CN116745550A - 流体输送用软管 - Google Patents
流体输送用软管 Download PDFInfo
- Publication number
- CN116745550A CN116745550A CN202280011127.6A CN202280011127A CN116745550A CN 116745550 A CN116745550 A CN 116745550A CN 202280011127 A CN202280011127 A CN 202280011127A CN 116745550 A CN116745550 A CN 116745550A
- Authority
- CN
- China
- Prior art keywords
- thermoplastic resin
- hose
- resin composition
- elastomer
- transporting
- 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.)
- Pending
Links
- 239000012530 fluid Substances 0.000 title claims abstract description 44
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 82
- 239000011342 resin composition Substances 0.000 claims abstract description 56
- 239000000806 elastomer Substances 0.000 claims abstract description 52
- 229920001971 elastomer Polymers 0.000 claims abstract description 49
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 25
- 238000003860 storage Methods 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 230000035699 permeability Effects 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 6
- 229920006122 polyamide resin Polymers 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
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- 238000004090 dissolution Methods 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims 1
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- 239000000463 material Substances 0.000 description 18
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- 238000000034 method Methods 0.000 description 11
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- 230000000694 effects Effects 0.000 description 6
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- 238000004132 cross linking Methods 0.000 description 5
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- 229920002647 polyamide Polymers 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
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- 239000002253 acid Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
