WO2023112692A1 - 積層チューブ - Google Patents

積層チューブ Download PDF

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Publication number
WO2023112692A1
WO2023112692A1 PCT/JP2022/044346 JP2022044346W WO2023112692A1 WO 2023112692 A1 WO2023112692 A1 WO 2023112692A1 JP 2022044346 W JP2022044346 W JP 2022044346W WO 2023112692 A1 WO2023112692 A1 WO 2023112692A1
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WIPO (PCT)
Prior art keywords
resin layer
layer
polypropylene resin
polyamide resin
organic particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/044346
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
正志 岡久
幸治 水谷
依史 瀧本
計宏 齋木
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Sumitomo Riko Co Ltd
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Sumitomo Riko Co Ltd
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Filing date
Publication date
Application filed by Sumitomo Riko Co Ltd filed Critical Sumitomo Riko Co Ltd
Priority to DE112022003678.8T priority Critical patent/DE112022003678T5/de
Priority to CN202280056996.0A priority patent/CN117859022A/zh
Publication of WO2023112692A1 publication Critical patent/WO2023112692A1/ja
Priority to US18/434,033 priority patent/US20240173936A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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 non-planar shape
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/30—Particles characterised by physical dimension
    • B32B2264/302—Average diameter in the range from 100 nm to 1000 nm
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/30—Particles characterised by physical dimension
    • B32B2264/303—Average diameter greater than 1µm
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/50—Particles characterised by their position or distribution in a layer
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width

