shape restoring property for a long time even when an organic solvent is fed.
本発明の積層チューブの断面の模式図Schematic diagram of cross section of laminated tube of the present invention 内層、中間層及び外層の積層状態を示す顕微鏡写真Photomicrograph showing the laminated state of the inner layer, intermediate layer and outer layer
　図１は、本発明の積層チューブの断面を模式的に示す。本発明の積層チューブは、内層１と外層３が中間層２を介して積層される構造をしている。内層１は、フッ素系エラストマーが含浸された多孔質フッ素樹脂からなる。高い耐有機溶剤性を有するフッ素系エラストマーが、高い耐有機溶剤性と高い柔軟性を有する多孔質フッ素樹脂に含浸されており、内層１は、有機溶剤の外層３への浸透を防止する。更に、多孔質フッ素樹脂のフィブリル構造は、内層１のエラストマーの機械的強度の向上に寄与し、耐久性を向上させている。 FIG. 1 schematically shows a cross section of the laminated tube of the present invention. The laminated tube of the present invention has a structure in which an inner layer 1 and an outer layer 3 are laminated via an intermediate layer 2. The inner layer 1 is made of a porous fluororesin impregnated with a fluoroelastomer. A fluorine-based elastomer having high organic solvent resistance is impregnated in a porous fluororesin having high organic solvent resistance and high flexibility, and the inner layer 1 prevents the organic solvent from penetrating into the outer layer 3. Furthermore, the fibril structure of the porous fluororesin contributes to the improvement of the mechanical strength of the elastomer of the inner layer 1 and improves the durability.
　中間層２は、内層１を構成するフッ素系エラストマーと同種のフッ素系エラストマーからなる。中間層２は、有機溶剤の外層３への浸透を防止すると共に、内層１と外層３を接着している。 The intermediate layer 2 is made of the same fluorine-based elastomer as the fluorine-based elastomer constituting the inner layer 1. The intermediate layer 2 prevents the organic solvent from penetrating into the outer layer 3 and bonds the inner layer 1 and the outer layer 3 together.
　外層３は、エラストマーからなる。内層１は、これ単体では形状復元性が低く、ポンプチューブのような用途には適さない。外層３には柔軟で形状復元性に富むものが適しており、外層３は、内層１及び中間層２を保護し、本発明の積層チューブに形状復元性を付与し、本発明の積層チューブのチューブポンプ用途として有効な機能を発現させる。 The outer layer 3 is made of an elastomer. The inner layer 1 is not suitable for uses such as a pump tube because the shape of the inner layer 1 is low. The outer layer 3 is suitable to be flexible and has a good shape restoring property. The outer layer 3 protects the inner layer 1 and the intermediate layer 2 and imparts the shape restoring property to the laminated tube of the present invention. Effective functions for tube pump applications.
　内層１と外層３の剥離強度は０．４８Ｎ/ｍｍ以上である。内層１のフッ素樹脂やフッ素系エラストマーと外層３のエラストマーとはそのままでは接着されない。内層１と外層３の十分に高い剥離強度は、本発明の積層チューブがチューブポンプ用チューブとして使用される時、繰り返しの径方向のつぶれに対してチューブの強度と形状復元性の維持に貢献し、チューブの寿命の長期化に寄与する。とくに本発明の内層１のフッ素樹脂やフッ素系エラストマーと外層３のエラストマーの組み合わせの積層チューブでは、チューブの剥離強度が０．４８Ｎ/ｍｍ以上であることで、外層がローラポンプから受けるチューブ長手方向の歪による剥離が抑えられることにより、チューブの繰り返しの径方向のつぶれによるチューブの破壊を抑えることが可能になる。 The peel strength between the inner layer 1 and the outer layer 3 is 0.48 N / mm or more. The fluororesin or fluoroelastomer of the inner layer 1 and the elastomer of the outer layer 3 are not bonded as they are. The sufficiently high peel strength of the inner layer 1 and the outer layer 3 contributes to the maintenance of the strength and shape restoration of the tube against repeated radial collapse when the laminated tube of the present invention is used as a tube for a tube pump. Contributes to longer tube life. In particular, in the laminated tube of the combination of the fluororesin or fluoroelastomer of the inner layer 1 of the present invention and the elastomer of the outer layer 3, the tube peel strength is 0.48 N / mm or more, so that the outer layer receives from the roller pump in the longitudinal direction. By suppressing the peeling due to the distortion of the tube, it is possible to suppress the breakage of the tube due to repeated radial collapse of the tube.