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- 230000008018 melting Effects 0.000 description 4
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- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 3
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 2
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- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 235000007297 Gaultheria procumbens Nutrition 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 241000333569 Pyrola minor Species 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
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- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000012001 immunoprecipitation mass spectrometry Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B32B2597/00—Tubular articles, e.g. hoses, pipes
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- 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
- F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
- F16L11/081—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more layers of a helically wound cord or wire
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- 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
- F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
- F16L11/085—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
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- 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
- F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
- F16L11/085—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
- F16L11/086—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers two layers
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
提供低温下的耐疲劳性和高温下的耐冲击压力性优异的流体输送用软管。其特征在于,是包括由包含热塑性树脂和弹性体的热塑性树脂组合物形成的内层、配置在内层的外侧的增强层、和配置在增强层的外侧的外层的流体输送用软管,热塑性树脂组合物的‑40℃下的储能模量E’L、与80℃下的储能模量E’H满足式(1)、(2)和(3),E’L≤1500MPa···(1)E’H≥40MPa···(2)E’H/E’L≥0.05···(3)。
Description
技术领域
本发明涉及流体输送用软管(hose)。
背景技术
已知具有由包含聚酰胺11和改性烯烃系弹性体的树脂组合物形成的氢气阻挡层、配设在上述氢气阻挡层的外侧的增强层、和配设在上述增强层的外侧的包含聚酰胺树脂的外覆层的氢输送部件(国际公开第2018/155491号)。
