TWI392820B - 用於空氣制動系統之塑膠管 - Google Patents
用於空氣制動系統之塑膠管 Download PDFInfo
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- TWI392820B TWI392820B TW096101744A TW96101744A TWI392820B TW I392820 B TWI392820 B TW I392820B TW 096101744 A TW096101744 A TW 096101744A TW 96101744 A TW96101744 A TW 96101744A TW I392820 B TWI392820 B TW I392820B
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- plastic tube
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- thermoplastic polymer
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- elastomer
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- 229920003023 plastic Polymers 0.000 title claims description 68
- 239000004033 plastic Substances 0.000 title claims description 68
- 239000000203 mixture Substances 0.000 claims description 60
- 229920001169 thermoplastic Polymers 0.000 claims description 37
- 229920006236 copolyester elastomer Polymers 0.000 claims description 24
- 239000002344 surface layer Substances 0.000 claims description 23
- 239000006229 carbon black Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 9
- 229920001634 Copolyester Polymers 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 description 27
- 239000000806 elastomer Substances 0.000 description 27
- 229920000728 polyester Polymers 0.000 description 22
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 20
- 239000002131 composite material Substances 0.000 description 15
- 239000003086 colorant Substances 0.000 description 10
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical group O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229920000767 polyaniline Polymers 0.000 description 9
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 208000013201 Stress fracture Diseases 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 150000002596 lactones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 241001295925 Gegenes Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000000805 composite resin Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002084 enol ethers Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