　本発明の積層チューブの製造方法は、特定の製造方法に限定されない。当該製造方法の具体例は以下のとおりである。まず、フッ素系エラストマーの前駆体である液状フッ素系エラストマー組成物を、多孔質フッ素樹脂チューブに含浸させて内層１とする。液状フッ素系エラストマー組成物を含浸させると同時に、または含浸させた後に、中間層となる液状フッ素系エラストマー組成物層を、多孔質フッ素樹脂チューブの表面に形成する。中間層を形成した後、一定時間静置する。中間層を形成したチューブを静置中に、中間層の液状フッ素系エラストマー組成物は一次架橋される。このときの一次架橋は、中間層の表面の硬度が適当な範囲になるまでで反応を止めることが重要である。中間層のフッ素系エラストマー表面の硬度は、外層に使用するエラストマーの架橋前の硬度より低くするが、低くしすぎた場合、形状を維持しにくくなりチューブの成形精度に問題が生じる。その後、外層となるエラストマー層を、押出成形により、一次架橋された中間層のフッ素系エラストマーの外側に形成する。得られたチューブは加熱され、中間層のフッ素系エラストマーと外層のエラストマーが同時に二次架橋されて、本発明の積層チューブが得られる。中間層の液状フッ素系エラストマー組成物は、多孔質フッ素樹脂チューブの細孔に入り込んだ状態で架橋される。内層の液状フッ素系エラストマー組成物と中間層のフッ素系エラストマーは同種のため、内層の外表面の細孔内の液状フッ素系エラストマー組成物と中間層のフッ素系エラストマーは一体化する。このため、一体化したフッ素系エラストマーのアンカー効果により、内層と中間層の界面は強固に接着している。通常、フッ素系の樹脂やエラストマーと、他材質のエラストマーは、そのままでは接着せず、表面処理、プライマー処理、電子線照射等の処理をして接着されるが、本発明の積層チューブでは、そのような処理が必要とされない。内層フッ素系エラストマーと外層エラストマーは、チューブの積層構造を形成した状態で同時に架橋されるため、中間層のフッ素系エラストマーと外層のエラストマーの界面間も、架橋反応により化学的に結合されていると推察される。しかし、同時に架橋されるだけでは接着強度は十分ではなく、中間層と外層が積層される前に、中間層のフッ素系エラストマーの硬度が、架橋前の外層エラストマーの硬度より、少しだけ低くされていることが重要である。つまり、内層と中間層を形成した後のフッ素系エラストマー表面の一次架橋反応が適度な範囲で止められておくことで、外層エラストマーが被覆される時に、外層のエラストマーの微細な凹凸に中間層のフッ素系エラストマーが入り込み、両者が接触する面積が大きくなり、両者間の反応が十分に進行され得る。従って、多層チューブの内層多孔質フッ素樹脂チューブと外層エラストマーは、中間層のフッ素系エラストマーを介して強固に接着されている。通常、フッ素樹脂と他材質のエラストマーは、これらの表面処理、プライマー処理等の前処理により接着されるが、本発明の積層チューブが備える内層を構成する多孔質フッ素樹脂と外層を構成するエラストマーは、前処理されずに中間層を構成するフッ素系エラストマーを介して接着され得る。 The manufacturing method of the laminated tube of the present invention is not limited to a specific manufacturing method. Specific examples of the production method are as follows. First, a porous fluororesin tube is impregnated with a liquid fluoroelastomer composition that is a precursor of a fluoroelastomer to form the inner layer 1. At the same time as or after impregnation with the liquid fluorine-based elastomer composition, a liquid fluorine-based elastomer composition layer serving as an intermediate layer is formed on the surface of the porous fluororesin tube. After forming the intermediate layer, it is allowed to stand for a certain time. While the tube in which the intermediate layer is formed is allowed to stand, the liquid fluorine-based elastomer composition of the intermediate layer is primarily crosslinked. In this case, it is important that the primary crosslinking is stopped until the hardness of the surface of the intermediate layer reaches an appropriate range. The hardness of the fluoroelastomer surface of the intermediate layer is lower than the hardness before crosslinking of the elastomer used for the outer layer, but if it is too low, the shape is difficult to maintain and a problem arises in the tube forming accuracy. Thereafter, an elastomer layer to be an outer layer is formed on the outer side of the primary cross-linked fluorinated elastomer by extrusion molding. The obtained tube is heated, and the fluoroelastomer of the intermediate layer and the elastomer of the outer layer are secondarily crosslinked at the same time to obtain the laminated tube of the present invention. The liquid fluoroelastomer composition of the intermediate layer is cross-linked while entering the pores of the porous fluororesin tube. Since the liquid fluorine-based elastomer composition of the inner layer and the fluorine-based elastomer of the intermediate layer are the same, the liquid fluorine-based elastomer composition in the pores on the outer surface of the inner layer