现有技术文献
专利文献
专利文献1:国际公开第2018/155491号
发明内容
发明所要解决的课题
国际公开第2018/155491号所记载的氢输送部件的高温下的耐冲击压力性不充分。
本发明提供低温下的耐疲劳性和高温下的耐冲击压力性优异的流体输送用软管。
用于解决课题的方法
本发明人等发现:在由包含热塑性树脂的连续相和包含弹性体的分散相构成的热塑性树脂组合物中,通过将分散相的弹性体交联,可以抑制高温下的弹性模量降低,从而完成了本发明。
本发明的特征在于,是包括由包含热塑性树脂和弹性体的热塑性树脂组合物形成的内层、配置在内层的外侧的增强层、和配置增强层的外侧的外层的流体输送用软管,热塑性树脂组合物的-40℃下的储能模量E’L、与80℃下的储能模量E’H满足式(1)、(2)和(3)。
E’L≤1500MPa···(1)
E’H≥40MPa···(2)
E’H/E’L≥0.05···(3)
本发明包含以下实施方案。
[1]一种流体输送用软管,其特征在于,包括由包含热塑性树脂和弹性体的热塑性树脂组合物形成的内层、配置在内层的外侧的增强层、和配置在增强层的外侧的外层,其中,热塑性树脂组合物的-40℃下的储能模量E’L、与80℃下的储能模量E’H满足式(1)、(2)和(3)。
E’L≤1500MPa···(1)
E’H≥40MPa···(2)
E’H/E’L≥0.05···(3)
[2]根据[1]所述的流体输送用软管,其特征在于,热塑性树脂组合物由包含热塑性树脂的连续相和包含弹性体的分散相构成,弹性体的至少一部分被交联。
[3]根据[1]或[2]所述的流体输送用软管,其特征在于,热塑性树脂组合物的21℃且相对湿度50%下的氧透过系数为0.1mm·cc/(m2·天·mmHg)以下。
[4]根据[1]~[3]中任一项所述的流体输送用软管,其特征在于,热塑性树脂为选自聚酰胺树脂、乙烯醇系树脂和聚酯树脂中的至少1种。
[5]根据[1]~[4]中任一项所述的流体输送用软管,其特征在于,弹性体为选自烯烃系弹性体、苯乙烯系弹性体、丁基系弹性体、二烯系橡胶和它们的改性物中的至少1种。
[6]根据[1]~[5]中任一项所述的流体输送用软管,其特征在于,将热塑性树脂组合物在30℃、压力90MPa的氢气气氛下暴露24小时,减压直到大气压时的体积(V)、与暴露前的体积(V0)之比V/V0小于1.08。
[7]根据[1]~[6]中任一项所述的流体输送用软管,其特征在于,将热塑性树脂组合物在30℃、压力90MPa的氢气气氛下暴露了24小时时的氢溶解量为3000质量ppm以下。
[8]根据[1]~[7]中任一项所述的流体输送用软管,其特征在于,热塑性树脂组合物在温度-35℃、应变18%和频率6.7Hz下的反复拉伸中的断裂次数为200万次以上。
[9]根据[1]~[8]中任一项所述的流体输送用软管,其特征在于,外层的25℃下的10%模量为10MPa以下。
[10]根据[1]~[9]中任一项所述的流体输送用软管,其特征在于,增强层包含拉伸弹性模量100GPa为以上的有机纤维或钢线。
发明的效果
本发明的流体输送用软管的低温下的耐疲劳性和高温下的耐冲击压力性优异。
具体实施方式
本发明涉及流体输送用软管。输送的流体没有限定,可举出氢、空调用制冷剂、非活性气体、燃料、油、水等。其中,本发明的流体输送用软管适合于氢软管。
本发明的流体输送用软管包括由包含热塑性树脂和弹性体的热塑性树脂组合物形成的内层、配置在内层的外侧的增强层、和配置在增强层的外侧的外层。
本发明的流体输送用软管的特征在于,热塑性树脂组合物的-40℃下的储能模量E’L、与80℃下的储能模量E’H满足式(1)、(2)和(3)。
E’L≤1500MPa···(1)
E’H≥40MPa···(2)
E’H/E’L≥0.05···(3)
热塑性树脂组合物的-40℃下的储能模量E’L满足
E’L≤1500MPa···(1),
优选满足
20MPa≤E’L≤1450MPa···(1’),
更优选满足
50MPa≤E’L≤1400MPa···(1”)。
通过E’L满足上述式,从而热塑性树脂组合物的低温下的耐疲劳性优异。
使E’L满足上述式的方法可举出热塑性树脂和弹性体的种类的选定、组成比的调整、增塑剂、软化剂等的添加等。
热塑性树脂组合物的80℃下的储能模量E’H满足
40MPa≤E’H···(2),
优选满足
45MPa≤E’H≤1000MPa···(2’)
更优选满足
50MPa≤E’H≤800MPa···(2”)。
通过E’H满足上述式,从而高温下的耐冲击压力性优异,紧固时不破损。
使E’H满足上述式的方法可举出热塑性树脂和弹性体的种类的选定、组成比的调整、纤维、填料的添加等。
80℃下的储能模量与-40℃下的储能模量之比(E’H/E’L)满足