- B32B27/18—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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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
-
- 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
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- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/107—Ceramic
- B32B2264/108—Carbon, e.g. graphite particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2274/00—Thermoplastic elastomer material
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/08—Cars
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
- Y10T428/1383—Vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit is sandwiched between layers [continuous layer]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
本發明係關於一種適合用於汽車空氣制動系統之塑膠管。本發明更特別係關於一種可得自包含聚酯彈性體之聚合物組成物之經拉伸之塑膠管。本發明亦係關於可得自包含聚酯彈性體之聚合物組成物之塑膠管，由該塑膠管可製造根據本發明之經拉伸之塑膠管。
於本發明之內文中，須瞭解聚酯彈性體為嵌段共聚物，該嵌段共聚物含有由高熔結晶性或半晶性芳香族聚酯或半芳香族聚酯之嵌段所組成之硬節段，以及由低熔聚合物成分之嵌段所組成之軟節段。此種聚酯彈性體也稱作為TPE－E及共聚酯嵌段共聚物。
管子典型包含二端部以及介於該二端部間之一細長部分。包含至少一個經拉伸之端部係經由機械方式拉伸該端部之至少一區段所得之管子於此處被視為經拉伸之塑膠管。該細長部分以及該二端部中之任選之一端部無需接受機械拉伸。
用於汽車空氣制動系統中之塑膠管的基本要求為此等管子之可撓性與剛性間有適當平衡，有足夠溫度耐性，具有對抗汽車引擎蓋內部之化學環境之化學耐性。習知此等管子係由聚醯胺12製成。由於趨勢係朝向於更加輕薄短小的汽車，引擎蓋區產生較高溫，造成於此項應用中使用聚醯胺12有問題。有鑑於此，進行研究尋求有更佳效能的材料。至於替代材料，發現聚酯彈性體由於於較高溫具有較佳效能(挺度)因此可用於此項用途。用於汽車空氣制動系統之塑膠管中之聚酯彈性體為黑色，碳黑填充材料類似多種其它用於其它汽車引擎蓋下方用途之塑膠材料。此等聚酯彈性體材料通常類似臭氧，對環境影響顯示良好耐性。但也觀察到對於有更高需求的情況，由該聚酯彈性體所製造之空氣制動管之臭氧耐性不足，當管子接觸包含臭氧之環境時，管子可能顯示環境應力斷裂。該機械應力斷裂可能出現於將管子安裝於引擎區段或安裝於制動系統之前管子遭遇機械拉伸時。此種機械拉伸係出現於例如當有倒刺的軟管接頭或其它類型包含較粗部分的軟管接頭插入塑膠管之一端部時。有倒刺的軟管接頭為包含向後凸起之增厚部之軟管接頭，意圖用來防止軟管接頭容易從管子中被拔出。接頭為安裝步驟所需。有倒刺的軟管接頭可以經濟方式製造及安裝，因此應用用途日增。由於該項理由故，需要有適合用於汽車空氣制動系統且更佳具有臭氧耐性之塑膠管。
因此本發明之目的係提供一塑膠管，更特別為一經拉伸之塑膠管，其比較得自包含聚酯彈性體之聚合物組成物之已知塑膠管，具有改良之臭氧耐性。