and the fluorine-based elastomer of the intermediate layer are integrated. For this reason, the interface between the inner layer and the intermediate layer is firmly bonded by the anchor effect of the integrated fluorine-based elastomer. Usually, fluororesins and elastomers and elastomers of other materials are not bonded as they are, but are bonded by surface treatment, primer treatment, electron beam irradiation, etc. In the laminated tube of the present invention, Such processing is not required. Since the inner layer fluoroelastomer and the outer layer elastomer are simultaneously cross-linked while forming a laminated structure of tubes, the interface between the intermediate layer fluoroelastomer and the outer layer elastomer is also chemically bonded by a cross-linking reaction. Inferred. However, the adhesive strength is not sufficient only by crosslinking at the same time, and before the intermediate layer and the outer layer are laminated, the hardness of the fluoroelastomer in the intermediate layer is slightly lower than the hardness of the outer layer elastomer before the cross-linking. It is important that In other words, the primary cross-linking reaction on the surface of the fluoroelastomer after forming the inner layer and the intermediate layer is stopped within an appropriate range, so that when the outer layer elastomer is coated, the fine irregularities of the outer layer elastomer are formed on the intermediate layer. The area where the fluoroelastomer enters and the two come into contact with each other increases, and the reaction between the two can proceed sufficiently. Therefore, the inner layer porous fluororesin tube of the multilayer tube and the outer layer elastomer are firmly bonded via the intermediate layer fluorine-based elastomer. Usually, fluororesin and elastomer of other materials are bonded by pretreatment such as surface treatment and primer treatment, but the porous fluororesin constituting the inner layer and the elastomer constituting the outer layer of the laminated tube of the present invention are It can be bonded via a fluorine-based elastomer constituting the intermediate layer without being pretreated.
　多孔質フッ素樹脂チューブを構成するフッ素樹脂は、特定のフッ素樹脂に限定されない。当該フッ素樹脂の具体例は、四フッ化エチレン樹脂(PTFE)、四フッ化エチレン－六フッ化プロピレン共重合樹脂(FEP)、四フッ化エチレン－パーフルオロアルキルビニルエーテル共重合樹脂(PFA)、四フッ化エチレン－六フッ化プロピレン－パーフルオロアルキルビニルエーテル共重合樹脂(EPE)、エチレン－四フッ化エチレン共重合樹脂(ETFE)、三フッ化塩化エチレン樹脂(PCTFE)、エチレン－三フッ化塩化エチレン共重合樹脂(ECTFE)、フッ化ビニリデン樹脂(PVdF)、フッ化ビニル樹脂(PVF)である。多孔質フッ素樹脂チューブは、当該フッ素樹脂が、延伸法、塩類抽出法、溶剤抽出法、エマルジョン法、放射線照射法、焼結法等の方法により多孔質構造に形成されて得られる。 The fluororesin that constitutes the porous fluororesin tube is not limited to a specific fluororesin. Specific examples of the fluororesin include tetrafluoroethylene resin (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), four Fluorinated ethylene-propylene hexafluoride-perfluoroalkyl vinyl ether copolymer resin (EPE), ethylene-tetrafluoroethylene copolymer resin (ETFE), trifluorochloroethylene resin (PCTFE), ethylene-trifluoroethylene chloride These are copolymer resin (ECTFE), vinylidene fluoride resin (PVdF), and vinyl fluoride resin (PVF). The porous fluororesin tube is obtained by forming the fluororesin into a porous structure by a stretching method, a salt extraction method, a solvent extraction method, an emulsion method, a radiation irradiation method, a sintering method, or the like.