Definitions

  • the present invention mainly relates to laminated tubes used for piping of cooling systems in vehicles such as automobiles.
  • polyamide resins have been used as piping materials for cooling systems in gasoline vehicles due to their superior strength and heat resistance.
  • Polyamide resin the same as that used in gasoline vehicles, has also been used as a piping material for cooling systems in electric vehicles.
  • the need for cooling the interior of electric vehicles is increasing.
  • tubes made of polyamide resin still have a problem in terms of price. Therefore, in order to solve the above problems, the use of a tube made of inexpensive polypropylene resin has been investigated.
  • a low-cost and high-performance tube that utilizes the properties of both layers by laminating a polyamide resin layer and a polypropylene resin layer has also been studied (see Patent Documents 1 and 2).
  • the interlayer adhesion of the polypropylene resin layer to the polyamide resin layer is low. Without such sufficient interlayer adhesion, the outer layer of the tube cannot be protected, and the internal pressure of the fluid flowing through the tube causes the tube to be easily ruptured. Further, when the laminated tube as described above is subjected to bending, etc., annealing (heat treatment) is performed near the melting point of the resin of each layer, so there is also the problem that interlayer adhesion tends to decrease at that time.
  • the polypropylene resin layer is a maleic anhydride-modified polypropylene resin layer, thereby improving the adhesiveness with the polyamide resin layer.
  • Annealing heat treatment
  • the present invention has been made in view of such circumstances, and provides a laminated tube that is excellent in strength, heat resistance, etc., exhibits excellent interlayer adhesion without an adhesive, and has good interlayer adhesion after annealing. offer.
  • the present inventors have made intensive studies in order to solve the above problems.
  • various experiments were conducted to investigate improvements in interlaminar adhesion and the like for a tube having a laminated structure of a maleic anhydride-modified polypropylene resin layer and a polyamide resin layer.
  • the polyamide resin in the polyamide resin layer a polyamide resin having an amine value of 15 to 100 mmol/kg is used, and organic particles exhibiting a specific particle size are added to the material of the polypropylene resin layer.
  • a large number of convex protrusions due to the organic particles appear on the side of the polypropylene resin layer.
  • the chemical bond between the amino group of the polyamide resin and the maleic anhydride-modified group of the polypropylene resin improves the interlaminar adhesion between the two layers, and furthermore, the anchoring effect (anchor Effect) increases the contact area between both layers and also improves the frictional force, leading to more effective interlayer adhesion. Therefore, it is possible to further improve the interlayer adhesion of both layers even without an adhesive (no adhesive), and furthermore, it is possible to solve the problem of tube rupture due to deterioration of interlayer adhesion due to annealing and the like. I found what I could do.
  • the gist of the present invention is the following [1] to [6].
  • a laminated tube having a layer structure in which a polypropylene resin layer and a polyamide resin layer are laminated in close contact The polypropylene resin in the polypropylene resin layer is maleic anhydride-modified polypropylene, and the polypropylene resin layer contains organic particles having an average particle size of 0.1 to 10 ⁇ m,
  • the polyamide resin in the polyamide resin layer is a polyamide resin having an amine value of 15 to 100 mmol/kg, At the interface between the polypropylene resin layer and the polyamide resin layer, on the side of the polypropylene resin layer, a large number of protrusions formed by the organic particles are formed, laminated tube.
  • the laminated tube of the present invention is excellent in strength, heat resistance, etc., exhibits excellent interlayer adhesion even without an adhesive, and further exhibits good interlayer adhesion even after annealing. be able to. Therefore, it is possible to solve problems such as deterioration of interlayer adhesion due to annealing and tube rupture resulting therefrom.
  • FIG. 3 is a schematic diagram showing a laminated state of laminated tubes according to the present invention.
  • the laminated tube (hereinafter referred to as "this laminated tube") which is one embodiment of the present invention has a structure in which a polypropylene resin layer and a polyamide resin layer are laminated (directly) in close contact. It is a tube with The polypropylene resin in the polypropylene resin layer is maleic anhydride-modified polypropylene, the polypropylene resin layer contains organic particles having an average particle size of 0.1 to 10 ⁇ m, and the polyamide resin in the polyamide resin layer is an amine It is a polyamide resin with a molecular weight of 15 to 100 mmol/kg. Further, the laminated tube has a large number of protrusions formed by the organic particles on the side of the polypropylene resin layer at the interface between the polypropylene resin layer and the polyamide resin layer.
  • the average particle diameter of the organic particles 3 is obtained by dividing the laminated tube in half, photographing the laminated cross section with a scanning electron microscope (SEM) at a magnification of 5000 times, and based on the image, the polypropylene resin layer The particle diameters of arbitrary ten organic particles 3 confirmed in 1 are measured, and the average is obtained.
  • SEM scanning electron microscope
  • the height of the convex bump 1a (the distance between the valley and the peak at the interface of the unevenness) is preferably in the range of 0.1 to 10 ⁇ m, more preferably in the range of 0.1 to 5 ⁇ m.
  • the number of the convex protrusions 1a in the straight line distance at the interface between the polypropylene resin layer 1 and the polyamide resin layer 2 is preferably 2 to 20/100 ⁇ m, and more preferably 3 to 15/100 ⁇ m. is more preferred. That is, by satisfying these regulations, the anchoring effect and the like of the convex protrusion 1a can be enhanced, and the interlayer adhesion between both layers can be improved, which is preferable.
  • SEM scanning electron microscope