0.05≤E’H/E’L···(3),
优选满足
0.06≤E’H/E’L≤0.30···(3’),
更优选满足
0.07≤E’H/E’L≤0.25···(3”)。
通过E’H/E’L满足上述式,从而弹性模量的温度依赖性小,软管的刚性不易被使用温度左右,因此可获得稳定的操作性。
使E’H/E’L满足上述式的方法可举出热塑性树脂和弹性体的种类的选定、组成比的调整、添加剂的使用等。
储能模量E’是指由向粘弹性体施加了动态应变时的应力-应变特性获得的复数弹性模量之中的、实数部,与粘弹性的弹性项对应。
动态储能模量可以按照JIS K7198所记载的方法求出。具体而言,在向试样施加了初始拉伸后,通过励振器而给予作为周期振动的正弦波的动态应变,测定此时的应力和位移从而可以求出复数弹性模量,作为其实数部的常数而求出。在本发明中,在初始拉伸5%、频率20Hz、动态应变0.1%下测定了。
流体输送用软管的内层由包含热塑性树脂和弹性体的热塑性树脂组合物形成。
热塑性树脂组合物优选由包含热塑性树脂的连续相和包含弹性体的分散相构成。换言之,热塑性树脂形成了连续相(基体),弹性体形成了分散相(结构域)。即,热塑性树脂组合物优选具有海岛结构。通过热塑性树脂组合物具有海岛结构,从而抑制输送的流体的透过,同时易于获得低温下的耐疲劳性。
热塑性树脂只要发挥本发明的效果就没有限定,优选为选自聚酰胺树脂、乙烯醇系树脂和聚酯树脂中的至少1种。
作为聚酰胺树脂,可举出聚酰胺11、聚酰胺12、聚酰胺6、聚酰胺6/66共聚物、聚酰胺610、聚酰胺6/12共聚物、聚酰胺1010、聚酰胺1012等,但优选为聚酰胺11、聚酰胺12、聚酰胺1012。
作为乙烯醇系树脂,可举出聚乙烯醇(PVA)、乙烯-乙烯醇共聚物(EVOH)、乙烯-乙酸乙烯酯-乙烯醇共聚物、乙烯-丁烯二醇共聚物等,但其中优选为乙烯-乙烯醇共聚物。乙烯-乙烯醇共聚物依赖于乙烯与乙烯醇的共聚比例而熔点和氧透过系数发生变化。优选的乙烯的共聚比例为25~48摩尔%。其中,优选为乙烯的共聚比例为48摩尔%的乙烯-乙烯醇共聚物、乙烯的共聚比例为38摩尔%的乙烯-乙烯醇共聚物。
作为聚酯树脂,可举出聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯等,但优选为聚对苯二甲酸丁二醇酯。
连续相在不损害本发明的效果的范围内,可以包含除聚酰胺树脂、乙烯醇系树脂和聚酯树脂以外的热塑性树脂、各种添加剂。
弹性体只要发挥本发明的效果就没有限定,但优选为选自烯烃系弹性体、苯乙烯系弹性体、丁基系弹性体、二烯系橡胶和它们的改性物中的至少1种。
作为烯烃系弹性体,可举出乙烯-α-烯烃共聚物、或乙烯-不饱和羧酸共聚物或其衍生物等。作为乙烯-α-烯烃共聚物,可举出乙烯-丙烯共聚物、乙烯-丁烯共聚物、乙烯-戊烯共聚物、乙烯-己烯共聚物、乙烯-辛烯共聚物和它们的酸改性物等。作为乙烯-不饱和羧酸共聚物,可举出乙烯-丙烯酸共聚物、乙烯-甲基丙烯酸共聚物等。
作为苯乙烯系弹性体,可举出苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)、苯乙烯-乙烯/丙烯-苯乙烯共聚物(SEPS)、苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-丁二烯-苯乙烯共聚物(SBS)、苯乙烯-异丁烯-苯乙烯嵌段共聚物(SIBS)、和它们的马来酸酐改性品等,但其中优选为苯乙烯-异丁烯-苯乙烯嵌段共聚物(SIBS)、马来酸酐改性苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物。
作为丁基系弹性体,可举出异丁烯-异戊二烯共聚物(IIR)及其卤化物、苯乙烯-异丁烯-苯乙烯共聚物(SIBS)及其改性物,其中优选为苯乙烯-异丁烯-苯乙烯共聚物。
作为二烯系橡胶,可举出天然橡胶(NR)、异戊二烯橡胶(IR)、丁二烯橡胶(BR)(高顺式BR和低顺式BR)、丁苯橡胶(SBR)(乳液聚合SBR、溶液聚合SBR)、氯丁橡胶(CR)、丁腈橡胶(NBR)、环氧化天然橡胶、它们的氢化物等,但优选为天然橡胶、异戊二烯橡胶、丁二烯橡胶、丁苯橡胶、氯丁橡胶、丁腈橡胶。
优选弹性体的至少一部分被交联。通过将弹性体的至少一部分交联,从而可以抑制热塑性树脂组合物的高温下的弹性模量降低,热塑性树脂组合物的高温下的耐冲击压力性优异。将弹性体的至少一部分交联的方法可举出在将热塑性树脂与弹性体熔融混炼时,添加能够将弹性体交联的交联剂的动态交联。作为交联剂,优选为1分子中具有多个氨基的化合物,其中优选为3,3’-二氨基二苯基砜(3,3’-DAS)、4,4’-二氨基二苯基砜(4,4’-DAS)、N-苯基-N’-(1,3-二甲基丁基)-对苯二胺(6PPD)等二胺。