　液状フッ素系エラストマー組成物は、硬化反応により架橋されてフッ素系エラストマーが形成されるフッ素系エラストマー前駆体と硬化触媒を含む液状の組成物である。液状フッ素系エラストマー組成物は市販されているものを用いることができる。液状フッ素系エラストマー組成物の市販品の具体例は、信越化学工業（株）製SIFEL2618である。 The liquid fluorine-based elastomer composition is a liquid composition containing a fluorine-based elastomer precursor that is crosslinked by a curing reaction to form a fluorine-based elastomer and a curing catalyst. A commercially available liquid fluorine-based elastomer composition can be used. A specific example of a commercially available liquid fluorine-based elastomer composition is SIFEL2618 manufactured by Shin-Etsu Chemical Co., Ltd.
　液状フッ素系エラストマー組成物は、硬化反応により架橋されてフッ素系エラストマーが形成されるフッ素系エラストマー前駆体と硬化触媒を含む液状の組成物であり、その硬度は、ＳｈｏｒｅＡ　２５～７０のものが好ましい。液状フッ素系エラストマー組成物は市販されているものを用いることができる。液状フッ素系エラストマー組成物の市販品の具体例は、信越化学工業（株）製SIFEL2618である。
中間層の肉厚は、５μｍ以上とすることが好ましい。積層チューブに加えられる応力に対して、積層チューブの内層と外層とは物性が異なる材料を用いているため、変形量が異なる。積層チューブの内層と外層の変形量が異なると層間の剥離が発生しやすい。ここに、架橋後も柔軟な中間層を配置し、その厚さを５μｍ以上とすることで、チューブの径方向のつぶれに対して、内層と外層の変形の差を緩和して層間が剥離することを抑えることができる。 The liquid fluorine-based elastomer composition is a liquid composition containing a fluorine-based elastomer precursor that is crosslinked by a curing reaction to form a fluorine-based elastomer and a curing catalyst, and preferably has a hardness of Shore A 25 to 70. . A commercially available liquid fluorine-based elastomer composition can be used. A specific example of a commercially available liquid fluorine-based elastomer composition is SIFEL2618 manufactured by Shin-Etsu Chemical Co., Ltd.
The wall thickness of the intermediate layer is preferably 5 μm or more. Due to the stress applied to the laminated tube, the inner layer and the outer layer of the laminated tube are made of materials having different physical properties, so that the amount of deformation is different. When the deformation amount of the inner layer and the outer layer of the laminated tube is different, peeling between layers tends to occur. Here, a flexible intermediate layer is disposed even after cross-linking, and the thickness thereof is set to 5 μm or more, so that the difference in deformation between the inner layer and the outer layer is mitigated with respect to the collapse in the radial direction of the tube, and the layers are separated. That can be suppressed.
