WO2008001870A1

WO2008001870A1 - Elastic laminated tube

Info

Publication number: WO2008001870A1
Application number: PCT/JP2007/063048
Authority: WO
Inventors: Hiroyasu Kikukawa
Original assignee: Japan Gore-Tex Inc.
Priority date: 2006-06-29
Filing date: 2007-06-28
Publication date: 2008-01-03

Abstract

Disclosed is an elastic laminated tube wherein the inner surface is composed of a fluororesin layer (20) and an elastic layer (10) is formed on the outer side of the fluororesin layer (20). In this elastic laminated tube, an intermediate layer (30) composed of a porous fluororesin (32) and an elastic body (31) filling the pores of the porous fluororesin (32) is formed between the fluororesin layer (20) and the elastic layer (10). The fluororesin layer (20) as the inner surface of the tube is joined with the porous fluororesin (32) of the intermediate layer (30), and the elastic layer (10) on the outer side is joined with the elastic body (31) of the intermediate layer (30).

Description

Specification

Laminated elastic tube

Technical field

TECHNICAL FIELD [0001] The present invention relates to an elastic tube having an inner surface made of fluorine resin, and more preferably to an elastic tube that repeatedly receives pressure in the tube radial direction, and more preferably used for a pinch valve or a roller pump. The present invention relates to an elastic tube useful for controlling the flow of fluid in the hollow of the tube by the radial pressing, such as an elastic tube.

Background art

[0002] In a pinch valve, the flow of a fluid (such as a liquid) is stopped by pressing an elastic tube in the radial direction, and the flow of the fluid is started by releasing the pressure. In the roller pump, the elastic tube is pressed with a roller in the radial direction, and fluid (liquid etc.) is sent out by moving the roller in the axial direction of the tube while maintaining this pressed state. With these pinch valves and roller pumps, the flow path structure can be simplified and the possibility of contaminating the fluid is less than that of ordinary valve pumps. For this reason, it is often used in the field of food and medical equipment, and in recent years, it is also used for the transfer of photoresist when manufacturing semiconductors.

[0003] For elastic tubes, silicone rubber is generally used because of its excellent elasticity (for example, Document 1). However, silicone rubber is inferior in chemical resistance compared to fluorine resin. For this reason, the elastic tube of Document 1 uses highly corrosive fluids (photoresist liquids, liquids for operating process machinery, highly corrosive liquids used in fields such as pharmaceuticals, foods, medicine, and chemistry). ), The durability of the tube is greatly impaired.

[0004] In order to improve the chemical resistance of the tube, a fluorine-based elastic tube is also known in which the elastomer is replaced with a silicone rubber-powered fluorine elastomer (Reference 2). However, a flexible fluorine-based elastomer that can be used as an elastic tube has high tackiness. Therefore, for example, if you leave the elastic tube pressed with a roller pump roller, The tubes may stick together and cannot be restored, and the tube may become blocked. In addition, when used repeatedly, the tackiness is high, so that the inner surface of the tube is damaged, and the durability is inferior to that of the silicone-based elastic tube.

[0005] In Reference 3, an ePTFE (stretched polytetrafluoroethylene) film impregnated with an elastomer (silicone elastomer, perfluoropolyether elastomer, etc.) is wound to cure the elastomer. The elastic tube obtained by this is disclosed. Tubes using silicone elastomer are sold under the name “STA—PUR EJ” by Japan Gore-Tex Co., Ltd., and tubes using perfluoropolyether elastomer are “CHEM—SURE Is sold under the product name. Although these tubes have dramatically improved durability due to the ePT FE membrane, they use silicone elastomers and perfluoroelastomers, so that they are essentially the same as those described in References 1 and 2. The problem is inherent. That is, when a silicone elastomer is used, the chemical resistance is inferior, and when a perfluoropolyether elastomer is used, the inner surface is more easily damaged than when a silicone elastomer is used.

[0006] In order to improve the chemical resistance of a tube using a silicone elastomer, it has also been proposed to protect the inner surface with a fluorocarbon resin layer (Reference 4, etc.). In order to improve the tackiness of the inner surface of the tube using a fluorine-based elastomer, it has also been proposed to protect the inner surface with a fluorine resin layer (Reference 5, etc.). However, these multi-layered tubes have insufficient adhesion between the elastomer layer and the inner surface of the fluororesin layer. In particular, when stress is repeatedly applied in the radial direction of the tube, the stress concentrates on the joint interface between the inner surface layer and the elastomer layer, and delamination occurs particularly at the bent portion, which is called the “teak portion”. Durability cannot be obtained.

[0007] Document 6 discloses that a fluorine-containing polymer layer and a thermoplastic elastomer layer are bonded via an intermediate layer. This intermediate layer has a sea-island structure of a thermoplastic elastomer and a fluoropolymer, and in the vicinity of the interface between the thermoplastic elastomer layer, the thermoplastic polymer forms a sea phase and the fluoropolymer forms an island phase. In the vicinity of the interface with the fluoropolymer layer, the fluoropolymer forms a sea phase and the thermoplastic polymer forms an island phase. The formation of such an intermediate layer is thought to improve the delamination problem. The However, the intermediate layer in Reference 6 is a complex structure in which the sea and islands of the sea-island structure are reversed on both sides of the layer. Such a complicated intermediate layer is obtained by co-extruding the intermediate layer with a thermoplastic elastomer layer and a fluorine-containing polymer layer. ) Can be formed by adjusting. For example, when the intermediate layer is made of polyester-based thermoplastic elastomer (TPEE) and ethylene-tetrafluoroethylene copolymer (ETFE), polymer temperature 200 to 260 ° C, cutting speed 0 to: Conditions of LOOOsec- ¹ (Condition 1) Then, TPEE forms the sea phase, ETFE forms the island phase, and the polymer temperature is 230 to 310 ° C and the shear rate is 0 to 100 sec- ¹ (condition 2). ETF E is the sea phase and TPEE is the island phase. It will be formed. However, with this method, the force that requires the polymer temperature to be different between the inside and outside of the intermediate layer, the actual intermediate layer thickness is only about 0.1 mm (Example), and this slight thickness difference It is highly questionable whether it is practically possible to vary the temperature between the two. In particular, since the polymer temperature range of 230 to 260 ° C is included in both conditions 1 and 2 above, it is unclear what phase structure it will be, and the polymer temperature must be set to ensure that TPEE is in the sea phase. The temperature must be 230 ° C or lower, and the polymer temperature must be 260 ° C or higher to ensure that TPEE is in the island phase. It seems virtually impossible to create a temperature difference of more than 30 ° C (= 260–230 ° C) in just 0.1 mm. Even if it can be realized, it seems extremely difficult to ensure quality that is poorly reproducible. Furthermore, according to Reference 6, it is necessary to adopt a complex structure in which the sea and islands of the sea-island structure are reversed on the front and back of the layer, so the usable combinations of elastomers and fluoropolymers are practically very limited. It must be a thing. Furthermore, the elastomer is heated for a long time due to co-extrusion. Therefore, the elastomer is thermally deteriorated and the elasticity is also lowered.

[0008] Note that Document 7 discloses that an elastic layer in which an elastic body is filled in the pores of a porous fluororesin film is laminated on a release layer having a fluororesin film force. However, this document 7 relates to a toner fixing member. The elastic layer is directly laminated on the fluorine resin film.

[0009] The present invention has been made paying attention to the circumstances as described above, and an object of the present invention is to provide an elastic tube capable of reliably improving durability against repeated pressing and chemical resistance. It is in.

[0010] Reference 1: Japanese Patent Laid-Open No. 2000-179753

Reference 2: Japanese Utility Model Publication 59-41687

Reference 3: Special Table 2002-502735

Reference 4: Japanese Utility Model Publication No. 4 47185

Reference 5: Japanese Patent Laid-Open No. 2001-193659

Reference 6: JP-A-9 131833

Reference 7: Japanese Unexamined Patent Application Publication No. 2005-257762

Disclosure of the invention

As a result of intensive studies to solve the above problems, the present inventor has determined that an intermediate layer in which the pores of porous fluorine resin are filled with an elastic body includes an inner layer fluorine resin layer and an outer elastic layer. The inner surface fluorine resin layer and the intermediate layer porous fluorine resin are joined together, and the outer elastic layer and the intermediate layer elastic body are joined together. The present inventors have found that the adhesion between the resin layer and the outer elastic layer can be remarkably improved, and the durability against repeated pressing and the chemical resistance can be reliably improved.

[0012] That is, the laminated elastic tube according to the present invention is

The inner surface (inner layer) is composed of a fluorine resin layer,

An elastic layer (outer layer) is formed on the outer side of this fluorocoagulant layer,

Between the fluorine resin layer (inner layer) and the elastic layer (outer layer), porous fluorine resin (such as porous polytetrafluoroethylene) and the elasticity filling the pores of the porous fluorine resin An intermediate layer composed of the body is formed,

The inner fluororesin layer and the intermediate porous fluororesin are joined (particularly heat-sealed),

The gist is that the elastic layer of the outer layer and the elastic body of the intermediate layer are joined.

The inner surface of the fluorine resin layer is preferably a tube wound with a fluorine resin film.

Further, it is desirable that this fluorine resin layer is stretched in a direction orthogonal to the length direction of the tube. A particularly preferred fluorine resin layer is a fully stretched fluorine resin layer (particularly a fully stretched polytetrafluoroethylene layer). The fluorine resin layer on the inner surface is a meltable fluorine resin layer. It may be formed from fat (PFA, FEP, PVDF, THV, EFEP, etc.).

[0014] Further, the inner surface of the fluorine resin layer may be formed by laminating two or more kinds of fluorine resins. For example, two or more types of fluorine resin may each be a tube, and this tube may be laminated in order of the inner force. Further, two or more kinds of fluorine resins may be laminated in a planar shape, and the planar laminate may be wound into a tube shape. It is preferable that one of the two or more types of fluorine resins is a fully expanded fluorine resin, and the other one is a meltable fluorine resin (PFA, FEP, PVDF, THV, EFEP, etc.). It is desirable to dispose the meltable fluorine resin on the outermost side of the fluorine resin layer on the inner surface.