此項目的可以根據本發明之經拉伸之塑膠管達成，其中該該經拉伸之端部包含一外表層區，其係由一第一熱塑性聚合物組成物(A)所組成，該組成物(A)包含一第一共聚酯彈性體(A－1)，以及相對於該熱塑性聚合物組成物(A)之總重，0－0.2 wt%碳黑。同時，該經拉伸之塑膠管包含由一第二熱塑性聚合物組成物(B)所組成之一內表面層，組成物(B)包含一第二共聚酯彈性體(B－1)，以及包含相對於該熱塑性聚合物組成物(B)之總重，超過0.2 wt%之碳黑。
根據本發明之經拉伸之塑膠管其中至少經拉伸之端部包含如前文說明之一外表層區，該經拉伸之塑膠管之效果為具有較佳臭氧抗性，比較由碳黑填充之聚酯彈性體所製成之已知之經拉伸之塑膠管，於含臭氧環境中顯示環境應力斷裂傾向降低獲得驗證。由於碳黑已知例如可於多種材料中用作為紫外光安定劑，因此觀察得之效果特別令人出乎意外。
臭氧耐性之測試方式，係將經拉伸之塑膠管置於含臭氧環境下，例如說明於ISO 1431，ISO 1431係有關硫化熱塑性橡膠對臭氧斷裂之耐性；及din 53509－1，係有關：「Bestimmung der Bestandigkeit gegen Rissbildung under Ozone Einwirkung」(對抗於臭氧影響下斷裂之耐性之測定)。
熱塑性聚合物組成物中之碳黑含量適合使用TGA測量測定，例如使用根據ASTM 5630之方法，於無氧環境下以及隨後於含氧環境下進行。
完全經拉伸之塑膠管包含由第一熱塑性聚合物組成物(A)所組組之一外表面層。於此經拉伸之塑膠管中，於端部之外表面層形成外表面層之整合一體之一部分。其優點為經拉伸之塑膠管整體之臭氧耐性改良。
一種包含由該第一熱塑性聚合物組成物(A)所組成之一外表面層之經拉伸之塑膠管可由一塑膠管製成，該塑膠管包含：a.一外表面層，其係由一第一熱塑性聚合物組成物(A)所組成，該組成物(A)包含一第一共聚酯彈性體(A－1)，以及相對於該熱塑性聚合物組成物(A)之總重，0－0.2 wt%碳黑，以及b.一內表面層，其係由一第二熱塑性聚合物組成物(B)所組成，該組成物(B)包含一第二共聚酯彈性體(B－1)，其中該第一熱塑性聚合物組成物(A)與該第二熱塑性聚合物組成物(B)為不同。
包含不同組成物所組成之一外表面層及一內表面層之一塑膠管於此處也稱作為「複合塑膠管」。本發明亦係關於如前文說明之複合塑膠管。
於根據本發明之複合塑膠管中，外表面層及內表面層係由碳黑含量有差異之不同的共聚酯彈性體組成物所組成，亦即相對於熱塑性聚合物組成物(B)之總重，第二熱塑性聚合物組成物(B)包含大於0.2 wt%碳黑。
組成物進一步之差異在於第一共聚酯彈性體(A－1)與第二共聚酯彈性體(B－1)不同。
較佳第一共聚酯彈性體(A－1)為比第二共聚酯彈性體(B－1)更具有臭氧耐性之共聚酯彈性體。也較佳第二熱塑性聚合物組成物(B)為著色組成物，或為色彩與第一熱塑性聚合物組成物(A)不同的著色組成物。也較佳組合此等變化。
當第二熱塑性聚合物組成物(B)為著色組成物之情況下，可包含適合用於汽車空氣制動系統之管子的任一種著色劑。較佳著色劑為著色劑或顏料。須瞭解於此處著色劑為可溶於或分子可分散於共聚酯彈性體之著色劑；於此處須瞭解顏料為不可溶於或分子可分散於共聚酯彈性體之固體著色劑。適當顏料之實例為碳黑。適當著色劑之實例為苯胺黑，俗名為苯胺黑(nigrosine)。苯胺黑為不同供應商所供應之商品(例如PD工業公司，印度馬哈拉許左；蘭色思公司(Lanxess)，美國賓州；羅伊司聯合公司(Royce Associates)，美國紐澤西州；及阿尼洛顏料公司(Anirox Pigments Ltd.)，印度西孟加拉)且有不同變化，諸如水溶性苯胺黑、油溶性苯胺黑及醇溶性苯胺黑。較佳著色劑為油溶性苯胺黑。
於第二熱塑性聚合物組成物(B)包含碳黑之情況下，相對於第二熱塑性聚合物組成物(B)之總重，包含用量低於2 wt%，更佳0.01－1.5 wt%或甚至0.1－1.0 wt%之碳黑。
根據本發明之複合塑膠管之外表面層具有於寬廣範圍改變之厚度。較佳外表面辭具有厚度至少為0.025毫米，更佳至少為0.05毫米，又更佳至少為0.1毫米。外表層厚度較大之優點為可更進一步提升臭氧耐性。
也較佳外表面層具有厚度至多為0.5毫米，更佳至多為0.25毫米。其優點為當複合塑膠管中之第一熱塑性聚合物組成物(A)為未經著色之組成物，而第二熱塑性聚合物組成物(B)為經著色之組成物之情況下，複合塑膠管有較為消光且更濃的色彩。
根據本發明之複合塑膠管除了內表面層(a)及外表面層(b)之外，進一步包含至少一層中間層(c)位在外表面層與內表面層間，且係由與(A)及(B)不同的聚合物組成物(C)所組成。
聚合物組成物(C)包含或係由包含共聚酯彈性體之熱塑性聚合物組成物所組成。只要不會去除根據本發明之複合塑膠管之臭氧耐性，則可包含另一種組成物或由另一種組成物所組成。