分散相在不损害本发明的效果的范围内,可以包含除烯烃系弹性体、苯乙烯系弹性体、丁基系弹性体、二烯系橡胶和它们的改性物以外的弹性体、各种添加剂。
构成内层的热塑性树脂组合物中的热塑性树脂的含有率优选为热塑性树脂组合物中的全部聚合物成分的10~97质量%,更优选为15~95质量%,进一步优选为20~93质量%。如果热塑性树脂的含有率过少,则难以抑制流体的透过,如果过多,则低温下的耐疲劳性易于变得不充分。
构成内层的热塑性树脂组合物中的弹性体的含有率优选为热塑性树脂组合物中的全部聚合物成分的3~85质量%,更优选为5~80质量%,进一步优选为7~75质量%。如果弹性体的含有率过少,则低温下的耐疲劳性易于变得不充分,如果过多,则难以抑制流体的透过,高温下的耐冲击压力性也难以平衡。
构成内层的热塑性树脂组合物中的连续相与分散相的体积比率优选为95:5~25:75,更优选为92:8~28:72,进一步优选为90:10~30:70。通过连续相与分散相的体积比率在上述数值范围内,从而易于取得流体的耐透过性、低温下的耐疲劳性、高温下的耐冲击压力性的平衡。
构成内层的热塑性树脂组合物的21℃且相对湿度50%下的氧透过系数优选为0.1mm·cc/(m2·天·mmHg)以下,更优选为0.00001~0.08mm·cc/(m2·天·mmHg),进一步优选为0.0001~0.06mm·cc/(m2·天·mmHg)。通过氧透过系数在该数值范围内,从而热塑性树脂组合物可以作为氢软管、空调软管等流体输送用软管的内层用材料而应用。使氧透过系数为该数值范围内的方法可举出热塑性树脂和弹性体的种类的选定、组成比的调整等。
将构成内层的热塑性树脂组合物在30℃、压力90MPa的氢气气氛下暴露24小时,减压直到大气压时的体积V、与暴露前的体积V0之比V/V0优选为小于1.08,更优选为1.00~1.07,进一步优选为1.00~1.06。通过V/V0在该范围内,从而在将氢、氦等分子尺寸小的流体以高压输送的情况下,减压时的尺寸变化小,可以抑制由内层陷入增强层引起的破坏起点的产生。
将构成内层的热塑性树脂组合物在30℃、压力90MPa的氢气气氛下暴露了24小时时的氢溶解量优选为3000质量ppm以下,更优选为2800质量ppm以下,进一步优选为2600质量ppm以下。通过氢溶解量在该范围内,从而在将氢、氦等分子尺寸小的流体以高压输送的情况下,留在内层中的流体分子少,可以抑制由减压时的内层内部的膨胀引起的破坏。
构成内层的热塑性树脂组合物在温度-35℃、应变18%和频率6.7Hz下的反复拉伸中的断裂次数优选为200万次以上,更优选为250万次以上,进一步优选为300万次以上。通过断裂次数在该数值以上,从而热塑性树脂组合物的低温下的耐疲劳性优异。使断裂次数为该数值以上的方法可举出热塑性树脂和弹性体的种类的选定、组成比的调整、能够将热塑性树脂与弹性体的界面增强的成分的添加等。
构成内层的热塑性树脂组合物的制造方法只要发挥本发明的效果就没有限定,例如,可以通过将热塑性树脂、弹性体、和根据需要的交联剂进行熔融混炼来制造。
内层的厚度优选为0.2~2.0mm,更优选为0.3~1.8mm,进一步优选为0.4~1.6mm。如果内层的厚度过薄,则可能熔融挤出变得困难,或挤出方法被限定,如果过厚,则可能软管的柔软性不足,操作性变差。
流体输送用软管包含配置在内层的外侧的增强层。增强层为设置在内层与外层之间的层,通常,包含将金属线材或有机纤维编织而形成了的编带层或螺旋层。作为金属线材,可举出钢线、铜和铜合金的线、铝和铝合金的线、镁合金的线、钛和钛合金的线等,但优选为钢线。金属线材的线径优选为0.25~0.40mm。作为有机纤维,可举出聚对苯撑苯并二唑(PBO)纤维、芳族聚酰胺纤维、碳纤维等,但优选为PBO纤维。有机纤维的线径优选为0.25~0.30mm。
增强层优选包含拉伸弹性模量100GPa以上的有机纤维或钢线。通过增强层包含拉伸弹性模量100GPa以上的有机纤维或钢线,从而即使施加高内压也可以使软管的变形小。有机纤维或钢线的拉伸弹性模量更优选为150GPa以上。
流体输送用软管包含配置在增强层的外侧的外层。
外层的25℃下的10%模量优选为10MPa以下,更优选为0.1~9MPa,进一步优选为0.2~8MPa。通过10%模量在该数值范围内,从而即使在使用时磨擦、接触,外层也不易破损,并且可以使弯曲刚性低,因此软管的操作性提高。
作为构成外层的材料,没有限定,可举出热塑性弹性体、硫化橡胶等,但优选为热塑性弹性体。作为热塑性弹性体,没有限定,但优选可举出聚酯弹性体、聚酰胺弹性体、聚氨酯弹性体。