　外層エラストマーは、特定のエラストマーに特定されないが、柔軟性、形状復元性に富むものが適している。例えば、シリコーンゴム、オレフィン系エラストマー等が挙げられる。なかでもシリコーンゴムは、耐熱性があり、低摩擦で形状復元性が高いことから、とくに好ましい。シリコーンゴムの具体例は、加熱硬化型ミラブルゴムから形成されるシリコーンゴム、加熱硬化型液状ゴムから形成されるシリコーンゴムであり、その硬度は、ＳｈｏｒｅＡ　４０～７０のものが好ましい。シリコーンゴムは市販されているものを使用可能である。シリコーンゴムの市販品の具体例は、信越化学工業（株）製KE561である。 The outer layer elastomer is not specified as a specific elastomer but is suitable for its flexibility and shape recovery. For example, silicone rubber and olefin-based elastomer can be used. Among these, silicone rubber is particularly preferable because it has heat resistance, low friction, and high shape recovery. Specific examples of the silicone rubber are silicone rubber formed from heat curable millable rubber and silicone rubber formed from heat curable liquid rubber, and the hardness thereof is preferably Shore A 40-70. A commercially available silicone rubber can be used. A specific example of a commercially available silicone rubber is KE561 manufactured by Shin-Etsu Chemical Co., Ltd.
　以下、実施例により本発明が詳細に説明されるが、本発明はこれらの実施例に限定されない。
実施例１
　液状フッ素系エラストマー組成物（信越化学工業（株）製SIFEL2618）が、外径４．４ｍｍ、内径３．２ｍｍの多孔質ポリテトラフルオロエチレン（ePTFE）チューブに含浸されると共に、５０μｍ程度の厚みの当該エラストマーの層が当該チューブの表面に形成された。当該エラストマーの層が適度な硬度になった後、厚さ１．０ｍｍのシリコーンゴム（信越化学工業（株）製KE561-U）の層が、押出成形機（（株）三葉製作所製）により当該エラストマー層の外側に形成された。得られたチューブは１５０℃に加熱され、フッ素系エラストマーとシリコーンゴムの加硫が行われ、積層チューブが得られた。図２は、当該チューブの断面の一部の顕微鏡写真である。内層を構成するePTFEと外層を構成するシリコーンゴムが、中間層のフッ素系エラストマー（SIFEL）を介して接着されている。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
Example 1
A liquid fluoroelastomer composition (SIFEL2618 manufactured by Shin-Etsu Chemical Co., Ltd.) is impregnated into a porous polytetrafluoroethylene (ePTFE) tube having an outer diameter of 4.4 mm and an inner diameter of 3.2 mm, and has a thickness of about 50 μm. The elastomer layer was formed on the surface of the tube. After the elastomer layer has reached an appropriate hardness, a layer of 1.0 mm thick silicone rubber (KE561-U manufactured by Shin-Etsu Chemical Co., Ltd.) It was formed outside the elastomer layer. The obtained tube was heated to 150 ° C., and the fluorinated elastomer and the silicone rubber were vulcanized to obtain a laminated tube. FIG. 2 is a micrograph of a part of the cross section of the tube. The ePTFE constituting the inner layer and the silicone rubber constituting the outer layer are bonded via a fluorine-based elastomer (SIFEL) as the intermediate layer.
比較例１
　液状フッ素系エラストマーの中間層が形成されない以外、実施例１と同様の操作が行われ、積層チューブが得られた。
　実施例１及び比較例１で得られた積層チューブの物性が測定され、結果が表１に示されている。 Comparative Example 1
A laminated tube was obtained in the same manner as in Example 1 except that the liquid fluoroelastomer intermediate layer was not formed.
The physical properties of the laminated tubes obtained in Example 1 and Comparative Example 1 were measured, and the results are shown in Table 1.
　各種物性と測定方法は下記のとおりである。
（１）内層と外層の層間剥離強度
　層間剥離強度は、自動引張試験機が用いられ、Ｔ形剥離試験により行った。
５０ｍｍの長さに切り出された積層チューブが縦に２分割され、２分割された片方のチューブの片端の１５ｍｍが手で剥離された。その後、剥離された層の両末端が引っ張り試験機のチャックに固定され、１ｍ／ｍｉｎの速度で引張試験が行われ、剥離されるときの応力が測定された。サンプルｎ数は５で、１サンプルあたり２回の測定が行われた。測定された応力は、測定されたサンプル幅の長さで除されて、単位長さ当たりの応力が算出された。 Various physical properties and measurement methods are as follows.
(1) Inner layer and outer layer delamination strength The delamination strength was measured by a T-type delamination test using an automatic tensile testing machine.