根據本發明之複合塑膠管可使用一種包含共同擠塑步驟之方法製造。於此種方法中，兩種或更多種材料擠塑通過有兩個或多個孔口之單一壓模，該等孔口係配置成擠塑產物可合併且熔合成為單一產物，於本發明中該產物為管子。該方法視需要可包含成形步驟。於此種成形步驟中，複合塑膠管可具有一細長部分，包含多個適合用於目標汽車制動系統之彎部及/或彎曲的形式。成形步驟可藉任一種適合用於彎曲及成形塑膠管之成形方法進行。成形步驟適合為熱成形步驟，亦即成形方法涉及塑膠管之加熱、變形、以及隨後冷卻之成形步驟。
因此本發明亦係關於一種製造根據本發明之複合塑膠管之方法，包含一共同擠塑步驟，以及任選地包含一(加熱)成形步驟。
根據本發明之經拉伸之塑膠管也可由整體由熱塑性聚合物組成物(A)所組成之塑膠管來製成。其優點為經拉伸之塑膠管有進一步改良之臭氧耐性。
可用於複合塑膠管及整合塑膠管作為第一共聚酯彈性體(A－1)，以及用於複合塑膠管作為第二共聚酯彈性體(B－1)之共聚酯彈性體以及由此等塑膠管所製成之經拉伸之塑膠管中之共聚酯彈性體，可為任一種適合用於塑膠管之共聚酯彈性體。共聚酯彈性體包含或為共聚醚酯彈性體、共聚酯酯彈性體、或共聚碳酸酯酯彈性體或其混合物。
於此處須瞭解共聚醚酯彈性體為一種嵌段共聚物，該嵌段共聚物含有由高熔結晶性或半晶性芳香族聚酯或半芳香族聚酯之嵌段所組成之硬節段，以及由低熔聚醚之嵌段所組成之軟節段。共聚醚酯彈性體適合係由衍生自芳香族二羧酸及脂肪族二醇之重複單位所製成之硬聚酯節段，以及由聚二醇醚也稱作為聚(伸烷基氧化物)所製成之軟節段所製成。適合用於共聚醚酯彈性體之軟節段之聚(伸烷基氧化物)為聚(伸乙基氧化物)、聚(伸丙基氧化物)及聚(四亞甲基氧化物)及其隨機共聚物及嵌段共聚物。
較佳於共聚醚酯彈性體中之軟節段係由聚(四亞甲基氧化物)所製成。有關共聚醚酯彈性體及其製備之綜合說明可參考聚合物科學及技術百科，第12期，第76－177頁(1985年)及其中報告之參考文獻。
此處須瞭解共聚酯酯彈性體為一種嵌段共聚物，該嵌段共聚物含有由高熔結晶性或半晶性芳香族聚酯或半芳香族聚酯之嵌段所組成之硬節段，以及由低熔聚酯二醇之嵌段所組成之軟節段。共聚酯酯彈性體適合係由衍生自芳香族二羧酸及脂肪族二醇之重複單位所製成之硬聚酯節段，以及軟節段係由脂肪族二醇及脂肪族二羧酸或內酯或其組合所組成，其中該硬節段及軟節段可以胺基甲酸酯基連接。共聚酯酯彈性體及其製備例如說明於歐洲專利EP－0102115－B1。
此處須瞭解共聚碳酸酯酯彈性體為一種嵌段共聚物，該嵌段共聚物含有由高熔結晶性或半晶性芳香族聚酯或半芳香族聚酯之嵌段所組成之硬節段，以及由含聚合物成分之低熔聚碳酸酯之嵌段所組成之軟節段。共聚碳酸酯酯彈性體適合係由衍生自芳香族二羧酸及脂肪族二醇之重複單位所製成之硬聚酯節段，以及軟節段係由脂肪族碳酸酯之重複單位所製成，及/或軟節段係由隨機分布之脂肪族碳酸酯重複單位以及脂肪族二醇及脂肪族二羧酸或內酯之隨機分布的重複單位或其組合所組成，其中該硬節段及軟節段係以胺基甲酸酯基團連接。共聚碳酸酯酯彈性體及其製備例如係說明於歐洲專利EP－0846712－B1。
於共聚酯彈性體之硬節段中之芳香族二羧酸例如可為對苯二甲酸、萘二羧酸、及聯苯二羧酸或其混合物。脂肪族二醇例如為伸乙基二醇(也稱作為乙二醇)、伸丙基二醇、伸丁基二醇(也稱作為1,4－丁二醇)、六亞甲基二醇或其混合物。於第一熱塑性聚合物組成物(A)以及若適用時，於第二熱塑性聚合物組成物(B)中之共聚酯彈性體節段較佳係由包含對苯二甲酸之芳香族二羧酸及包含乙二醇及/或1,4－丁二醇之脂肪族二醇衍生得之重複單位所組成。較佳硬節段係由對苯二甲酸及1,4－丁二醇製成。
於第一熱塑性聚合物組成物(A)中之共聚酯彈性體較佳為共聚碳酸酯酯彈性體或共聚酯酯彈性體，更佳為共聚碳酸酯酯彈性體。其優點為更進一步改良臭氧耐性。
第一熱塑性聚合物組成物(A)及第二熱塑性聚合物組成物(B)除了共聚酯彈性體之外也包含其它成分。可能存在的成分可為任一種適合用於空氣制動器之塑膠管中之任一種添加劑。較佳，第一熱塑性聚合物組成物(A)及/或第二熱塑性聚合物組成物(B)包含選自於由安定劑、著色劑及加工助劑所組成之組群之至少一種添加劑；更佳包含至少一種安定劑，又更佳包含至少一種抗臭氧劑。適合加工助劑包括潤滑劑及離型劑。適當安定劑之實例為紫外光安定劑、熱安定劑、抗氧化劑及抗臭氧劑。適當抗臭氧劑之實例為經拉伸之對伸苯基二胺類(例如N,N’－二苯基－對二伸苯基二胺)、環狀縮醛(例如福卡宗(Vulkazon)AFS/LG)及烯醇醚類(例如福卡宗AFD)。