[0015] As the elastic body of the intermediate layer or the outer layer, a silicone elastomer, a fluorine elastomer, a fluorosilicone elastomer, or the like can be used. The elastic material of the intermediate layer and outer layer is polyester thermoplastic elastomer, polyurethane thermoplastic elastomer, polyolefin thermoplastic elastomer, styrenic block copolymer elastomer, thermoplastic vulcanized elastomer, polyamide. It may be a thermoplastic elastomer. In the present invention, it is recommended to use the same resin for the elastic body of the intermediate layer and the elastic body of the outer layer. The storage elastic modulus E of the elastic layer (outer layer) is, for example, about 1 × 10 ² to 1 × 10 ⁸ Pa. The elastic layer includes (1) a first layer having elastic force, (2) a porous polytetrafluoroethylene film, and an elastic body filling the pores of the porous polytetrafluoroethylene film. It may have a spiral laminated structure in which the second layer is overlapped. The ratio of the thickness of the first layer to the thickness of the second layer (first layer Z second layer) is, for example, about 6.5 Z1 or less.

[0016] The thickness of the laminated elastic tube of the present invention is, for example, as follows.

Inner layer (Fluororesin layer): 1 to 200 μm

Intermediate layer: 10-2000 / z m

Outer layer (elastic layer): 0.15-80mm

The thickness of the elastic layer is, for example, about 10 to 200% with respect to the inner diameter of the laminated elastic tube.

[0017] A wear-resistant layer (such as a polytetrafluoroethylene tube) may be formed outside the elastic layer.

[0018] The laminated elastic tube of the present invention has a porous tube made of a fluorine resin layer (inner layer). After coating with fluorine resin and heat-sealing them,

Porous fluorine resin side force By filling the pores of the porous fluorine resin with a liquid elastic material, and forming a three-dimensional network structure after filling, the elastic material is made into an elastic body. Can be manufactured. Preferably, a three-dimensional network structure is formed after forming a layer containing an elastic material on the outer side of the porous fluorine resin.

The laminated elastic tube of the present invention is useful for a pinch valve or a roller pump.

Brief Description of Drawings

FIG. 1 is a schematic cross-sectional view showing an example of a laminated elastic tube according to the present invention.

FIG. 2 is an enlarged view of a main part of the laminated elastic tube of the present invention.

FIG. 3 is a schematic cross-sectional view showing an example of an outer layer (elastic layer) used in the present invention.

FIG. 4 is a schematic cross-sectional view showing another example of the laminated elastic tube of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

[0021] Hereinafter, the present invention will be described in more detail with reference to the drawings as appropriate. However, the present invention is not limited to the illustrated examples, and is suitable within a range that can meet the purpose described above. It is also possible to carry out the invention with modifications, and these are all included in the technical scope of the present invention.

FIG. 1 is a schematic cross-sectional view showing an example of a laminated elastic tube of the present invention, and FIG. 2 is an enlarged view of a main part of the cross-sectional view. As shown in FIG. 1, the laminated elastic tube of the present invention has an inner surface composed of a fluorine resin layer 20, and an elastic layer 10 formed outside the fluorine resin layer 20. An intermediate layer 30 is formed between the oil layer 20 and the elastic layer 10. The intermediate layer 30 is composed of a porous fluorine resin 32 and an elastic body 31 that fills the pores of the porous fluorine resin. The inner surface of the fluorocarbon resin layer 20 and the intermediate layer 30 of the porous fluorocarbon resin 32 are bonded together, and the outer elastic layer 10 and the intermediate layer 30 of the elastic body 31 are bonded together.

When the intermediate layer 30 is employed, the adhesion between the fluorine resin layer 20 and the elastic layer 10 can be remarkably improved. In the sea-island structure, even if the sea part is a continuous structure, the island part becomes an independent structure, whereas in the intermediate layer 30 according to the present invention in which the pores of the porous fluorocarbon resin 32 are filled with the elastic body 31, , Both porous fluororesin 32 and elastic body 31 have a continuous structure As a result, the area of the continuous interface between the elastic body and the fluorocoagulant increases dramatically. This is thought to have led to a dramatic improvement in adhesion. In addition, this laminated type rigid tube can be manufactured without thermally degrading the elastic layer 10 and the elastic body 31, and the elasticity can be reliably ensured.

Hereinafter, each configuration will be described in more detail.

[0025] 1: Elastic layer (outer layer) 10

The elasticity of the laminated elastic tube of the present invention is achieved by an elastic layer 10 including an elastic body 11 (hereinafter also referred to as an outer layer). Examples of the elastic body 11 include silicone elastomer, fluorine elastomer (crosslinked fluorine elastomer, fluorine thermoplastic elastomer, etc.), fluorosilicone elastomer, polyester elastomer, and polyurethane. Elastomer (polyurethane rubber, polyurethane thermoplastic elastomer, etc.), polyolefin elastomer, styrene elastomer, polyamide elastomer, fluoro-phosphazene elastomer, phosphazene rubber, nitrinole rubber, styrene butadiene rubber ( SBR), chloroprene rubber and the like. These elastic bodies 11 can be used alone or in combination of two or more.

[0026] The elastic body 11 may be a thermoplastic elastomer that may be a crosslinked elastomer (for example, a crosslinked elastomer corresponding to a silicone elastomer, a fluorine elastomer, a fluorosilicone elastomer, etc.). Elastomers (preferably polyester-based thermoplastic elastomers (especially Copolyester Thermoplastic Elastomers: C OPE)), polyurethane-based thermoplastic elastomers (Thermoplastic Polyurethane Elastomers: TPU), polyolefin-based thermoplastic elastomers (Thermoplastic Olefin Elastomers: TPO), Fluorine Thermoplastic Elastomers, Styrenic Block Copolymer Elastomers (SBC), Thermoplastic Elastomers (COPE) , Polyamide Thermoplastic Elastomers: P EBA) and the like; preferably COPE, TPU, TPO, SBC, COPE, PEBA). The cross-linked elastomer is excellent in that the operating temperature of the laminated elastic tube can be increased. Thermoplastic elastomers are excellent in that they can be produced continuously by extrusion and have a high elasticity. [0027] Particularly preferred elastic bodies 11 are silicone elastomers, fluorine elastomers, fluorosilicone elastomers, and the like. These particularly preferred elastic bodies 11 are excellent in any of heat resistance, chemical resistance, and durability against repeated pressing. For example, silicone elastomers are particularly excellent in mechanical strength, elasticity sustainability, and shape recovery when releasing compressive stress. The fluorine-based elastomer is excellent in chemical resistance. Fluorosilicone elastomers exhibit intermediate properties between both silicone elastomers and fluorine elastomers.

[0028] The silicone elastomer has a crosslinked organopolysiloxane (methylsilicone rubber or the like) in which a methyl group is bonded to the key chain, and an aromatic hydrocarbon bonded to the key! Silicone rubber such as cross-linked products (such as vinyl silicone rubber) are included.

[0029] The fluorine-based elastomer includes a crosslinked polymer having fluoromethylene as a main chain, a fluorine-based thermoplastic elastomer, and the like. The cross-linked products include FKM (binary FKM, ternary FKM, perfluorobule ether-containing FKM), FFKM, TFE-Pr fluororubber, TFE-Pr-VdF fluororubber, fluorinated poly This includes rubber (such as liquid fluororubber) in which the ether skeleton is Si-crosslinked (see the following formula). Liquid fluororubber is available from Shin-Etsu Chemical Co., Ltd. as “SIFEL” (trade name).

[0030] [Chemical 1]

Binary F KM

― (CF ₂ -CH _{2) m-} ( ^CF 2- _n-

^CF 3

Ternary F KM

-(CF ₂ -CH ₂ ) (CF ₂ -CF) _n -CC F ₂ -CF ₂ )

^CF 3

Perfluorovinyl ester containing F KM

-(CF ₂ -CH ₂ ) _m- (CF ₂ -CF ₂ ) _n- (CF ₂ -CF)

FF KM ° " ^{R f}

(Perfect full-fledged rubber rubber)

-(CF „-C FJ-(CF ₉ — CF)-2 2 m ZI n

O-R f

F E P

T F E- P r series fluoro rubber

-(CF ₂ —CF ₂ ) _m- (CF ₂ -CH) _n-

^CH 3

T F E- P r-d F series fluororubber

-(CF ₂ — CF ₂ ) _m — (CH ₂ -CH) _n — (CF ₂ -CH ₂ )

^CH 3

Fluorine-based thermoplastic elastomer

One (H S) m— (F KM) One CH S) n—

H S: Hard segment (E T F E, etc.)

Liquid fluoro rubber

~ S i-(OC F ₂ -CF) _m -S i ~

^CF 3 fluorosilicone elastomers include fluorosilicone rubbers such as crosslinked organopolysiloxanes in which fluoroalkyl groups are bonded to silicon. A cross-linked polysiloxane bonded with a fluoroalkyl group (FMVQ, etc .; see the following formula) corresponds to a fluorosilicone rubber.

[Chemical 2] ^ ^H 2 ^CH 2 ^CF 3

F M V Q — (S i-O)-

I ^π

^CH 3

[0032] This means that the cross-linked elastomer is cross-linked or the hard segments of the thermoplastic elastomer are allowed to interact with each other to finally cure (not limited to cross-linking, and widely forms a three-dimensional network structure). Hereinafter, unless otherwise specified, the elastic body 11 may not be cured at the raw material stage. The elastic material 11 may be solid (kneadability) or liquid. The elastic body 11 obtained from the solid (kneadable) elastic material 11 is particularly excellent in mechanical strength and shape recovery property when releasing compressive stress. As the solid elastic material 11, a millable (kneaded) type silicone rubber can be used. Millable silicone rubber is a rubber that contains a high viscosity silicone rubber compound and a curing agent (vulcanizing agent) and cures when heated. Heat-curing silicone rubber (HCR (Heat Cured Rubber), HVR (Heat) Vulcanizing Rubber) and HTV (High Temperature Vulcanizing; rubber).