  • the polypropylene resin used as the material for forming the polypropylene resin layer 1 is maleic anhydride-modified polypropylene, as described above.
  • maleic anhydride-modified polypropylene accounts for 50% by mass or more of the material for the polypropylene resin layer 1, and the case where the material for forming the polypropylene resin layer 1 other than the organic particles 3 consists only of maleic anhydride-modified polypropylene is also included.
  • the maleic anhydride-modified polypropylene preferably has a modification amount of 0.05 to 7% by mass, more preferably 0.1 to 5% by mass.
  • the maleic anhydride-modified polypropylene preferably has a melting point of 130 to 180°C, more preferably 140 to 170°C. That is, if the melting point is too low, the heat resistance tends to be poor, and if the melting point is too high, the interlayer adhesion tends to be poor.
  • the organic particles 3 contained in the polypropylene resin layer 1 include particles made of an organic material such as rubber (ethylene-propylene copolymer, ethylene octene, ethylene butene, ethylenehexene, ethyl acrylate, etc.) and resin (polyethylene, etc.). mentioned. These are used alone or in combination of two or more. Among them, organic particles made of at least one of polyethylene and ethylene-propylene copolymer are preferable from the viewpoint of compatibility. It should be noted that the organic particles 3 may be granulated in advance so as to satisfy the above-mentioned specific average particle size, and may be added to the material for the polypropylene resin layer 1 .
  • an organic material such as rubber (ethylene-propylene copolymer, ethylene octene, ethylene butene, ethylenehexene, ethyl acrylate, etc.) and resin (polyethylene, etc.). mentioned. These are used alone or in combination of two or more.
  • the resin or rubber as the material of the organic particles 3 is melt-kneaded with maleic anhydride-modified polypropylene under specific conditions (melt-kneading at 200 to 250 ° C. for 1 to 10 minutes by a twin-screw kneader).
  • the organic particles 3 may be made to appear in the polypropylene resin as a result by pelletizing and subjecting the pellets to melt extrusion molding according to the conditions described later.
  • the proportion of the organic particles 3 in the polypropylene resin layer 1 is preferably 5-20 mass %, more preferably 10-15 mass %. That is, by including the organic particles 3 in such a ratio, it is possible to improve the interlayer adhesion after annealing.
  • the ratio of the organic particles 3 in the polypropylene resin layer 1 is the organic particles 3 blended in the material for the polypropylene resin layer 1 (or the resin that is the material of the organic particles 3) before manufacturing the laminated tube. and rubber).
  • the polypropylene resin layer 1 can be photographed with a scanning electron microscope (SEM) at a magnification of 1000 and binarized, for example.
  • SEM scanning electron microscope
  • the polyamide resin used as the material for forming the polyamide resin layer 2 has an amine value of 15 to 100 mmol/kg, as described above. Polyamide resins with an amine value of 20 to 80 mmol/kg are preferred, and polyamide resins with an amine value of 25 to 60 mmol/kg are more preferred.
  • the interlaminar adhesion to the polypropylene resin layer 1 is more excellent. If the amine value is too low, the interlayer adhesion tends to deteriorate, and if the amine value is too high, the extrusion moldability tends to deteriorate.
  • the amine value of the polyamide resin indicates the number of mmoles of amine contained in 1 kg of the solid content of the polyamide resin.
  • polyamide resins exhibiting an amine value examples include polyamide 46 (PA46), polyamide 410 (PA410), polyamide 6 (PA6), polyamide 66 (PA66), polyamide 610 (PA610), polyamide 612 (PA612), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010 (PA1010) and other aliphatic polyamide resins, and polyamide 6T (PA6T), polyamide 9T (PA9T), polyamide 10T (PA10T) and other aromatic polyamide resins. be done. These may be used alone or in combination of two or more. Among these, an aliphatic polyamide resin is preferable because it is superior in interlayer adhesion to the polypropylene resin layer 1 and the like.
  • the polyamide resin preferably has a melting point of 160 to 280°C, more preferably 170 to 270°C. That is, if the melting point is too low, the heat resistance tends to be poor, and if the melting point is too high, the interlayer adhesion tends to be poor.
  • 50% by mass or more of the material for the polyamide resin layer 2 is occupied by the amine-valued polyamide resin, and preferably 70% by mass or more of the material for the polyamide resin layer 2 is the amine-valued polyamide resin. More preferably, 100 mass % of the material for the polyamide resin layer 2 is the amine-valent polyamide resin.
  • the material for the polyamide resin layer 2 may contain weather stabilizers, lubricants, pigments, dyes, antistatic agents, plasticizers, heat-resistant antiaging agents, etc., as necessary. There is no problem even if it mixes. Moreover, as the material for the polyamide resin layer 2, a material obtained by melt-kneading these materials and pelletizing them is used, if necessary.
  • the polypropylene resin layer 1 and the polyamide resin layer 2 are preferably formed by co-extrusion molding in order to bond the layers without an adhesive.
  • the polypropylene resin layer 1 is an inner layer (inner layer) and the polyamide resin layer 2 is an outer layer (outer layer) from the viewpoint of hydrolyzability.
  • the polypropylene resin layer 1 is an inner layer (inner layer) and the polyamide resin layer 2 is an outer layer (outer layer) from the viewpoint of hydrolyzability.
  • the polyamide resin layer 2 is an outer layer (outer layer) from the viewpoint of hydrolyzability.
  • each layer is extruded by an extruder at a temperature of 200 to 350° C. (preferably 220 to 280° C.) at a take-up speed of 1 to 15 m/min (preferably 3 to 5 m/min).
  • melt extrusion molding co-extrusion molding
  • the laminated tube thus obtained is annealed (heat treated) at a temperature near the melting point of the resin of each layer, or bent during the annealing, if necessary.
  • the present laminated tube (see FIG. 1) can be manufactured.
  • the inner diameter of the laminated tube thus obtained is preferably in the range of 2 to 40 mm, more preferably in the range of 4 to 35 mm.
  • the thickness of the inner layer 11 is preferably in the range of 0.1 to 1.9 mm, more preferably in the range of 0.2 to 1.8 mm.
  • the thickness of the outer layer 12 is preferably in the range of 0.1 to 1.9 mm, more preferably in the range of 0.2 to 1.8 mm.
  • This laminated tube is used for radiator hoses, heater hoses, air conditioner hoses, etc., as well as cooling tubes for battery packs for electric vehicles and fuel cell vehicles. Moreover, the laminated tube can be used not only for automobiles but also for other transport machines (airplanes, forklifts, excavators, industrial transport vehicles such as cranes, railway vehicles, etc.).
  • Inner layer material (A) Maleic anhydride-modified polypropylene (manufactured by Mitsui Chemicals, Admer QF500, modified amount 0.27% by mass, melting point 165 ° C.) 100 parts by weight and ethylene-propylene copolymer (manufactured by Mitsui Chemicals, Tafmer DF840) 15 parts by weight , and mixed at 200° C. for 1 to 5 minutes using a twin-screw extruder to prepare an inner layer material (A) (pellets).
  • Inner layer material (E) Maleic anhydride-modified polypropylene (manufactured by Mitsui Chemicals, Admer QF500, modified amount 0.27% by mass, melting point 165 ° C.) 100 parts by weight and ethylene-propylene copolymer (manufactured by Mitsui Chemicals, Tafmer DF8200) 15 parts by weight , and mixed at 200° C. for 1 to 5 minutes using a twin-screw extruder to prepare an inner layer material (E) (pellets).
  • Inner layer material (F) 100 parts by mass of maleic anhydride-modified polypropylene (manufactured by Mitsui Chemicals, ADMER QF500, modified amount 0.27% by mass, melting point 165° C.) and 15 parts by mass of ethylene-propylene copolymer (manufactured by Mitsui Chemicals, Tafmer XM-7070) The parts were mixed with a twin-screw extruder at 200° C. for 1 to 5 minutes to prepare inner layer material (F) (pellets).
  • outer layer materials (a) to (e) Commercially available polyamide resins shown in Table 1 below were prepared as outer layer materials (a) to (d). In addition, polyphthalamide (PPA), which is the outer layer material (e) shown in Table 1 below, was prepared as described below.
  • PPA polyphthalamide
  • the low condensate was pulverized with a pulverizer and dried at 100° C. for 48 hours.
  • the lower condensates were nitrogen-substituted.
  • the low condensate thus nitrogen-substituted was heated to 220° C. over 1 hour and 30 minutes in an autoclave, allowed to undergo a solid-phase polymerization reaction for 1 hour in that state, and then cooled to room temperature.
  • the prepolymer thus obtained was extruded in a twin-screw extruder having a screw diameter of 30 mm and a ratio of shaft diameter to screw shaft length (L/D) of 54 at a cylinder temperature of 330°C, a screw rotation speed of 170 rpm, and a discharge rate of 5 kg/.
  • Melt polymerization was performed with H to obtain polyphthalamide (PPA) having a melting point of 320° C. and an amine value of 110.0 mmol/g.
  • the laminated tube thus obtained was divided in half, and the laminated cross section was photographed with a scanning electron microscope (SEM) at a magnification of 5000 times, and ten images thereof were connected. Then, based on the image, the particle diameters of arbitrary 10 ethylene-propylene copolymer particles (organic particles) found in the inner layer were measured, and the average particle diameter ( ⁇ m) was determined.
  • the linear distance at the interface is The number of convex bumps (pieces/100 ⁇ m) was counted.
  • ⁇ Extrudability> The appearance of the laminated tube produced by co-extrusion molding as described above was visually observed and evaluated according to the following evaluation criteria.
  • ⁇ Evaluation criteria> ⁇ (very good): A tube with a specified wall thickness could be obtained without disturbance of the inner layer and the outer layer.
  • the value of Example 4 is set to 100 in exponential notation, and based on the value of Example 4, each "adhesive strength (N / cm) )” was converted to an index. Then, the interlayer adhesion was evaluated according to the following evaluation criteria. ⁇ Evaluation criteria> ⁇ (very good): the index value is 70 or more. x (poor): the index value is less than 70;
  • Comparative Example 1 the average particle diameter of the organic particles (ethylene-propylene copolymer particles) in the inner layer was too large, and it was considered that the stress concentration site was formed. was not obtained.
  • Comparative Example 2 the average particle size of the organic particles (ethylene-propylene copolymer particles) in the inner layer was too small, presumably resulting in insufficient anchoring effect. As a result, the desired interlayer adhesion was obtained. I could't.
  • Comparative Example 3 as the polyamide resin used as the material for the outer layer, a polyamide resin having an amine value lower than that specified in the present invention was used, and as a result, it is thought that the proportion of chemical bonds formed was low.
  • Comparative Example 4 a polyamide resin having a higher amine value than the stipulations of the present invention was used as the polyamide resin used as the material for the outer layer. ) easily accumulated, it was not possible to obtain a tube with a specified wall thickness by extrusion molding, and the appearance of the tube became abnormal.
  • the laminated tube of the present invention can be preferably used as a cooling tube for radiator hoses, heater hoses, air conditioner hoses, etc., and battery packs for electric vehicles and fuel cell vehicles. Moreover, the laminated tube can be used not only for automobiles but also for other transport machines (airplanes, forklifts, excavators, industrial transport vehicles such as cranes, railway vehicles, etc.).

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
PCT/JP2022/044346 2021-12-14 2022-12-01 積層チューブ Ceased WO2023112692A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE112022003678.8T DE112022003678T5 (de) 2021-12-14 2022-12-01 Mehrschichtschlauch
CN202280056996.0A CN117859022A (zh) 2021-12-14 2022-12-01 层叠管
US18/434,033 US20240173936A1 (en) 2021-12-14 2024-02-06 Multilayer tube

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JP2021202598A JP7788272B2 (ja) 2021-12-14 2021-12-14 積層チューブ
JP2021-202598 2021-12-14

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US18/434,033 Continuation US20240173936A1 (en) 2021-12-14 2024-02-06 Multilayer tube

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