The laminated tube cut out to a length of 50 mm was vertically divided into two parts, and 15 mm at one end of one of the two divided tubes was peeled off by hand. Thereafter, both ends of the peeled layer were fixed to a chuck of a tensile tester, a tensile test was performed at a speed of 1 m / min, and the stress when peeled was measured. The number of samples n was 5, and measurement was performed twice per sample. The measured stress was divided by the measured sample width length to calculate the stress per unit length.
（２）ポンプチューブ寿命
　ポンプ本体としてMASTERflex L/S、ポンプヘッドとしてeasy-load model 77201-60、流体としてアセトンが使用された。長さ３００ｍｍに切断された積層チューブがポンプヘッドに接続され、ポンプが６００ｒｐｍの回転数で稼働された。３０秒間に送り出されるアセトンの量が計量され、送り出し量が半減するか、もしくは積層チューブが破壊されるまでの時間が、ポンプチューブ寿命とされた。 (2) Life of pump tube MASTERflex L / S was used as the pump body, easy-load model 77201-60 was used as the pump head, and acetone was used as the fluid. A laminated tube cut to a length of 300 mm was connected to the pump head, and the pump was operated at a rotation speed of 600 rpm. The amount of acetone delivered for 30 seconds was weighed, and the time until the delivery amount was halved or the laminated tube was destroyed was the pump tube life.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１の積層チューブの内層と外層の剥離強度は高く、０.７Ｎ/ｍｍであった。アセトンが送液された場合でも、当該積層チューブのポンプチューブ寿命は３５０時間であり、十分な耐久性が確認された。中間層が設けられていない比較例１の積層チューブの内層と外層の剥離強度は低く、アセトンが送液されると、当該積層チューブは１時間でポンプチューブとして機能しなくなった。従来のオレフィン系エラストマー製チューブがポンプチューブとして使用された時のポンプチューブ寿命は９０時間であり、実施例１の積層チューブのポンプチューブ寿命よりかなり短かった。 The peel strength of the inner layer and the outer layer of the laminated tube of Example 1 was high, and was 0.7 N / mm. Even when acetone was fed, the life of the laminated tube was 350 hours, and sufficient durability was confirmed. The peel strength of the inner layer and the outer layer of the laminated tube of Comparative Example 1 in which no intermediate layer was provided was low, and when acetone was fed, the laminated tube did not function as a pump tube in 1 hour. The pump tube life when a conventional olefin-based elastomer tube was used as a pump tube was 90 hours, which was considerably shorter than the pump tube life of the laminated tube of Example 1.
実施例２
　液状フッ素系エラストマーの中間層の厚みを５μｍ程度にした以外は、実施例１と同様の操作が行われ、積層チューブが得られた。
実施例３
　液状フッ素系エラストマーの中間層の厚みを１０μｍ程度にした以外は、実施例１と同様の操作が行われ、積層チューブが得られた。
比較例２
　液状フッ素系エラストマーの中間層の厚みを１μｍ程度にした以外は、実施例１と同様の操作が行われ、積層チューブが得られた。
　実施例１～３及び比較例２で得られた積層チューブの物性が測定され、結果が表２に示されている。 Example 2
A laminated tube was obtained in the same manner as in Example 1 except that the thickness of the liquid fluoroelastomer intermediate layer was about 5 μm.
Example 3
A laminated tube was obtained in the same manner as in Example 1 except that the thickness of the liquid fluoroelastomer intermediate layer was about 10 μm.
Comparative Example 2
A laminated tube was obtained in the same manner as in Example 1 except that the thickness of the liquid fluoroelastomer intermediate layer was about 1 μm.