On the other hand, the liquid elastic material 11 is useful when the elastic body 11 is reinforced with another material, as will be described later. For example, the elastic body 11 may be reinforced by filling the pores of the porous body. If the liquid elastic material 11 is used, the pores of the porous body can be easily impregnated.

[0034] The liquid elastic material 11 means a liquid material 11 that is liquid before curing and exhibits elasticity after curing. For example, a liquid silicone elastomer (such as liquid silicone rubber) ), Liquid fluoroelastomers (liquid fluororubber, etc.), liquid fluorosilicone elastomers (liquid fluorosilicone rubber, etc.), heat heated to liquid (fluid) by dissolving in a solvent For example, a plastic elastomer.

[0035] Liquid silicone rubber, liquid fluororubber, liquid fluorosilicone rubber, etc. are crosslinked reaction methods, such as a condensation reaction type that crosslinks with moisture in the air, an addition reaction type that crosslinks with a noble metal catalyst, and a crosslink by heating. In view of mass productivity, the addition reaction type and the thermosetting type are preferred. The viscosity (25 ° C.) before curing (crosslinking) is, for example, about 1000 boise or less, preferably about 200 boise or less. The lower the viscosity As will be described later, it becomes easy to impregnate the porous material with the elastic material 11. Such a liquid silicone rubber can be obtained from Shin-Etsu Chemical Co., Ltd. as “RTV rubber for electric / electronic / general industry”. Further, as described above, the liquid fluororubber is available as rsiFELj (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). The liquid fluorosilicone rubber can be obtained from Shin-Etsu Chemical Co., Ltd. as “oil resistant / solvent resistant fluorosilicone”, for example.

[0036] The elastic body 11 of the elastic layer 10 may be used in combination with other materials. For example, if the elastic body 11 is mixed with fabric, organic fibers, inorganic fibers, carbons, metal fine particles, inorganic powder, etc., the elastic layer 10 is formed in terms of mechanical strength, electrical characteristics, thermal conductivity, and the like. Can improve. By improving the mechanical strength, when the elastic tube of the present invention is used for a pinch valve or a roller pump, it is possible to prevent the elastic layer 10 from being damaged by the pressing force to a higher degree. If the elastic layer 10 is improved in terms of electrical characteristics, thermal conductivity, etc., the antistatic property of the resulting laminated elastic tube will be improved, and the heating of the laminated elastic tube will be easier.

[0037] In order to increase the mechanical strength of the elastic layer 10, it is most desirable to fill the pores of the porous body with the elastic body 11. By supporting the elastic body 11 with the porous body, the mechanical strength of the elastic layer 10 can be increased without impairing the elasticity. A particularly preferred reinforced elastic layer 10 is a spiral laminate in which a first layer 12 composed of an elastic body 11 and a layer 13 (second layer) of a porous film filled with pores by the elastic body 11 are overlapped. It has a structure (hereinafter referred to as a spiral elastic layer 10). FIG. 3 is a schematic sectional view showing an example of the spiral elastic layer 10. The spiral elastic layer 10 can be produced by winding a porous film impregnated (coated) inside and on the surface of a porous film, as described in JP-T-2002-502735. The mechanical strength of the elastic layer 10 can be dramatically increased. In addition, the spiral elastic layer 10 is remarkably superior in terms of shape recovery when releasing the compressive stress!

[0038] The porous film constituting the spiral elastic layer 10 is not particularly limited as long as it is flexible and does not impair the elasticity of the elastic body 11. The porous fluororesin 32 constituting the intermediate layer 30 and A porous film (for example, a polyimide porous film) formed from a resin other than fluorine resin may be used. A preferable porous film is a porous film excellent in heat resistance (such as a porous fluororesin film and a polyimide porous film). A particularly preferred porous film is a porous body (porous fluororesin film, particularly porous polytetrafluoroethylene film) excellent in chemical resistance, heat resistance, flexibility and the like. The elastic tube consisting of the spiral elastic layer 10 in which the elastic body 11 is silicone rubber and the porous film is porous polytetrafluoroethylene film is a product of “STA-PURE” from Japan Gore-Tex Co., Ltd. Available by name. An elastic tube comprising a spiral elastic layer 10 in which the elastic body 11 is a fluoro rubber and the porous film is a porous polytetrafluoroethylene film is a product of “CHEM—SURE” from Japan Gore-Tex Co., Ltd. Available under the trade name.

[0039] Thickness ratio (first layer Z) of the first layer 12 (elastic body) and the second layer 13 (porous film with pores filled with an elastic body) of the spiral elastic layer 10 The second layer) is, for example, about 6.5Z1 or less. As the thickness ratio decreases, the strength of the elastic layer 10 increases. A preferred thickness ratio (first layer Z second layer) is about 5Z1 or less, particularly about 3Z1 or less. On the other hand, the lower limit of the thickness ratio (first layer Z second layer) is not particularly limited, and the elastic layer 10 may be substantially composed of the second layer 13 alone. The thickness ratio is the ratio of the elastic body formed on the surface of the porous film when the spiral elastic layer is manufactured by winding the porous film impregnated (coated) with the elastic body. It can be adjusted by controlling the thickness.

[0040] The tensile strength (JIS K 6249) of the elastic layer 10 is higher because the durability of the tube is improved as it is higher. For example, 0. IMPa or higher, preferably 3 MPa or higher, more preferably 7 MPa or higher (for example, 7MPa to 75MPa).

[0041] It is desirable that the elastic body 11 constituting the elastic layer 10 also has high mechanical strength. If the mechanical strength of the elastic body 11 is high, not only can the mechanical strength of the elastic layer 10 be increased to increase the durability of the elastic layer 10, but also the bondability with the intermediate layer 30 can be improved. The tensile strength (JIS K 6249) of the elastic body 11 can be set, for example, in the range of about 0.1 to 75 MPa, preferably about 0.3 to 75 MPa.

[0042] The storage elastic modulus E '(temperature 20 ° C, frequency 1Ηζ, compression method) of the elastic layer 10 is, for example, about 1 X 10 2 to 1 X 10 ⁸ Pa. If the storage elastic modulus is too low, the shape recoverability when releasing the compressive stress will be poor. On the other hand, if the storage modulus is too high, it will be difficult to crush the tube, It becomes difficult to use for pinch valves and roller pumps. A preferable storage elastic modulus E is about 1 × 10 4 to 1 × 10 ⁸ Pa, particularly about 1 × 10 ^{5 to} 5 × 10 ⁷ Pa.

[0043] The storage elastic modulus E by the compression method is the value obtained by dividing the normal stress component in phase with the normal strain by the amount of strain described in Japanese Industrial Standard CFIS) K6200 Term No. 621 1. "Means. The storage elastic modulus E ′ can be measured by using, for example, a dynamic viscoelasticity measuring device “DMS6100” (manufactured by SII Nanotechnology Co., Ltd.).

[0044] The thickness of the elastic layer 10 (outer layer) is, for example, about 10 to 200%, preferably about 20 to 150%, more preferably, with respect to the inner diameter of the laminated elastic tube constituted by the inertia layer 10. It is about 25-125%. The thickness of the elastic layer 10 (outer layer) is, for example, about 0.15 to 80 mm, preferably about 0.3 to 60 mm, and more preferably about 0.4 to 50 mm. If the elastic layer 10 is too thin, when the tube is used for a pinch valve or a roller pump, the tube may not withstand the internal pressure of the fluid in the tube and may burst. In addition, the shape recoverability when releasing the compressive stress (pressing force) becomes insufficient. Conversely, if the elastic layer 10 is too thick, it becomes difficult to close the tube by pressing.

[0045] 2: Fluororesin layer (inner layer) 20

The laminated elastic tube of the present invention includes a fluorine resin layer 20 in addition to the elastic layer 10. The fluorine resin layer 20 is formed on the inner side of the elastic layer 10 and constitutes the inner surface of the tube. Hereinafter, the fluororesin layer 20 may be referred to as an inner layer. The inner surface of the fluororesin layer 20 has excellent chemical resistance and low tack (adhesiveness). When the elastic body 11 of the elastic layer 10 is inferior in chemical resistance such as silicone rubber, the chemical resistance of the tube itself is generally lowered, but the inner surface is made into the fluorine resin layer 20 as in the present invention. In this case, the fluorine resin layer 20 on the inner surface can be used as a barrier layer, and the chemical resistance of the tube can be increased. Furthermore, it is possible to prevent the fluid from adhering to the inner surface of the tube. In addition, the elastic body 11 of the elastic layer 10 has a high tackiness (adhesiveness) like a fluorine elastomer! In general, in this case, as described above, the inner surfaces adhere to each other and the tube is blocked, or the tube inner surface is damaged. On the other hand, the inner surface is made into the fluorine resin layer 20 as in the present invention. If so, these problems can be reduced. Furthermore, elution and swelling of the tube material can be prevented. [0046] The fluorine resin used for the inner layer 20 has low tackiness (adhesiveness). It also has excellent chemical resistance, for example, excellent durability against acids, alkalis and organic solvents. Therefore, it is also possible to distribute fluids such as photoresist liquids, liquids for operating process machinery, and highly corrosive liquids used in fields such as pharmaceuticals, food, medicine, and chemistry. It is. Examples of such a fluorine resin include a non-meltable (polytetrafluoroethylene (PTFE) having melt viscosity (for example, viscosity at 340 ° C) force of 10 ^1Q Pa · s or more). ), Etc.), fluororesin (tetrafluoroethylene perfluoroalkoxyethylene copolymer (PFA) having a melt viscosity (for example, a viscosity at 340 ° C of less than 10 ^1Q Pa's)) , Tetrafluoroethylene Monohexafluoropropylene Copolymer (FEP), Ethylene Tetrafluoroethylene Copolymer (ETFE), Polychlorinated Trifluoroethylene (PCTFE), Polyvinylidene Fluoride (PVDF) ), Polybulufluoride (PVF), Tetrafluoroethylene Hexafluoropropylene Bi-Ridene Fluoride Ternary Copolymer (THV), EFEP (Neoflon EFEP (trade name) manufactured by Daikin Industries, Ltd.) ), Etc. PTFE has a relatively small amount of comonomer, such as tetrafluoroethylene (relative to tetrafluoroethylene, for example, about 1% by mass or less (preferably about 0.1 to 0.3% by mass)). (Hexafluoropropylene (HFP), perfluoropropyl butyl ether (P PVE), perfluoroethyl butyl ether (PEVE), black trifluoroethylene (C TFE), perfluoro Also included are modified PTFE copolymerized with alkylethylene, etc. From the viewpoint of adhesion to other layers, meltable fluorine resin (especially PFA, FEP, PVDF, THV, EFEP, etc.) is excellent. From the viewpoint of chemical resistance and heat resistance, PTFE is excellent, and PTFE is also excellent in that it can be thinned by stretching. In the case of PTFE, it is recommended to use PTFE for the fluorine resin of the inner layer 20. Inner layer If both 20 and the intermediate layer 30 are formed of PTFE, the inner layer 20 and the intermediate layer 30 can be easily heat-sealed.