特別係用於第一熱塑性聚合物組成物(A)，但也可用於第二熱塑性聚合物組成物(B)之適當著色劑為苯胺黑。當塑膠管必須製作成黑色時，較佳施用苯胺黑。當至少一外表面層含有苯胺黑時，比較有碳黑於至少一外表面層之相對應之黑色塑膠管，前者可製造有較佳臭氧耐性之塑膠管。
於本發明之另一個實施例中，經拉伸之塑膠管係由不含碳黑之複合塑膠管所製成，具有包含苯胺黑之一內表面層及由未經著色之熱塑性聚合物組成物所組成之一外表面層。
根據本發明之複合塑膠管及其較佳實施例以及整體由熱塑性聚合物組成物(A)所組成之塑膠管可使用包含拉伸步驟之方法，亦即其中至少一端部接受機械拉伸之步驟，而被轉成根據本發明之經拉伸之塑膠管。該機械拉伸例如可將具有插入管內部分之外徑係大於塑膠管內徑之軟管接頭插入管內來達成。軟管接頭可為任一型適合用於安裝空氣制動系統管至引擎之管狀接頭。較佳軟管接頭為圓柱形軟管接頭或錐形軟管接頭。也適合軟管接頭包含錐形節段，亦即於接頭之伸長方向之尺寸遞增或遞減之節段。適合錐形節段具有倒刺形，亦即具有尖銳緣從軟管接頭之欲插入管內部該端向後凸起。
由於機械拉伸結果，經拉伸之端部包含一經拉伸之節段，其直徑係比該塑膠管之細長部分直徑以及拉伸前之端部直徑更大。較佳細長部分有第一外徑D1，細長端部包含有第二外徑D2之經拉伸區段，D2至少比D1大1%。較佳D2至少比D1大2%，更佳至少大5%，又更佳至少大10%。D2甚至可比D1大20%。D1與D2間之差異愈大，則根據本發明之臭氧耐性的改良愈顯著。
根據本發明之複合塑膠管具有第一外徑於寬廣範圍改變，可低抵例如3毫米或甚至更低，大至例如25毫米，甚至更大。用於汽車用途，直徑較佳係於5－20毫米，更佳8－15毫米，又更佳10－12.5毫米之範圍。通常以D1愈小，D2有較大增量為實用，可獲得根據本發明之較大效果。
根據本發明之經拉伸之塑膠管也具有於寬廣範圍改變之壁厚度(T)。經拉伸之塑膠管適合具有壁厚度至少為0.2毫米，較佳0.5－3毫米，或甚至1－2毫米。
本發明亦係關於一種製造根據本發明之經拉伸之塑膠管之方法。根據本發明之方法包含拉伸步驟。拉伸步驟可整合於塑膠管之製造程序，結果獲得包含一(共)擠塑步驟、任選地一(加熱)成形步驟及一拉伸步驟之此種順序之方法。
本發明也係關於一種空氣制動管路系統，包含根據本發明之經拉伸之塑膠管或其任何較佳實施例，以及插入經拉伸之端部之一軟管接頭。
本發明亦係關於包含根據本發明之空氣制動管路系統之一種空氣制動系統。該空氣制動系統適合為真空空氣制動系統或壓力空氣制動系統。
1．．．圓柱形有倒刺之軟管接頭
2．．．筒形部
4．．．中部
6．．．錐形部
8．．．端
10．．．錐形有倒刺節段
12．．．遞減直徑
14．．．尖銳緣
第1圖.圓柱形有倒刺之軟管接頭之示意三維仰視圖。第1圖顯示圓柱形有倒刺之軟管接頭之示意三維仰視圖。該圓柱形有倒刺之軟管接頭(1)包含一筒形部(2)、一中部(4)及一螺紋部(6)。筒形部(2)有一端部(8)，包含數個個別錐形有倒刺節段(10)，可由遞減的直徑(12)以及由端部(8)伸出之尖銳緣(14)辨識。
1．．．圓柱形有倒刺之軟管接頭
2．．．筒形部
4．．．中部
6．．．錐形部
8．．．端
10．．．錐形有倒刺節段
12．．．遞減直徑
14．．．尖銳緣
Claims (3)
- 一種空氣制動系統，其包含一經拉伸之塑膠管，而該經拉伸之塑膠管含有一經拉伸之端部及插入該經拉伸之端部內的一軟管接頭，其特徵在於：該經拉伸之端部包含一外表面層區域，其係由一第一熱塑性聚合物組成物(A)所組成，而該組成物(A)含有一第一共聚酯彈性體(A-1)以及相對於該熱塑性聚合物組成物(A)之總重為0-0.2 wt%的碳黑。
- 如申請專利範圍第1項之空氣制動系統，其中該經拉伸之塑膠管包含一第二聚合物組成物(B)之內表面層，該組成物(B)包含一第二共聚酯彈性體(B-1)以及相對於該第二聚合物組成物(B)之總重為大於0.2 wt%的碳黑。
- 如申請專利範圍第1項之空氣制動系統，其中該經拉伸之塑膠管係整體由該熱塑性聚合物組成物(A)所組成。
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW096101744A TWI392820B (zh) | 2006-01-17 | 2007-01-17 | 用於空氣制動系統之塑膠管 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US8206799B2 (zh) |
| EP (1) | EP1973732A1 (zh) |
| KR (1) | KR101357435B1 (zh) |
| CN (1) | CN101370647B (zh) |
| TW (1) | TWI392820B (zh) |