The physical properties of the laminated tubes obtained in Examples 1 to 3 and Comparative Example 2 were measured, and the results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例１～３の積層チューブは、中間層が５μｍ以上で十分な厚さを有しているため、アセトンが送液された場合でも、当該積層チューブのポンプチューブ寿命は３００時間以上であり、十分な耐久性が確認された。比較例２のチューブは、中間層の厚さが５μｍ以下であり十分な厚さを有していないため、積層チューブの内層と外層の剥離を抑えることはできず、アセトンが送液されると、当該積層チューブは５０時間でポンプチューブとして機能しなくなった。 In the laminated tubes of Examples 1 to 3, since the intermediate layer has a sufficient thickness of 5 μm or more, even when acetone is fed, the life of the laminated tube is 300 hours or more, Sufficient durability was confirmed. In the tube of Comparative Example 2, since the intermediate layer has a thickness of 5 μm or less and does not have a sufficient thickness, peeling of the inner layer and the outer layer of the laminated tube cannot be suppressed, and acetone is fed. The laminated tube stopped functioning as a pump tube in 50 hours.
　本発明の積層チューブは、ポンプチューブとして好適に使用される。 The laminated tube of the present invention is suitably used as a pump tube.
１・・・内層、２・・・中間層、３・・・外層

  1 ... inner layer, 2 ... intermediate layer, 3 ... outer layer

Claims (2)

  1. 　フッ素系エラストマーが含浸された多孔質フッ素樹脂からなる内層と、
    　上記フッ素系エラストマーからなる中間層と、
    　シリコーンゴムからなる外層を備え、
    　内層と外層の層間剥離強度が０．４８Ｎ/ｍｍ以上である積層チューブ。     An inner layer made of a porous fluororesin impregnated with a fluoroelastomer,
    An intermediate layer comprising the above-mentioned fluorine-based elastomer;
    With an outer layer made of silicone rubber,
    A laminated tube having an inner layer and outer layer delamination strength of 0.48 N / mm or more.
  2. 　前記フッ素系エラストマーからなる中間層の厚さが、５μｍ以上である請求項1に記載の積層チューブ。
     

          2. The laminated tube according to claim 1, wherein a thickness of the intermediate layer made of the fluorine-based elastomer is 5 μm or more.


PCT/JP2016/085647 2015-11-30 2016-11-30 Multilayer tube WO2017094807A1 (en)

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US20210094253A1 (en) * 2019-09-27 2021-04-01 Saint-Gobain Performance Plastics Corporation Multilayer tube and method for making same
JPWO2021149783A1 (en) * 2020-01-21 2021-07-29
WO2023008473A1 (en) 2021-07-28 2023-02-02 株式会社 潤工社 Tube and pump using same

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JPS56109727A (en) * 1980-02-05 1981-08-31 Nippon Erasutoran Kk Flexible tube and manufacture thereof
JPS62200301U (en) * 1986-06-12 1987-12-21
JPH0584861A (en) * 1991-09-30 1993-04-06 Japan Gore Tex Inc Composite material using silicone resin
JP2002502735A (en) * 1998-02-13 2002-01-29 ゴア エンタープライズ ホールディングス，インコーポレイティド Flex-resistant composite elastomer composition
JP2008030471A (en) * 2006-06-29 2008-02-14 Japan Gore Tex Inc Layered type elastic tube
JP2009119243A (en) * 2008-08-01 2009-06-04 Tachibana Shoten Co Ltd Chemical and medical component, and chemical and medical apparatus
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Publication number Priority date Publication date Assignee Title
US20210094253A1 (en) * 2019-09-27 2021-04-01 Saint-Gobain Performance Plastics Corporation Multilayer tube and method for making same
CN114514394A (en) * 2019-09-27 2022-05-17 美国圣戈班性能塑料公司 Multilayer pipe and method for producing same
JPWO2021149783A1 (en) * 2020-01-21 2021-07-29
WO2021149782A1 (en) * 2020-01-21 2021-07-29 株式会社 潤工社 Tube
WO2021149783A1 (en) 2020-01-21 2021-07-29 株式会社 潤工社 Tube and pump using same
KR20220121249A (en) 2020-01-21 2022-08-31 가부시키가이샤 쥰코샤 tube and pump using it
JP7445999B2 (en) 2020-01-21 2024-03-08 株式会社潤工社 Tube and pump using it
WO2023008473A1 (en) 2021-07-28 2023-02-02 株式会社 潤工社 Tube and pump using same

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