[0047] As the fluorinated resin, one type may be used, or two or more types may be used. First, the inner layer 20 will be described in more detail on the assumption that one type of fluorine resin is used, and later, the change points when two or more types of fluorine resin are used will be described.

[0048] The fluorinated resin of the inner layer 20 is usually a solid (folly-dense fluororesin). However, it may be a porous body (porous fluororesin). The porous body can be used when the elastic body 31 of the intermediate layer 30 has excellent chemical resistance such as a fluorine-based elastomer.

[0049] The solid fluorine resin means a fluorine resin substantially free of pores, and the porosity is, for example, less than 10%, preferably 5% or less, more preferably 1% or less. Especially 0%. The solid fluorine resin is usually obtained by extrusion as in the case of a general resin film, and after that, it can be obtained by stretching if necessary. The solid PTFE is obtained in the same manner as a general resin film. It is difficult. Solid PTFE can be obtained, for example, by scraping the non-porous sintered PTFE force (generally referred to as skived PTFE), or densifying the porous fluororesin (ePTFE) described later by compression or the like. (This is called densified PTFE). Details of the method for producing densified PTFE are described in JP-A-2002-275280. In addition, a fluorine resin having both a full structure and a stretched structure may be hereinafter referred to as a folly-dense expanded fluororesin.

[0050] The porous fluorine resin may be a fluorine resin obtained by forming a mixture of a fluorine resin powder and a solvent-soluble fine powder and then eluting the soluble fine powder with a solvent. Is preferably a porous PTFE obtained by stretching (expanded porous PTFE (ePT FE: also known as expanded porous polytetrailuoroethylene)) ePTFE is a mixture of PTFE fine powder and molding aid. This ePTFE may be uniaxially stretched, but preferably biaxially stretched, after being stretched at a high temperature and high speed after being removed. Microscopically, uniaxially stretched PTFE has thin island-like nodes (folded crystals) that are substantially perpendicular to the stretch direction, and interdigital fibrils that connect between the nodes (the folded crystals are stretched by stretching). The biaxially stretched PTFE has a fibril spreading radially and islands connecting the fibrils in islands. It has a microscopic feature in that it has a spider web-like fibrous structure that is dotted with many spaces defined by fibrils and nodes. Can be set as appropriate according to the amount of the fine particles and the draw ratio, for example, 10% or more, 30 It may be% or more. The upper limit of the porosity is not particularly limited, but is, for example, about 95% or less, preferably about 85% or less.

[0051] It should be noted that the porosity is the apparent density p (unit: g / cm ³ , JIS K 6885)

1

) And the original density (true density) p (2.2 g / cm ^{3 in} the case of PTFE) of the fluorocarbon resin when it is not made porous. Value.

2

Porosity (%) =-) / _β X IOO

2 1 2

[0052] Among the various types of fluorine resins, stretched fluorine resins (solid expanded fluorine resin, expanded porous fluorine resin, etc .; hereinafter, these are combined and referred to as expanded fluororesin) In particular, a fluorinated resin that is biaxially stretched is preferred. The inner layer 20 can be strengthened by stretching.

[0053] The stretching direction is not particularly limited, but it is preferably stretched in a direction (circumferential direction) orthogonal to the longitudinal direction of the tube. When the tube is stretched in the circumferential direction, the phenomenon that the tube tears in the longitudinal direction (vertical crack) when the tube is repeatedly pressed can be reduced.

[0054] Most preferred! / ヽ Fluororesin is a fully stretched fluorinated resin. Fully stretched fluorinated resin is excellent in all of barrier properties against chemicals, slidability, and mechanical strength. In particular, when densification treatment such as compression is applied, both the effect of improving the strength in the surface direction by stretching and the improvement of the strength in the thickness direction by densification are exhibited, and the mechanical strength of the inner layer 20 is remarkably increased. Can do. Further, it is excellent in flexibility, and even when subjected to repeated pressing, peeling occurs between the inner layer 20 and the intermediate layer 30. Furthermore, according to the fully-stretched fluorinated resin, a thin film made of the fluorinated resin can be easily obtained, which is advantageous for producing a wound film described later.

[0055] The form of the inner-layer fluorine resin layer 20 is not particularly limited, and is obtained by extruding a wound film obtained by winding a fluorine resin film or a fluorine resin in a tube shape. Any of an extruded tube and a coating layer obtained by coating a fluorine resin-containing liquid on the inner surface of the tube molded body may be used. Preferred forms are wound films, particularly wound films and extruded tubes. According to the wound film, an inner layer having high mechanical strength can be formed, and it is easy to match the stretching direction of the fluorine resin with the circumferential direction of the tube. [0056] In the wound film, the films that are wound and laminated may be bonded as appropriate. For example, the films may be bonded together with an adhesive via a primer or the like, or the films may be heat-sealed. Preferably, the films are heat-sealed. If heat-sealed, the film layers can be bonded extremely firmly. In general, fluorine resin has a high molecular weight to ensure practical mechanical strength with low intermolecular cohesion. For example, the molecular weight of PTFE is about 5 to 8 million according to an indirect measurement method such as an isop method. Even when such a high molecular weight fluorocobalt is heated above its melting point, the viscosity is high (for example, the viscosity when PTFE is heated above its melting point is about 10 ^1Q to 10 ¹² Pa's). Melt molding is considered difficult. On the other hand, when the fluororesin films are pressed to each other above the melting point of the fluororesin (and under conditions (temperature, time) that do not cause thermal decomposition), the fluororesin films may be fused. Are known. The interlayer adhesive force obtained by this heat fusion is strong, and an adhesive force equal to or higher than that obtained when the fluororesin films are bonded to each other with an adhesive via a primer or the like can be obtained. When it is difficult to heat-seal the fluorine resin films, it is possible to heat-seal the film through a meltable fluorine resin film or fluorine resin dispersion. Note that the melting point and thermal decomposition conditions (temperature, time) of fluorocarbon resin differ depending on the type, grade, and processing conditions (processing environment, etc.) of fluorocarbon resin, so DSC (differential scanning calorimeter) and TG ( It is desirable to know in advance using a thermogravimetric analyzer.

[0057] In the case where the inner layer 20 is a wound film, a process (tapering process) for inclining the corners of the wound end (end on the inner surface side, end on the outer surface side) may be performed. If the inner side edge is tapered, the adverse effect on the fluid in the tube can be reduced. Further, if the outer side edge portion is tapered, the adhesion between the inner layer 20 and the intermediate layer 30 can be improved. In order to taper, for example, a heating plate may be pressed against the winding end. Further, for the same purpose, the film thickness that can be inclined with respect to the tube center axis is sufficiently thin (for example, about 0.1 to 30 111, preferably 0). 5: about LO / zm, more preferably about 1-5 / ζ πι).

[0058] Further, on one side or both sides of the film, a table such as corona discharge treatment, excimer laser treatment, sand blast treatment, etching treatment with metallic sodium or liquid ammonia, etc. Surface treatment may be performed. By applying these surface treatments, the films can be bonded more firmly. In addition, the outer surface of the fluorine resin layer 20 may be subjected to the same surface treatment for the same purpose.

[0059] As described above, the inner layer 20 may be formed of two or more (for example, about 2 to 4 types, particularly 2 types) fluorine resins. Functions (chemical resistance, adhesiveness, etc.) can be shared among multiple fluorocarbons so that excellent functions can be exhibited as a whole. For example, a combination of fluorine resin with excellent chemical resistance and mechanical strength (such as fully-stretched fluorine resin) and fluorine resin with excellent adhesion (such as meltable fluorine resin) Fluororesin, which is particularly excellent in properties and mechanical strength, can be firmly bonded to the intermediate layer 30.

[0060] When the inner layer 20 is formed of two or more types of fluorine resin, each fluorine resin may be formed into a tube shape, and two or more types of tubes (fluorine resin) may be laminated in order from the inside. Good. Two or more kinds of fluorine resins may be laminated in a planar shape, and the planar laminate may be wound once or more (preferably a plurality of times) to form a tube. In the latter case, two or more kinds of fluorine resins can be arranged without being biased, so that the performance of the inner layer 20 as a whole can be further improved. Regardless of the former or the latter, it is recommended that the outermost side of the inner layer 20 be composed of a meltable fluorocarbon resin. This is because adhesion to the intermediate layer 30 is enhanced.

[0061] The thickness of the inner surface of the fluororesin layer 20 is, for example, about 1 to 200 μm, preferably about 5 to 100 μm, and more preferably about 5 to 40 / zm. If the inner layer 20 is too thin, the mechanical strength decreases. Therefore, it becomes difficult to improve the chemical barrier properties and the slidability of the tube inner surface. On the other hand, if the inner layer 20 is too thick, the entire tube becomes hard. Therefore, the shape recoverability when releasing the compressive stress (pressing force) tends to be insufficient. In addition, defects such as cracks are likely to occur due to repeated pressing.

[0062] The inner surface of the fluororesin layer 20 may be mixed with carbon or metal powder in order to impart conductivity or improve thermal conductivity.

[0063] 3: Intermediate layer 30

A feature of the laminated elastic tube of the present invention is that an intermediate layer 30 is formed between the fluorine resin layer 20 (inner layer) and the elastic layer 10 (outer layer). The intermediate layer 30 includes a porous fluorine resin 32 and an elastic body 31 that fills the pores of the porous fluorine resin 32. The inner layer fluorine resin layer 20 and the intermediate layer 30 porous fluorine resin 32 are joined. Further, the elastic layer 10 of the outer layer and the elastic body 31 of the intermediate layer 30 are joined. By forming such an intermediate layer 30, the peeling force acting between the inner layer 20 and the outer layer 10 can be buffered by the pressing force. In addition, the inner layer 20 and the intermediate layer 30 can be securely and firmly connected to each other by the bonding. Therefore, durability against repeated pressing and chemical resistance can be improved reliably.

[0064] For the porous fluorocarbon resin 32 of the intermediate layer 30, the fluorocarbon power exemplified in the above-mentioned inner layer 20 can also be selected, and preferably PTFE, PFA, PVDF, etc. (particularly PTFE) can be selected. As the porous PTFE, the aforementioned ePTFE can be used. As the porous PFA, PFA having pores formed by forming a mixture of PFA powder and solvent-soluble fine powder and then dissolving the soluble fine powder with a solvent can be used. As the porous PVDF, PVDF having pores formed by a dissolution method or the like can be used.

[0065] A preferred porous fluorocarbon resin 32 is a stretched porous fluorocarbon resin 32. The stretching direction of the elongated porous fluorocarbon resin 32 is not particularly limited, but it is preferably stretched in a direction (circumferential direction) perpendicular to the longitudinal direction of the tube. If the tube is stretched in the circumferential direction, it is possible to reduce a phenomenon (longitudinal crack) in which the tube tears in the longitudinal direction when the tube is repeatedly pressed. The stretched porous fluororesin 32 may be uniaxially stretched or biaxially stretched, but is preferably biaxially stretched.

[0066] Preferable! / The expanded porous fluorocarbon resin 32 is ePTFE. According to ePTFE, the porosity can be made sufficiently high, and a sufficient amount of the elastic body 31 can be filled in the pores. Moreover, it is excellent in flexibility, and there is no possibility that the function of the elastic body 31 is lowered. Furthermore, it is excellent in mechanical strength. ePTFE is available from Japan Gore-Tex Co., Ltd. as “ePTFE film”.

[0067] The porosity of the porous fluorocarbon resin 32 of the intermediate layer 30 is, for example, about 40 to 98%, preferably about 50 to 95%, and more preferably about 60 to 90%. If the porosity is too small, the filling amount of the elastic body 31 becomes small and the pressing force buffering function is lowered. On the other hand, if the porosity is too large, the mechanical strength of the porous fluorocarbon resin 32 is lowered and the bonding force with the inner layer 20 is lowered.

[0068] The maximum pore diameter of the porous fluororesin 32 of the intermediate layer 30 is the elastic body or elastic to be filled. From the viewpoint of the properties (ease of filling) of the elastic body raw material (details will be described later in detail) for forming a solid body, it may be set as appropriate, for example, 0.01 μm or more, preferably 0 .: L m or more, and below, preferably 10 m or less. If the maximum pore size is too small, it is difficult to fill the elastic body. If the maximum pore diameter is too large, the mechanical strength may be insufficient. The maximum pore size can be measured in accordance with the provisions of ASTM F316-86 (agent used: ethanol).

[0069] The form of the porous fluororesin 32 of the intermediate layer 30 is not particularly limited, and a wound porous film obtained by winding a porous fluororesin film, the fluororesin in a tube shape. Any of a porous extruded tube obtained by extrusion molding may be used. A preferred form is a wound porous film. According to the wound porous film, an intermediate layer having high mechanical strength can be formed, and it is easy to match the stretching direction of the fluorine resin with the circumferential direction of the tube.

[0070] When the intermediate layer 30 is formed of a wound porous film, the same treatment as in the case of forming the inner layer 20 of a wound film may be performed. In other words, the film thickness can be obtained by heat-bonding the films together or by tapering the wound end of the film or by making the edge of the wound end (end line) oblique to the central axis of the tube. The film may be sufficiently thin (for example, 1 to: about LOO / zm, preferably about 5 to 50 / ζ πι, more preferably about 10 to 40 / ζ πι). Good. Note that the surface treatment may be performed on the inner surface and the ridge or the outer surface of the intermediate layer 30.

[0071] On the other hand, as the elastic body 31 filling the pores of the porous fluorocarbon resin 32, various cured liquid elastic material raw materials exemplified in the outer layer 10 can be used. Preferably, the liquid elastic material is the same as in the outer layer 10.

[0072] The elastic body 31 of the intermediate layer 30 and the elastic body 11 of the outer layer 10 are preferably selected from the same resin. If the same resin is selected, the bondability between the intermediate layer 30 and the outer layer 10 can be improved. By the way, the “same rosin” means the same viewpoint power of bonding properties, and preferably refers to completely the same repellency, a group of rosins having a common monomer component, etc., but the main monomer is common. And a group of rosins whose main monomers are of the same strain.

[0073] The elastic body 31 of the intermediate layer 30 is combined with other materials in the same manner as the elastic body 11 of the outer layer 10. May be used. For example, the elastic body 31 may be mixed with organic fibers, inorganic fibers, carbons, metal fine particles, inorganic powders, and the like.

[0074] The tensile strength of the elastic body 31 of the intermediate layer 30 can be designed from the viewpoint of the bondability with the outer layer 10, and the range is approximately the same as the tensile strength of the elastic body 11 of the outer layer 10.

[0075] The tensile strength (JIS K 6249) of the intermediate layer 30 formed from the elastic body 31 and the porous fluororesin 32 is, for example, about 0.1 to 75 MPa, preferably about 2 to 75 MPa, and more preferably. Is about 5 to 75 MPa. The storage elastic modulus E of the intermediate layer 30 (temperature 20 ° C, vibration frequency 1Ηζ, compression method) is, for example, about 1 X 10 ² to 1 X 10 ⁸ Pa, preferably 1 X 10 ³ to 1 X 10 ^It is about ⁸ Pa, more preferably about 1 × 10 ⁶ to 1 × 10 ⁸ Pa. If the mechanical strength or storage elastic modulus E ′ is too low, the durability of the tube against repeated pressing is reduced. On the other hand, if the storage elastic modulus E ′ is too high, the followability to the outer layer 10 (elastic layer) is lowered, and the durability of the tube against repeated pressing is lowered.

[0076] The thickness of the intermediate layer 30 is, for example, about 10 to 2000 μm, preferably about 20 to 1500 μm, and more preferably about 50 to about LOOO m. If the intermediate layer 30 is too thin, durability during tube pressing will decrease. On the other hand, if the intermediate layer 30 is too thick, it begins to inhibit the elastic function of the outer layer 10.

[0077] Since the intermediate layer 30 of the present invention is bonded to the inner surface fluorine resin layer 20, the porous fluorine resin 32 is exposed on the inner surface side. Further, the elastic body 31 is exposed on the outer surface side of the intermediate layer 30 in order to join with the outer elastic layer 10.

[0078] 4: Manufacturing method

The laminated elastic tube of the present invention joins the inner fluororesin layer 20 and the porous fluororesin 32 of the intermediate layer 30, and the elastic body 31 of the intermediate layer 30 and the elastic body 11 of the outer layer 10. Can be obtained by joining. By joining them, the inner layer 20, the intermediate layer 30, and the outer layer 10 can be integrated.

[0079] Although it is recommended that the inner layer fluorine resin layer 20 and the porous fluorine resin layer 32 of the intermediate layer 30 be bonded by thermal fusion, a fluorine resin (melting property) for bonding to the interface is recommended. Adhesion (heat fusion) after interposing fluorine resin, fluorine resin dispersion, etc.). When heat-sealing, it is important to prevent thermal decomposition of fluorine resin. Therefore, As described above, it is desirable to know in advance the melting point and thermal decomposition conditions (temperature, time) of fluorinated resin using DSC (differential scanning calorimeter) or TG (thermogravimetric analyzer).

[0080] The elastic body 31 of the intermediate layer 30 and the elastic body 11 of the outer layer 10 may be joined by primer treatment or may be joined via an adhesive, but may be joined directly. It is desirable to do. If directly joined, there is no risk of impairing the elasticity of the intermediate layer 30 and the outer layer 10. When the elastic body 31 of the intermediate layer 30 and the elastic body 11 of the outer layer 10 are directly joined, at least one elastic material is brought into contact with the other elastic body (or elastic material) to form a three-dimensional network structure ( Curing). The rubbery body can be three-dimensional network structured (cured) by crosslinking. Further, the thermoplastic elastomer can be cured (cured) by, for example, cooling the thermoplastic state force or removing the cause of fluidization such as a solvent. The most preferable joining method is a method in which the elastic raw material 31 of the intermediate layer 30 and the elastic raw material 11 of the outer layer 10 are brought into contact with each other, and both elastic raw materials 31 and 11 are made into a three-dimensional network structure (cured). . According to this method, higher bonding strength can be obtained.

[0081] Various production methods can be adopted for the laminated elastic tube of the present invention as long as the above-described joining is possible. For example, (Method 1) After the outer side of the inner layer 20 is coated with the intermediate layer 30, the outer side of the intermediate layer 30 may be coated with the outer layer 10. (Method 2) A laminate of the intermediate layer 30 and the outer layer 10 is formed. Thereafter, the inner layer 20 may be coated on the inner surface of the intermediate layer 30. In either case of the methods 1 and 2, the filling of the liquid elastic material 31 into the intermediate layer 30 may be performed before or after the intermediate layer 30 is stacked. Also, the timing of curing the liquid elastic material 31 of the intermediate layer 30 is not particularly limited!

A preferred production procedure is (Method 1) in which the outer side of the inner layer 20 is coated with the intermediate layer 30 and then the outer side of the intermediate layer 30 is coated with the outer layer 10. According to Method 1, the inner layer fluorine resin 20 and the intermediate layer 30 porous fluorine resin 32 can be heat-sealed.

[0083] According to this method 1, the filling of the liquid elastic material 31 into the intermediate layer 30 (porous fluorine resin 32) is preferably performed after the intermediate layer 30 (porous fluorine resin 32) is laminated ( Method 1-When Doo liquid elastic material 31 is filled after lamination, porous fluorine resin 32 is exposed before being laminated without being covered with liquid elastic material 31. Therefore, the inner layer fluorine resin 20 is The intermediate layer of porous fluorocarbon resin 32 can be reliably heat-sealed, and the elastic body 31 can be heat-sealed. There is no risk of thermal degradation under certain conditions. Then, after covering the inner layer 20 (the tube made of the fluorine resin layer) with the porous fluorine resin 32 and heat-sealing them, the porous fluorine resin 32 side force is also reduced in the pores of the porous fluorine resin 32. The liquid elastic material 31 may be filled in and a three-dimensional network structure may be formed after filling.

[0084] When the liquid elastic material 31 is filled in the intermediate layer 30 (porous fluorine resin 32), it may be filled in the required amount accurately or excessively, and then the excess may be removed by force. Good. It can also be used as the outer layer 10 (elastic layer) by hardening without surrendering excess.

[0085] When the laminated elastic tube is manufactured by the method 1-1, the outer layer 10 may be laminated on the intermediate layer 30 after being cured (Method A), or the intermediate layer in an uncured state. It may be stacked on 30 and cured (Method B). In the case of Method A, the intermediate layer 30 and the outer layer 10 can be joined by using a primer treatment or an adhesive. A preferred method is Method B. According to method B, the elastic body 31 of the intermediate layer 30 and the elastic body 11 of the outer layer 10 can be directly joined.

[0086] When uncured outer layer 10 (liquid elastic material, solid (kneadable) elastic material, etc.) is laminated on intermediate layer 30 (method B), uncured outer layer 10 is intermediate layer 30. After filling the elastic material 31 into the intermediate layer 30, the intermediate layer 30 may be laminated (Method Bl), and the intermediate layer 30 may also be filled with the elastic material 31 (particularly the liquid elastic material). Laminate 30 (Method B2). In the case of Method B1, the uncured outer layer 10 may be laminated after the elastic material 31 of the intermediate layer 30 is cured (Method Bla), and is uncured before the elastic material 31 of the intermediate layer 30 is cured. The outer layer 10 may be laminated (Method Bib). In the case of the method B2 and the method Bib, the elastic material 31 of the intermediate layer 30 and the elastic material 11 of the outer layer 10 can be cured at the same time, and the bonding strength can be significantly increased. In the case of the method Bib, it is desirable to select the elastic body 31 of the intermediate layer 30 and the elastic body 11 of the outer layer 10 from the same resin, but different types of resin may be used.

A specific method for forming the outer layer 10 is exemplified as follows.

(i) A cylindrical intermediate body obtained by heat-sealing the inner layer 20 (a tube made of a fluorine resin layer) and the porous fluorine resin 32 is a cylinder having an inner diameter larger than the outer diameter of the intermediate body. A method of setting in the center of the body, casting an elastic material 11 (liquid elastic material, solid (kneading) elastic material, etc.) into the void, and then demolding after curing. Use a die as a cylinder. In order to set the center of the cylindrical intermediate correctly, -pull is often used

(ii) Method of laminating elastic material 11 (especially solid (kneadable) elastic material) on the outer surface of the cylindrical intermediate body by extrusion, preparing the outer surface, and curing

(iii) A method in which elastic material 11 (especially solid (kneadable) elastic material) is laminated on the outer surface of the cylindrical intermediate body by extrusion and cured, and then the outer surface is prepared by polishing or the like.

(iv) a laminated film 10 comprising an elastic material 11 (first layer 12) and a porous film (second layer 13) impregnated with the elastic material 11 (particularly a liquid elastic material), A method in which the elastic raw material 11 (first layer 12) is wound around the outer surface of the cylindrical intermediate body and cured while being in contact with the intermediate layer 30.

(V) A method in which the cylindrical intermediate body is inserted into an outer layer 10 (elastic tube) that has been molded and cured in advance into a cylindrical shape, and these are bonded together with an adhesive or the like.

These (i) to (V) may be continuously manufactured by appropriately changing the force that assumes batch production. Further, after forming a cured or uncured elastic layer by the method (iv), an elastic layer is further formed by the method (i) to (iii) or (V). They can be manufactured in any suitable combination.

[0088] 5: Wear resistant layer 40

In the laminated elastic tube of the present invention, as shown in the schematic cross-sectional view of FIG. 4, a wear resistant layer 40 (wear resistant tube) may be further formed outside the outer layer 10 (elastic layer) as required. Yes. The wear resistant layer 40 can further enhance the durability of the tube.

[0089] The wear resistant layer 40 (wear resistant tube) includes polymer materials such as butyl chloride, polystyrene, polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polyamide, polyimide, fluorine resin, Various materials such as inorganic materials such as glass fiber can be used.

[0090] The wear-resistant layer 40 (wear-resistant tube) is composed of a coated body, an extrusion-molded tube, an extruded stretched tube, a stretched film roll, a full film roll, a porous film roll, Any shape such as a knitted body in which yarns are knitted in a tube shape, a woven fabric, a knitted fabric, a braided body, a wound body such as a lace or a net may be used. The wear resistant layer 40 has a followability and resistance to the elastic layer 10. It is important to have both wear characteristics, and the shape can be selected according to the hardness of the material.

[0091] The wear resistant layer 40 (wear resistant tube) may or may not be fixed to the elastic layer 10, but is preferably fixed from the viewpoint of further improving the wear resistance. When the wear-resistant layer 40 and the elastic layer are fixed, the fixing method is not particularly limited. For example, it may be fixed using an adhesive, but by using the same elastic body as the outer layer 10 as an adhesive. It is preferable to fix the wear-resistant layer 40. It is also preferable to laminate and fix the wear resistant layer 40 (wear resistant tube) using the shrinkage force of the wear resistant layer 40 (wear resistant tube). If the contraction force is used, the elasticity of the tube will not be impaired.

[0092] Preferably, the wear-resistant layer 40 (wear-resistant tube) is a fluorine resin tube, particularly a PTFE tube. Fluororesin tubing (especially PTFE tubing) has excellent wear resistance, chemical resistance, and heat resistance.

[0093] When the wear-resistant tube 40 is formed of fluorine resin (particularly PTFE), the tube includes a wound body of a porous fluorine resin film, a knitted body obtained by knitting fluorine resin yarn in a tube shape, fluorine It is desirable to use a wound body of woven fabric, knitted fabric, braided fabric, lace, net, etc. made of a resin yarn. If these are used, since the adhesive or elastic material penetrates into the pores or between the fibers, the wear-resistant layer 40 can be firmly joined to the elastic layer 10.

[0094] It should be noted that a plurality of wear-resistant layers 40 (wear-resistant tubes) may be stacked, for example, a fluorocarbon resin tube and a glass cloth roll may be stacked.

[0095] 6: Laminated elastic tube

The size of the laminated elastic tube of the present invention differs depending on the application and is difficult to define uniformly. For example, when used for an elastic tube for a pinch valve and a roller pump, an inner diameter: lmm or more (for example, l ˜40 mm), outer diameter: 100 mm or less (eg, about 3 to 100 mm, especially about 5 to 60 mm), and length of about 50 to 1500 mm.

[0096] 7: Fluid flow control member

The laminated elastic tube of the present invention can be used as a member that controls the flow of fluid by pressing, and can be used, for example, as an elastic tube of a pinch valve or a roller pump. A pinch nore is a pinch operated by fluid pressure (pneumatic, hydraulic, etc.) or electricity. This is a device that controls the flow of fluid in the tube by pressing the elastic tube in the radial direction from the side with a valve and flattening (especially closing) the cross section of the tube. A roller pump is a roller or other pressing member that presses the inertial tube in the radial direction and moves the pressing member in the axial direction of the elastic tube while maintaining this pressing state (especially repeated from the upstream side to the downstream side). It is a device that sends out the fluid in the tube by moving.

[0097] The type of fluid flowing through the tube is not particularly limited, and may be gas or liquid! /, But is preferably liquid. In particular, since the laminated elastic tube of the present invention has excellent chemical resistance, it is highly corrosive used in the fields of photoresist liquids, liquids for operating process machinery, pharmaceuticals, food, medicine, chemistry, etc. It is also possible to circulate fluids such as other liquids. In addition, since the laminated elastic tube of the present invention has low tackiness, it can be used even for applications that dislike the flow component adhering to the inner surface of the tube.

Furthermore, the laminated elastic tube of the present invention can also be used as a cable tube (push-pull tube) in which a metal wire for transmitting torque or the like is passed through the tube. Since the elastic tube of the present invention has a high slip property of the fluorine resin layer 20 on the inner surface, torque can be transmitted smoothly.

[0099] When the laminated elastic tube of the present invention is used for an application where elasticity is not necessarily required such as a hose or piping, the outer elastic layer 10 is not necessary.

[0100] According to the present invention, the intermediate layer in which the pores of the porous fluorine resin are filled with an elastic body is interposed between the fluorine resin layer on the inner surface and the outer elastic layer. Thus, the adhesion between the fluorine resin layer and the outer elastic layer can be remarkably improved, and the durability against repeated pressing and the chemical resistance can be reliably improved.

Example

[0101] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples as well as the present invention, and is appropriately modified within a range that can meet the purpose described above and below. Of course, the present invention can be carried out in addition to the above, and they are all included in the technical scope of the present invention.

[0102] Example 1

Outer diameter: 300mm, width: 600mm, meta rolling reaction force: 1MN (maximum) calendar roll device Roll temperature: 70 ° C, linear pressure: 8NZmm ² , feed rate: 6mZ biaxially stretched porous PTFE film ("ePTFE film" manufactured by Japan Gore-Tex Co., Ltd.), width: 500m m , Porosity: 90%, thickness: 20 m) was compressed to obtain a cloudy white film having a width: 500 mm, a length: 500 mm, a porosity: 5%, and a thickness of 2.1 m. This white turbid film is sandwiched between two polyimide films ("UPILEX 20S" (trade name) manufactured by Ube Industries, Ltd.). Press surface size: 750mm x 750mm, maximum pressure: 2MN hot Using a press machine, press the plate temperature: 400 ° C, surface pressure: lONZm ² for 5 minutes, press the plate for 5 minutes, and gradually increase the plate temperature to 25 ° C over 60 minutes while maintaining the surface pressure. Was cooled to a width of 500 mm, length: 500 mm, porosity: 0%, thickness: 2 m, and a transparent PTFE film (densified PTFE film) was obtained.

[0103] The densified PTFE film is cut into a size of width: 400 mm, length (depth): 158 mm, and a stainless steel rod so that the length (depth) direction is the winding direction (circumferential direction). The material (outer diameter: 5 mm) was wound 10 times to form an inner layer having a thickness of about 20 m.

[0104] Biaxially stretched porous PTFE film ("ePTFE film" manufactured by Japan Gore-Tex Co., Ltd.), width: 400mm, length (depth): 81mm, porosity: 85 %, Maximum pore diameter: 0.5 m, thickness: 20 m) on the inner layer so that its length (depth) direction is the winding direction (circumferential direction) (number of times of winding: 5 )did. This wound product is heated for 30 minutes at a temperature of 375 ° C using a forced hot air circulation / ventilation-type constant temperature and humidity chamber (Espec Co., Ltd., “STPH-201”). Cylindrical intermediate with an outer diameter of 5.2 mm using a stainless steel rod with an outer diameter of 5 mm as the core material between the films of the fluororesin film and between the inner layer film and the porous fluorine resin film. Got the body. Apply 10g of addition reaction type liquid silicone rubber (“KE1031” manufactured by Shin-Etsu Chemical Co., Ltd.) to the porous fluororesin film surface of the cylindrical intermediate using a rubber spatula. Was impregnated. Excess silicone rubber was rubbed off with a rubber spatula and non-woven wiper.

[0105] Heat-curing type mirabilized silicone rubber (ΓΚΕ551—U ”manufactured by Shin-Etsu Chemical Co., Ltd.) and a vulcanizing agent "C-23" manufactured by Shin-Etsu Chemical Co., Ltd.) was blended at a mass ratio of 100: 1 and kneaded using a mixing roll machine. Metal extrusion with a concentric arrangement of dies with an inner diameter of 9.6 mm and -pulls with an inner diameter of 5.2 mm The cylindrical intermediate body was inserted into the crosshead for use with an inlet side force. The kneaded heat-vulcanized silicone rubber was pushed in from the middle side of the inlet and outlet of the crosshead for extrusion with a screw. Due to the rubber pressure flow caused by the indentation, the cylindrical intermediate is also discharged from the outlet side of the extrusion head, then heated at a primary vulcanization temperature of 170 ° C for 20 minutes, and then at a secondary vulcanization temperature of 200 ° C. Both liquid silicone rubber and millable silicone rubber were crosslinked by heating for a period of time.

[0106] After cooling, twist the outer layer (elastic layer) by hand, loosen the inner layer densified PTFE and the core material (stainless steel bar), and pull out the stainless steel bar to laminate elasticity The tube was obtained (inner diameter: 5mm, outer diameter: 9.6mm, axial length: 400mm, inner layer thickness: 20m, middle layer thickness: 100m, outer layer thickness: 2.2mm ).

[0107] Example 2

In the same manner as in Example 1, a cylindrical intermediate body impregnated with liquid silicone rubber was obtained.

[0108] Biaxially stretched porous PTFE film ("ePTFE film" manufactured by Japan Gore-Tex Co., Ltd.), width: 400mm, length (depth): 816mm, porosity: 78%, maximum pore diameter: 0.4 / ζ πι, thickness: 18 m), addition reaction type liquid silicone rubber (“KE1 031” manufactured by Shin-Etsu Chemical Co., Ltd.) was applied from one side. The coated film was wound around the cylindrical intermediate body to make an outer layer while keeping the coated surface inward and preventing air from being entrained (number of wrinkles: 35 times).

[0109] The liquid silicone rubber in the intermediate layer and the outer layer was crosslinked by heating at a temperature of 150 ° C for 30 minutes.

[0110] After cooling, twist the outer layer (elastic layer) by hand, loosen the inner layer densified PTFE and the core material (stainless steel bar), and pull out the stainless steel bar to laminate elasticity The tube was obtained (inner diameter: 5mm, outer diameter: 9.6mm, axial length: 400mm, inner layer thickness: 20m, middle layer thickness: 100m, outer layer thickness: 2.2mm , Outer silicone rubber layer (first layer) thickness: 1550 / ζ πι, outer layer PTFE film layer (second layer) thickness: 630 m, first layer thickness Z second Layer thickness = 2.5Zl).

[0111] Example 3

Heat-cured liquid fluororubber (“SIFEL—8070A / BJ” manufactured by Shin-Etsu Chemical Co., Ltd.), biaxially stretched outer layer An elastic tube was obtained in the same manner as in Example 2 except that the heat-curing liquid fluororubber (“SIFEL-610” manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the rubber applied to the expanded porous PTFE film. (Inner diameter: 5 mm, outer diameter: 9.6 mm, axial length: 400 mm, inner layer thickness: 20 πι, middle layer thickness: 100 m, outer layer thickness: 2.2 mm, outer layer fluorine Rubber layer (first layer) thickness: 1550 / ζ πι, outer PTFE film layer (second layer) thickness: 630 m, first layer thickness Z second layer thickness = 2.5Zl).

[0112] Comparative Example 1

Heat vulcanized millable silicone rubber (“KE551—U” manufactured by Shin-Etsu Chemical Co., Ltd.) and a vulcanizing agent (manufactured by Shin-Etsu Chemical Co., Ltd.) C-23 ") was blended at a mass ratio of 100: 1 and kneaded using a mixing roll machine. A stainless steel bar with an outer diameter of 5 mm was inserted into a metal extrusion cloth head concentrically arranged with a die having an inner diameter of 9.6 mm and a 5-pull inner diameter. The kneaded heat-vulcanized silicone rubber was pushed in by a screw from the intermediate side surface of the inlet and outlet of the extrusion cloth head. Due to the pressure flow of the rubber due to indentation, the stainless steel bar is also discharged at the outlet side of the extrusion head, then heated at a primary vulcanization temperature of 170 ° C for 20 minutes, and further heated at a secondary vulcanization temperature of 200 ° C for 4 hours. By doing so, the millable silicone rubber was crosslinked.

[0113] After cooling, twist the outer silicone rubber by hand to loosen the crimping with the inner stainless steel bar, and pull out the stainless steel bar to obtain an elastic tube (inner diameter: 5mm, outer diameter : 9.6mm, axial length: 400mm, thickness: 2.3mm).

[0114] Comparative Example 2

Biaxially stretched porous PTFE film used in Example 2 ("eP TFE film" manufactured by Japan Gore-Tex Co., Ltd.), width: 400mm, length (depth): 826mm, porosity: 78%, maximum pore diameter : 0.4 m, thickness: 18 m), an addition reaction type liquid silicone rubber (“KE1031” manufactured by Shin-Etsu Chemical Co., Ltd.) was applied from one side. The coated film was wound around a stainless steel bar (outer diameter: 5 mm) while keeping the coated surface inward and without entraining air (number of creases: 36 times). Liquid silicone rubber was crosslinked by heating at 150 ° C for 30 minutes. [0115] After cooling, the rubber part was twisted by hand to loosen the crimping with the inner stainless steel bar, and the elastic tube was obtained by pulling out the stainless steel bar (inner diameter: 5mm, outer diameter: 9.6 mm, axial length: 400 mm, total thickness: 2.3 mm, silicone rubber layer (first layer) thickness: 1650 μm, PTFE film layer (second layer) thickness Thickness: 650 μm, first layer thickness Z second layer thickness = 2.5 Zl).

[0116] Comparative Example 3

An elastic tube was obtained (inner diameter: 5 mm, outer diameter) in the same manner as in Comparative Example 2 except that the rubber to be applied was heat-cured liquid fluororubber (“SEIFEL-6 10” manufactured by Shin-Etsu Chemical Co., Ltd.). : 9.6 mm, axial length: 400 mm, overall thickness: 2.3 mm, fluororubber layer (first layer) thickness: 1650 μm, PTFE film layer (second layer) thickness 650 μm, first layer thickness Z second layer thickness = 2.5 Zl).

[0117] Comparative Example 4

A densified PTFE film was obtained in the same manner as in Example 1.