| WO (1) | WO2007082710A1 (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1973732A1 (en) * | 2006-01-17 | 2008-10-01 | DSMIP Assets B.V. | Plastic tube for air-brake systems |
| KR20090118927A (ko) * | 2007-02-12 | 2009-11-18 | 디에스엠 아이피 어셋츠 비.브이. | 중합체 조성물 및 이로부터 제조된 플라스틱 튜브 |
| JP5532437B2 (ja) * | 2007-11-21 | 2014-06-25 | ディーエスエム アイピー アセッツ ビー．ブイ． | クラスｅ区分のケーブルおよびチューブ |
| US9759353B2 (en) * | 2012-09-24 | 2017-09-12 | Eaton Corporation | Air brake tubing and compositions for making the same |
| WO2015038729A1 (en) | 2013-09-13 | 2015-03-19 | Dersham Jeffrey L | Bungee cord / strap and method of use |
| WO2015144520A1 (en) * | 2014-03-24 | 2015-10-01 | Dsm Ip Assets B.V. | Apparatus for dosing a urea solution to a selective catalytic reduction (scr) catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6207752B1 (en) * | 1997-12-10 | 2001-03-27 | Advanced Elastomer Systems Lp | Thermoplastic vulcanizates of carboxylated nitrile rubber and thermoplastic polyurethanes |
| TW482810B (en) * | 1997-12-10 | 2002-04-11 | Advanced Elastomer Systems | Thermoplastic vulcanizate composition and its preparation process |
| US20030136457A1 (en) * | 2002-01-24 | 2003-07-24 | Tokai Rubber Industries, Ltd. | Fuel hose |
| US20040058111A1 (en) * | 2002-09-23 | 2004-03-25 | Saint-Gobain Performance Plastics Corp. | Compounded nylon 6, nylon 12 material for air brake systems |
| US20040134555A1 (en) * | 2002-11-26 | 2004-07-15 | Powell Steven M. | Tubular polymeric composites for tubing and hose constructions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06107804A (ja) * | 1991-12-14 | 1994-04-19 | Nippon Zeon Co Ltd | チューブおよびホース |
| US5514299A (en) * | 1994-07-11 | 1996-05-07 | Bridgestone/Firestone, Inc. | Static dissipative container liner and method of making same |
| JP3606204B2 (ja) | 2001-01-19 | 2005-01-05 | 日産自動車株式会社 | 樹脂製チューブ |
| EP1973732A1 (en) * | 2006-01-17 | 2008-10-01 | DSMIP Assets B.V. | Plastic tube for air-brake systems |