聚酯弹性体(TPEE)是硬链段为聚酯(例如聚对苯二甲酸丁二醇酯)、软链段为聚醚(例如聚丁二醇)或聚酯(例如脂肪族聚酯)的热塑性弹性体。聚酯弹性体有市售,本发明中可以使用市售品。作为聚酯弹性体的市售品,可举出东洋纺株式会社制“ペルプレン”(注册商标)、東レ·デュポン株式会社制“ハイトレル”(注册商标)等。
聚酰胺弹性体(TPA)是硬链段为聚酰胺(例如聚酰胺6、聚酰胺66、聚酰胺11、聚酰胺12)、软链段为聚醚(例如聚乙二醇、聚丙二醇)的热塑性弹性体。聚酰胺弹性体有市售,本发明中可以使用市售品。作为聚酰胺弹性体的市售品,可举出宇部兴产株式会社制“UBESTA”(注册商标)XPA系列、アルケマ公司制“PEBAX”(注册商标)等。
聚氨酯弹性体为由具有氨基甲酸酯键的硬链段、与聚醚、聚酯、聚碳酸酯等软链段构成的嵌段共聚物。聚氨酯弹性体有市售,本发明中可以使用市售品。作为聚氨酯弹性体的市售品,可举出BASF公司制“エラストラン”(注册商标)、日本ミラクトラン制“ミラクトラン”(注册商标)、大日精化工业制“レザミン”(注册商标)等。
外层的厚度优选为0.2~1.2mm,更优选为0.3~1.0mm,进一步优选为0.4~0.8mm。如果外层的厚度过薄,则通过对软管进行操作时的磨擦、变形、冲击等而易于被破坏,可能不能充分保护增强层,如果过厚,则软管重量变大,操作性变差。
流体输送用软管的制造方法没有特别限定,可以如以下那样操作而制造。可以通过首先将内层(内管)通过挤出成型而管状地挤出,接着在该管上编织成为增强层的纤维,进一步在该纤维上将外层(外管)通过挤出成型进行被覆来制造。
实施例
[原材料]
在以下实施例和比较例中使用了的原材料如下所述。
(内层用热塑性树脂)
PA11:聚酰胺11,アルケマ公司制“RILSAN”(注册商标)BESN OTL
PA12:聚酰胺12,宇部兴产株式会社制“UBESTA”(注册商标)3020U
PA1010:聚酰胺1010,ダイセル·エボニック株式会社制“ベスタミド”(注册商标)DS16
PA610:聚酰胺610,東レ株式会社“アミラン”(注册商标)CM2001
PA6/12:聚酰胺6/12共聚物,宇部兴产株式会社制“UBEナイロン”7024B
PA6/66:聚酰胺6/66共聚物,宇部兴产株式会社制“UBEナイロン”5023B
PA6:聚酰胺6,宇部兴产株式会社制“UBEナイロン”1013B
EVOH:乙烯-乙烯醇共聚物,三菱ケミカル株式会社制“Soarnol”(注册商标)H4815B
(内层用弹性体)
酸改性EBR-1:马来酸酐改性乙烯-1-丁烯共聚物,三井化学株式会社制“タフマー”(注册商标)MH7010
酸改性EBR-2:马来酸酐改性乙烯-1-丁烯共聚物,三井化学株式会社制“タフマー”(注册商标)MH5020
酸改性SEBS:马来酸酐改性苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物,旭化成株式会社制“タフテック”(注册商标)M1943
酸改性SBS:马来酸酐改性苯乙烯-丁二烯-苯乙烯嵌段共聚物,旭化成株式会社制“タフプレン”(注册商标)912
Br-IPMS:溴化异丁烯-对甲基苯乙烯共聚物,エクソンモービル·ケミカル公司制“EXXPRO”(注册商标)3745
(交联剂)
3,3’-DAS:3,3’-二氨基二苯基砜,三井化学ファイン株式会社制
4,4’-DAS:4,4’-二氨基二苯基砜,三井化学ファイン株式会社制
6PPD:N-苯基-N’-(1,3-二甲基丁基)-对苯二胺,フレキシス株式会社制“サントフレックス”(注册商标)
(外层材料)
TPEE:热塑性聚酯弹性体,東レ·デュポン株式会社制“ハイトレル”(注册商标)4057N(25℃下的10%模量=3.9MPa)
(1)热塑性树脂组合物的调制
在将料筒温度设定为220℃的双螺杆混炼挤出机(株式会社日本制钢所制)中,以表1~表3所示的混配,导入热塑性树脂、弹性体和交联剂,以滞留时间约5分钟进行熔融混炼,将熔融混炼物从被安装在排出口的模头条状地挤出了。将所得的条状挤出物用树脂用造粒机制粒,获得了颗粒状的热塑性树脂组合物。
(2)软管的制作
将在上述(1)的步骤中调制出的颗粒状的热塑性树脂组合物挤出为内径9mm、厚度1mm的管状。将该管设为内层,在其外侧编织3层PBO纤维的编带层作为增强层,进一步在其外侧编织了1层钢线的编带层。进一步,在增强层的外侧将热塑性聚酯弹性体(東レ·デュポン株式会社制“ハイトレル”(注册商标)4057N)以厚度0.7mm挤出而设为外层,制作出软管。
关于在上述(1)的步骤中调制出的热塑性树脂组合物(内层材料),测定-40℃下的储能模量(E’L)、80℃下的储能模量(E’H)、氧透过系数、和低温(-35℃)下的耐疲劳性,关于外层材料的热塑性聚酯弹性体,测定10%模量,关于在上述(2)中制作出的软管,评价了低温(-40℃)和高温(80℃)下的耐冲击压力性。将结果示于表1~表3中。
另外,各测定/评价项目的测定/评价方法如下所述。
[热塑性树脂组合物(内层材料)的储能模量E’的测定]
将在上述(1)的步骤中调制出的颗粒状的热塑性树脂组合物使用带有550mm宽度T型模头的40mmφ单螺杆挤出机(株式会社プラ技研),将料筒和模头的温度设定为组合物中熔点最高的材料的熔点+20℃,在冷却辊温度50℃、牵引速度3m/分钟的条件下成型为平均厚度0.2mm的片。
将该片切为规定大小的长条,按照JIS K7198所记载的方法,在初始拉伸5%、频率20Hz、动态应变0.1%下测定了动态储能模量。
[热塑性树脂组合物(内层材料)的氧透过系数的测定]
与上述[热塑性树脂组合物(内层材料)的储能模量E’的测定]同样地,将热塑性树脂组合物(内层材料)成型为平均厚度0.2mm的片。
将该片切为规定大小,使用MOCON公司制OXTRAN1/50,在21℃、相对湿度50%的条件下求出氧透过系数。
[内层材料的由氢暴露引起的体积变化率的测定]
将在(1)的步骤中调制出的颗粒状的热塑性树脂组合物使用带有200mm宽度T型模头的40mmφ单螺杆挤出机(株式会社プラ技研),将料筒和模头的温度设定为组合物中熔点最高的材料的熔点+20℃,在冷却辊温度50℃、牵引速度1m/分钟的条件下成型为平均厚度1.0mm的片。将该片切为直径13mm的圆盘状,加入到耐压容器中,在30℃、90MPa下进行了24小时氢暴露。在减压到刚到大气压后,利用基恩士(キーエンス)2维多点尺寸测定仪TM-3000测定圆盘状样品的面积,算出了体积变化率。随着氢的脱离,体积变小,将在该过程中最大的体积(最大值)除以同样地测定了的暴露前的体积而得的值设为体积变化率。体积变化率为1.08以上时,如果作为软管而反复输送氢,则由于体积变化而内层陷入增强层,耐久性降低。
[内层材料的由氢暴露引起的氢溶解量的测定]
与上述[内层材料的由氢暴露引起的体积变化的测定]同样地,在30℃、90MPa下氢暴露24小时,在减压到刚到大气压后,在30℃下在充满了氮的管内静置圆盘,从管的端部每隔一定时间将管内的气体向气相色谱导入,检测从试样内部脱离出来的氢,继续测定直到检测不到氢,将被检测到的氢量进行累计,从而求出通过暴露而向试样溶解了的氢量。
[热塑性树脂组合物(内层材料)的低温下的耐疲劳性的测定]
与上述[热塑性树脂组合物(内层材料)的储能模量E’的测定]同样地,成型为平均厚度0.2mm的片,从该片切出宽度5mm、长度200mm的长条20条,通过株式会社上岛制作所制的恒应变恒荷重疲劳试验机,在温度-35℃、应变18%、速度6.7Hz的条件下给予了反复拉伸变形。将20条之中的12条(60%)断裂了的次数定义为断裂次数,断裂次数越高,则对低温下的重复变形越有利,是优选的,将断裂次数小于200万次的情况判定为“不合格”,200万次以上且小于500万次的情况判定为“良”,将500万次以上的情况判定为“优”。
[外层材料的10%模量的测定]
将外层材料的热塑性聚酯弹性体使用带有550mm宽度T型模头的40mmφ单螺杆挤出机(株式会社プラ技研),将料筒和模头的温度设定为230℃,在冷却辊温度50℃、牵引速度3m/分钟的条件下成型为平均厚度0.2mm的片。将该片冲裁为JIS 3号哑铃形状,按照JISK6301“加硫ゴム物理試験方法(硫化橡胶物理试验方法)”,以25℃和拉伸速度500mm/分钟进行了拉伸试验。从所得的应力应变曲线求出10%拉伸时的应力(10%模量)。
[软管的耐冲击压力性的评价]
按照JIS K6330-8“ゴム及び樹脂ホース試験方法-第8部:衝撃圧力試験(橡胶和树脂软管试验方法-第8部:冲击压力试验)”,使流体在固定为U字的软管内循环,以频率1Hz、升压速度50MPa/s施加90MPa的冲击波形的压力直到10万次或软管破损为止,在结束后关于没有内层的破损的情况设为〇,在内层观察到了破损的情况设为×。
低温(-40℃)下的耐冲击压力性的试验使用冷却为-40℃的氮气作为流体而实施了。
高温(80℃)下的耐冲击压力性的试验使用80℃的油作为流体而实施了。
表3
产业可利用性
本发明的流体输送用软管可以适合作为从设置于氢站的分配器向燃料电池汽车等填充氢气的软管、汽车的空调的制冷剂输送用软管等流体输送用软管而利用。
Claims (10)
1.一种流体输送用软管,其特征在于,包括由包含热塑性树脂和弹性体的热塑性树脂组合物形成的内层、配置在内层的外侧的增强层、和配置在增强层的外侧的外层,其中,热塑性树脂组合物的-40℃下的储能模量E’L、与80℃下的储能模量E’H满足式(1)、(2)和(3),
E’L≤1500MPa···(1)
E’H≥40MPa···(2)
E’H/E’L≥0.05···(3)。
2.根据权利要求1所述的流体输送用软管,其特征在于,热塑性树脂组合物由包含热塑性树脂的连续相和包含弹性体的分散相构成,弹性体的至少一部分被交联。
3.根据权利要求1或2所述的流体输送用软管,其特征在于,热塑性树脂组合物的21℃且相对湿度50%下的氧透过系数为0.1mm·cc/(m2·天·mmHg)以下。
4.根据权利要求1~3中任一项所述的流体输送用软管,其特征在于,热塑性树脂为选自聚酰胺树脂、乙烯醇系树脂和聚酯树脂中的至少1种。
5.根据权利要求1~4中任一项所述的流体输送用软管,其特征在于,弹性体为选自烯烃系弹性体、苯乙烯系弹性体、丁基系弹性体、二烯系橡胶和它们的改性物中的至少1种。
6.根据权利要求1~5中任一项所述的流体输送用软管,其特征在于,将热塑性树脂组合物在30℃、压力90MPa的氢气气氛下暴露24小时,减压到大气压时的体积V、与暴露前的体积V0之比V/V0小于1.08。
7.根据权利要求1~6中任一项所述的流体输送用软管,其特征在于,将热塑性树脂组合物在30℃、压力90MPa的氢气气氛下暴露了24小时时的氢溶解量为3000质量ppm以下。
8.根据权利要求1~7中任一项所述的流体输送用软管,其特征在于,热塑性树脂组合物在温度-35℃、应变18%和频率6.7Hz下的反复拉伸中的断裂次数为200万次以上。
9.根据权利要求1~8中任一项所述的流体输送用软管,其特征在于,外层的25℃下的10%模量为10MPa以下。
10.根据权利要求1~9中任一项所述的流体输送用软管,其特征在于,增强层包含拉伸弹性模量为100GPa以上的有机纤维或钢线。
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JPH09314752A (ja) * | 1996-05-29 | 1997-12-09 | Yokohama Rubber Co Ltd:The | ゴム・熱可塑性エラストマー積層体 |
US8479775B2 (en) * | 2004-03-11 | 2013-07-09 | Parker-Hannifin Corporation | Push-on hose construction |
JP7041663B2 (ja) * | 2017-02-24 | 2022-03-24 | 株式会社ブリヂストン | 水素輸送部品 |
IT201800006714A1 (it) * | 2018-06-27 | 2019-12-27 | Tubo multistrato per il trasporto di fluidi in pressione. | |
US10837580B2 (en) * | 2018-09-07 | 2020-11-17 | Contitech Schlauch Gmbh | Flexible air conditioning barrier or veneer suction hose |
JP7163118B2 (ja) * | 2018-09-21 | 2022-10-31 | 横浜ゴム株式会社 | タイヤ用インナーライナーおよび空気入りタイヤ |
-
2021
- 2021-02-10 JP JP2021020142A patent/JP7211442B2/ja active Active
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2022
- 2022-01-20 EP EP22752554.0A patent/EP4293077A1/en active Pending
- 2022-01-20 WO PCT/JP2022/002061 patent/WO2022172723A1/ja active Application Filing
- 2022-01-20 CN CN202280011127.6A patent/CN116745550A/zh active Pending
- 2022-01-20 US US18/264,375 patent/US20240100802A1/en active Pending
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WO2022172723A1 (ja) | 2022-08-18 |
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JP7211442B2 (ja) | 2023-01-24 |
US20240100802A1 (en) | 2024-03-28 |
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