[0118] This densified PTFE film is cut into a size of width: 400mm, length (depth): 158mm, and a stainless steel rod so that the length (depth) direction is the winding direction (circumferential direction) The material (outer diameter: 5 mm) was wound 10 times. Next, using a forced hot air circulation / ventilation type constant temperature and humidity chamber (Espec Co., Ltd., “STPH-201”), heated at a temperature of 375 ° C for 30 minutes, heat-sealed between the PTFE films, A 20 m inner layer was formed.

[0119] Heat-curing type mirabil silicone rubber (Γ 551—U, manufactured by Shin-Etsu Chemical Co., Ltd.) and vulcanizing agent (Shin-Etsu Chemical Co., Ltd.), which are pre-mixed with various additives such as reinforcing fillers and plasticizers. “C-23” manufactured by Kogyo Co., Ltd. was blended at a mass ratio of 100: 1 and kneaded using a mixing roll machine. The inlet side force was inserted into a metal extrusion cross head in which a die having an inner diameter of 9.6 mm and a 5-pull inner diameter were concentrically arranged while the inner layer was wound around a stainless steel bar. The kneaded heat vulcanized silicone rubber was pushed in from the middle side of the inlet and outlet of the extrusion crosshead with a screw. The inner layer wound around the stainless steel bar is discharged by the pressure flow of the rubber due to the indentation, the outlet side force of the extrusion head is discharged, then heated at the primary vulcanization temperature of 170 ° C for 20 minutes, and further the secondary vulcanization temperature The millable silicone rubber was crosslinked by heating at 200 ° C for 4 hours. [0120] After cooling, twist the outer layer (elastic layer) by hand to loosen the inner layer densified PTFE and the core material (stainless steel bar), and pull out the stainless steel bar to pull out the elastic tube. Obtained (inner diameter: 5 mm, outer diameter: 9.6 mm, axial length: 400 mm, inner layer thickness: 20 m, outer layer thickness: 2.3 mm).

[0121] The chemical resistance and durability of the elastic tubes obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were examined as follows.

[0122] Chemical resistance

Cyclohexane was filled in the hollow of the elastic tube and kept at a temperature of 20-25 ° C for 70 hours. After discharging cyclohexane, the change in mass of the tube before and after the test was measured and evaluated according to the following criteria.

Excellent: Less than 30% mass change

Impossible: Mass change is 30% or more

[0123] Durability

Resin pinch valve for wet process (manufactured by Asahi Organic Materials Co., Ltd., trade name “Dymatri _X

AVPV3 ”) was fitted with an elastic tube. This pinch valve can press a 15 mm x 10 mm prismatic piston (the peripheral edge of the tip is chamfered (curvature 0.4)) toward the flat plate with compressed air. Press the tube between. The elastic tube was repeatedly pressed with a piston that did not allow liquid to pass through the tube. The conditions for pressing are as follows.

Pressing time: 1.5 seconds Z times

Pressure release time: 1.5 sec Z times

Compressed air pressure: 0.4MPa

[0124] The outer surface of the tube was visually confirmed, and the number of repetitions until damage occurred was counted.

In addition, the cross section of the tube was visually confirmed, and the number of repetitions until delamination occurred was counted.

[0125] [Table 1]

* Indicates not evaluated.

[0126] As is clear from Table 1, the elastic tubes of Examples 1 to 3 have durability against repeated pressing and resistance because the inner layer and outer layer (elastic layer) are joined by an appropriate intermediate layer. Excellent chemical properties.

Industrial applicability

[0127] The laminated elastic tube of the present invention is used, for example, for applications in which a fluid flows in the tube (especially an elastic tube used for a pinch valve or a roller pump). For applications such as controlling the flow of fluid in a tube) or applications that allow non-fluid to pass through a tube (for example, a cable tube (push-pull tube) with a metal wire passed through it to transmit torque, etc.) Can be used.

Claims

The scope of the claims

[I] A laminated elastic tube having an inner surface composed of a fluorine resin layer and an elastic layer formed outside the fluorine resin layer,

Between the fluorine resin layer and the elastic layer, an intermediate layer composed of a porous fluorine resin and an elastic body filling the pores of the porous fluorine resin is formed,

A laminated elastic tube characterized in that an inner surface fluorine resin layer and an intermediate layer porous fluorine resin are bonded, and an outer elastic layer and an intermediate layer elastic body are bonded. .

[2] The fluorine resin layer on the inner surface is a tube wound with a fluorine resin film.

1. The laminated elastic tube according to 1.

[3] The laminated elastic tube according to [1] or [2], wherein the fluorine resin layer on the inner surface is a stretched fluorine resin layer.

4. The laminated elastic tube according to claim 3, wherein a stretching direction of the stretched fluororesin layer is orthogonal to a length direction of the tube.

[5] The laminated elastic tube according to [3] or [4], wherein the stretched fluorine resin layer is a solid stretched fluorine resin layer.

[6] The laminated elastic tube according to [5], wherein the solid stretched fluorine resin layer is a solid stretched polytetrafluoroethylene layer.

[7] The laminated elastic tube according to [1] or [2], wherein the fluorine resin layer on the inner surface is formed of a meltable fluorine resin.

[8] The meltable fluorine resin is PFA, FEP, PVDF, THV, or EFEP.

The laminated elastic tube according to 7.

[9] The laminated elastic tube according to [1], wherein the fluorine resin layer on the inner surface is a laminate of two or more kinds of fluorine resins.

10. The laminated elastic tube according to claim 9, wherein the two or more types of fluorine resin are each in a tube, and the tubes are laminated in order from the inner cover.

[II] The fluorine resin layer on the inner surface is formed by laminating the two or more kinds of fluorine resins in a planar shape and winding the planar laminate into a tube shape. Described in Laminated elastic tube.

[12] The laminated elastic tube according to any one of [9] to [11], wherein one of the two or more types of fluorine resin is a fully-stretched fluorine resin.

[13] The method according to any one of [9] to [12], wherein one of the two or more types of fluorine resin is a meltable fluorine resin.

V, laminated elastic tube according to any of the above.

[14] The meltable fluorine resin is disposed on the outermost side of the fluorine resin layer on the inner surface.

13. The laminated elastic tube according to 13.

[15] The meltable fluorine resin is PFA, FEP, PVDF, THV, or EFEP.

The laminated elastic tube according to 13 or 14.

16. The laminated elastic tube according to any one of claims 1 to 15, wherein the fluorine resin layer on the inner surface and the porous fluorine resin on the intermediate layer are heat-sealed.

17. The laminated elastic tube according to any one of claims 1 to 16, wherein the porous fluorine resin in the intermediate layer is porous polytetrafluoroethylene.

18. The elastic material of the intermediate layer is at least one selected from silicone elastomer, fluorine elastomer, and fluorosilicone elastomer.

V, laminated elastic tube according to any of the above.

[19] The elastic body of the intermediate layer includes a polyester-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, a styrene-based block copolymer elastomer, a thermoplastic vulcanized elastomer, a polyamide. The laminated elastic tube according to any one of claims 1 to 17, which is at least one kind selected from the group of thermoplastic elastomers.

[20] The laminated elastic tube according to any one of [1] to [19], wherein the outer elastic layer is at least one selected from the group consisting of a silicone elastomer, a fluorine elastomer, and a fluorosilicone elastomer. .

[21] The outer elastic layer comprises a polyester thermoplastic elastomer, a polyurethane thermoplastic elastomer, a polyolefin thermoplastic elastomer, a styrene block copolymer elastomer, a thermoplastic vulcanized elastomer, a polyamide system. The laminated elastic tube according to any one of claims 1 to 19, which is at least one kind selected from thermoplastic elastomers.

The laminated elastic tube according to any one of claims 1 to 21, wherein the elastic body of the intermediate layer and the elastic body of the outer elastic layer are both formed from the same resin.

23. The laminated elastic tube according to claim 1, wherein the outer elastic layer has a storage elastic modulus E and a force of 1 × 10 ² to 1 × 10 ⁸ Pa.

[24] The outer elastic layer fills the pores of (1) a first layer also having elastic force, (2) a porous polytetrafluoroethylene film, and the porous polytetrafluoroethylene film. 2. A spiral laminated structure in which a second layer made of an elastic body overlaps with the second layer.

The laminated elastic tube according to any one of?

25. The laminated elastic tube according to claim 24, wherein a ratio of the thickness of the first layer to the thickness of the second layer (first layer Z second layer) is 6.5Z1 or less.

[26] The thickness of the fluorine resin layer on the inner surface is 1 to 200 / ζ πι, and the thickness of the intermediate layer is 10 to 2000.

26. The laminated elastic tube according to any one of claims 1 to 25, wherein / z m and the thickness of the outer elastic layer is 0.15 to 80 mm.

[27] The laminated elastic tube according to any one of [1] to [26], wherein the thickness force of the outer elastic layer is 10 to 200% with respect to the inner diameter of the laminated elastic tube.

[28] The laminated elastic tube according to any one of [1] to [27], wherein an abrasion-resistant layer is formed on the outer side of the outer elastic layer.

29. The laminated elastic tube according to claim 28, wherein the wear-resistant layer is a polytetrafluoroethylene tubular material.

[30] A pinch valve using the laminated elastic tube according to any one of claims 1 to 29.

[31] A roller pump using the laminated elastic tube according to any one of claims 1 to 29.

[32] After coating the tube made of the fluorine resin layer with porous fluorine resin, and heat-sealing them,

Porous Fluororesin Side Force A porous elastic raw material is filled with a liquid elastic raw material, and after filling, a three-dimensional network structure is formed to make the elastic raw material into an elastic body. A method for producing a laminated elastic tube according to any one of the above.

[33] A tube composed of a fluorine resin layer was coated with porous fluorine resin, and these were heat-sealed. rear,

Porous fluorine resin side force After filling the pores of the porous fluorine resin with a liquid elastic material, and further forming a layer containing the elastic material on the outside of the porous fluorine resin, a three-dimensional network The method for producing a laminated elastic tube according to any one of claims 1 to 29, wherein a structure is formed to make both of the elastic body materials into an elastic body.