| KR20090042826A (ko) * | 2006-07-28 | 2009-04-30 | 디에스엠 아이피 어셋츠 비.브이. | 난연성 열가소성 조성물 |
| KR20090118927A (ko) * | 2007-02-12 | 2009-11-18 | 디에스엠 아이피 어셋츠 비.브이. | 중합체 조성물 및 이로부터 제조된 플라스틱 튜브 |
| KR20090119769A (ko) * | 2007-03-13 | 2009-11-19 | 디에스엠 아이피 어셋츠 비.브이. | 자동차용 에어 브레이크 시스템에서 사용하기 위한 플라스틱 튜브 |
-
2007
- 2007-01-16 EP EP07711347A patent/EP1973732A1/en not_active Withdrawn
- 2007-01-16 WO PCT/EP2007/000332 patent/WO2007082710A1/en active Application Filing
- 2007-01-16 KR KR1020087017277A patent/KR101357435B1/ko not_active IP Right Cessation
- 2007-01-16 US US12/160,843 patent/US8206799B2/en not_active Expired - Fee Related
- 2007-01-16 CN CN2007800025295A patent/CN101370647B/zh not_active Expired - Fee Related
- 2007-01-17 TW TW096101744A patent/TWI392820B/zh not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6207752B1 (en) * | 1997-12-10 | 2001-03-27 | Advanced Elastomer Systems Lp | Thermoplastic vulcanizates of carboxylated nitrile rubber and thermoplastic polyurethanes |
| TW482810B (en) * | 1997-12-10 | 2002-04-11 | Advanced Elastomer Systems | Thermoplastic vulcanizate composition and its preparation process |
| US20030136457A1 (en) * | 2002-01-24 | 2003-07-24 | Tokai Rubber Industries, Ltd. | Fuel hose |
| US20040058111A1 (en) * | 2002-09-23 | 2004-03-25 | Saint-Gobain Performance Plastics Corp. | Compounded nylon 6, nylon 12 material for air brake systems |
| US20040134555A1 (en) * | 2002-11-26 | 2004-07-15 | Powell Steven M. | Tubular polymeric composites for tubing and hose constructions |
Also Published As
| Publication number | Publication date |
|---|---|
| US20110177274A1 (en) | 2011-07-21 |
| KR20080089399A (ko) | 2008-10-06 |
| CN101370647B (zh) | 2012-08-29 |
| EP1973732A1 (en) | 2008-10-01 |
| TW200738989A (en) | 2007-10-16 |
| CN101370647A (zh) | 2009-02-18 |
| KR101357435B1 (ko) | 2014-02-03 |
| US8206799B2 (en) | 2012-06-26 |
| WO2007082710A1 (en) | 2007-07-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |