TW200840890A

TW200840890A - Buffer layer for strings

Info

Publication number: TW200840890A
Application number: TW096143229A
Authority: TW
Inventors: Zvi Yaniv; yun-jun Li; dong-sheng Mao
Original assignee: Nano Proprietary Inc
Priority date: 2006-11-16
Filing date: 2007-11-15
Publication date: 2008-10-16
Also published as: WO2008061229A9; EP2083928B1; EP2083928A1; WO2008061229A1; JP2010510400A; ATE530230T1; CN101534909A; US20080124546A1

Abstract

A thin buffer layer is used to coat on the multi-filament wrapped string to fill the gaps. The polymers of the buffer-layer coating have a high melt-flow (low viscosity) during coating process to fill all the gaps between the filaments, and the filaments are fixed by the coatings onto base core materials.

Description

200840890 九、發明說明【發明所屬之技術領域】本申請案主張美國臨時申請案序號優先權，其以引用方式納入本文中。本層經用來塗覆在多絲纏繞弦線以塡充間聚合物在塗覆程序中具有高熔融流速（諸絲間的所有間隙，且諸絲係藉由塗覆予以固定。【先前技術】用於運動設備（例如，網球拍）或在彼等的最外表面塗覆一薄層以改良彼、觸覺、等。聚醯胺（尼龍（nylon) 聚合物業經用來塗覆在弦線上。 nanocomposites )，諸如黏土及奈米碳化之尼龍6奈米複合材料（具有比純尼性）皆有可能爲具其他功能性之高耐用使用具有局縱橫比（aspect ratio)之奈該強化聚合物複合材料業經自1 9 8 0年美國專利第4,73 9,007號）。弦線常爲心絲、在核心絲上的纏繞絲、及塗層之具有多層結構之弦線，塗覆材料皆需要某一溫度要具有良好的熔融流動性質（使彼等滲透到介於纏繞絲之間的間隙內第 60/866,1 99 號之案係關於一薄緩衝隙。緩衝層塗層之低黏度）以塡充在在基礎核心材料上音樂樂器之弦線常等的耐久性、旋轉 )、聚酯、及其他奈米複合材料（管（Nanotube)強龍6較佳的物理特性弦線塗覆材料。米尺寸黏土粒子之代硏究至今（參閱具有多層結構··核聚合物材料。對於匹配基礎材料及在可接受的黏度）以。奈米複合材料之 -5- 200840890 黏度在相同溫度下常高於純的尼龍6。如此，奈米複合材料可能不容易滲透入介於纏繞絲間之間隙內。圖1顯示一種塗覆在纏繞絲上的尼龍6/黏土奈米複合材料之橫截面圖之SEM影像。可看出奈米複合材料材料未成功地塡充該間隙。在弦線中留下的許多缺陷導致弦線之不可接受的耐久性。該等間隙會在球的高衝擊拍擊中導致塗層的落屑（ c h i p p i n g 〇 f f )或不可接受的耐久性。再者，由於間隙之造成，塗層亦不能將絲固定在弦線的核心材料上。圖2顯示在弦線上的高衝擊檢驗後從絲和塗層切落之材料。【發明內容】雖然聚合物奈米複合材料具有比純聚合物材料更高的物理/機械性質，不過彼等在擠壓或塗覆程序中通常具有較高的黏度或熔融流速。爲解決此問題，係使用薄緩衝層塗覆在多絲纏繞弦線上以塡充間隙。緩衝層塗料之聚合物在塗覆程序中具有高熔融流速（低黏度）以塡充介於諸絲之間的所有間隙，及藉由塗料將絲固定在基礎核心材料上【實施方式】實施例1 :具有尼龍6緩衝層之塗料系統200840890 IX. INSTRUCTIONS OF THE INVENTION [Technical Field of the Invention] This application claims priority to U.S. Provisional Application Serial No. This layer is used to coat the multifilament-wound string to interpret the polymer with a high melt flow rate in the coating process (all gaps between the filaments, and the filaments are fixed by coating.) 】 for sports equipment (eg tennis rackets) or a thin layer on their outermost surface to improve the feel, touch, etc. Polyamide (nylon) polymer is used to coat the string Nanocomposites), such as clay and nanocarbonized nylon 6 nanocomposites (with a purer than the pure nature), are likely to be highly durable with other functionalities and have a local aspect ratio of the reinforced polymer. Composite materials have been used in U.S. Patent No. 4,73,007, 1987. The string is usually a core wire, a wound wire on the core wire, and a coated string having a multi-layer structure. The coating material needs a certain temperature to have good melt flow properties (so that they penetrate into the winding The 60/866,1 99 case in the gap between the wires is about a thin buffer gap. The low viscosity of the buffer layer coating is used to fill the string of the string of musical instruments on the base core material. , Rotating), Polyester, and other nanocomposites (Nanotube) Strong physical properties of string coating materials. The generation of rice-sized clay particles has been studied so far (see Multilayer Structure··Nuclear Polymerization) Materials. For matching base materials and acceptable viscosity), the viscosity of nanocomposite -5 - 200840890 is often higher than pure nylon 6 at the same temperature. Thus, nanocomposites may not easily penetrate into the medium. In the gap between the wound filaments. Figure 1 shows an SEM image of a cross-sectional view of a nylon 6/clay nanocomposite coated on a wound wire. It can be seen that the nanocomposite material did not successfully fill the gap. . Many of the defects left in the strings result in unacceptable durability of the strings, which can cause chipping 〇ff or unacceptable durability in the high impact slap of the ball. Due to the gap, the coating cannot fix the wire to the core material of the string. Figure 2 shows the material cut from the wire and the coating after high impact inspection on the string. [Summary] Although polymer nano Composite materials have higher physical/mechanical properties than pure polymer materials, but they typically have a higher viscosity or melt flow rate during extrusion or coating procedures. To solve this problem, a thin buffer layer is used to coat The multifilament winding string is filled with a gap. The polymer of the buffer layer coating has a high melt flow rate (low viscosity) in the coating process to fill all the gaps between the filaments, and the filament is fixed by the coating. Basic core material [Embodiment] Example 1: Coating system with nylon 6 buffer layer

圖3 A示出用於塗覆的弦線之橫截面，其包括一用較小直徑的複絲3 0 2纏繞的一卓絲核心3 0 1。將純尼龍6九粒如可得自 UBE Industries Inc.者（產品名稱·· UBE SF 200840890 1018 A)熔化。經由在從220 °C至270 1範圍之溫度壓製程施加緩衝層塗層3 03。緩衝層塗層3〇3之厚度從10至100微米。藉由純尼龍6塗覆完全塡充介於 3 02間之間隙。接著經由在從240 °C至2 80 °C範圍的溫度下之濟序塗覆一耐磨耗塗層304 (圖3C)。可以使用尼龍土或尼龍6/奈米碳管奈米複合材料作爲耐磨耗塗覆 304。藉由原位聚合產生的尼龍6奈米複合材料可含年奈米黏土塡充料。藉由熔融調配製程產生的其他尼龍米複合材料亦可用於耐磨耗塗層304。除了黏土之外米碳管、陶瓷粒（諸如Si02及Al2〇3)、或玻璃粒也來製造尼龍6奈米複合材料。尼龍6奈米複合材料亦橡膠改質劑改質以改良延展性及韌度。耐磨耗塗層之可爲從1至100微米。實施例2 :具有尼龍1 1緩衝層之塗料系統再參照圖3A，用於塗覆之弦線係一用較小直徑 3 02纏繞的單絲核心301。純尼龍1 1可得自ARKEMA 獲得。尼龍1 1在超過22(TC的溫度下具有非常好的熔動性。良好的抗衝擊強度及抗剪強度也使尼龍1 1成好的緩衝層材料。在圖3B中，緩衝層塗層3 03係藉 190°C至2 7(TC範圍的溫度之擠壓製程所施加。緩衝層303之厚度可爲從10至100微米。藉由龍Π塗覆將介於複絲3 02間之間隙完全塡充。的擠可爲複絲壓程 6/黏材料 r 4% 6奈，奈可用可用厚度複絲 Inc. 融流爲良由在純尼 200840890 參照圖3C，接著藉由在從24(TC至280°C範圍的溫度下之擠壓程序塗覆耐磨耗塗層304。可採用尼龍6 /黏土或尼龍6/奈米碳管之奈米複合材料作爲耐磨耗塗覆材料304 。藉由原位聚合產生的尼龍6奈米複合材料可含4%奈米黏土塡充料。藉由熔融調配程序產生的其他尼龍6奈米複合材料亦可用於耐磨耗塗層3 04。尼龍6奈米複合材料亦可用橡膠改質劑改質以改良延展性及韌度。耐磨耗塗層 304之厚度可爲從1至100微米。除了用於在弦線上沉積塗層之擠壓程序之外，其他方法諸如噴塗、浸塗、旋塗、刷塗、漆塗、及浸沒等程序可用來在弦線表面上沉積塗層。尼龍6奈米複合材料可在高於190°C下熔化及擠壓以在弦線上沉積塗層。尼龍6奈米複合材料可溶解在溶劑諸如甲酸之中且在室溫或高溫下經噴塗、浸塗、旋塗、刷塗、漆塗、或浸沒以在弦線上沉積塗層。接著可藉由後續程序諸如蒸發方法移除該溶劑。圖4示出本發明另一具體實例。基本上，接著係在圖 3 C之塗覆弦線結構上再用較小直徑複絲40 1塗覆。藉由在從190°C至270°C範圍的溫度下之擠壓程序施加一緩衝層塗層402，類似於塗層303。緩衝層塗料402之厚度可爲從1 0至1 0 0微米。藉由純尼龍1 1塗覆將複絲4 0 1間之間隙完全塡充。然後，藉由在從2 4 0 °C至2 8 0 °C範圍的溫度下之擠壓程序塗覆一耐磨耗塗層403。可以採用尼龍6/ 黏土或尼龍6/奈米碳管奈米複合材料作爲耐磨耗塗覆材料 403。藉由原位聚合產生的尼龍6奈米複合材料可含4 %奈 200840890 米黏土塡充料。藉由熔融調配程序產生的其他尼龍6奈米複合材料亦可用於耐磨耗塗層403。尼龍6奈米複合材料亦可用橡膠改質劑改質以改良延展性及韌度。耐磨耗塗層 403之厚度可爲從1至1〇〇微米。【圖式簡單說明】圖1顯示塗覆在纏繞絲上的尼龍6/黏土奈米複合材料的橫截面圖之SEM影像。圖2顯示在弦線的高衝擊檢驗後，自該絲和塗層切落的材料之SEM影像。圖3A示出具有環繞其的纏繞絲的核心絲之橫截面；圖3 B示出施用於纏繞絲上之緩衝層；圖3C示出施用於緩衝層上之塗層；且圖4示出本發明另一具體實例。【主要元件符號說明】 30 1，401 :單絲核心 3 02 :複絲 3 03, 402 :緩衝層塗層 3 04, 403 :耐磨耗塗層Figure 3A shows a cross section of a string for coating comprising a wire core 301 wound with a smaller diameter multifilament 306. Pure nylon 6 nine particles were melted as available from UBE Industries Inc. (product name·· UBE SF 200840890 1018 A). The buffer layer coating 3 03 is applied via a temperature press from 220 ° C to 270 1 . The thickness of the buffer layer coating 3〇3 is from 10 to 100 μm. The gap between the 3 02 is completely filled by pure nylon 6 coating. An abradable coating 304 (Fig. 3C) is then applied via a process at a temperature ranging from 240 °C to 280 °C. A nylon or nylon 6/nano carbon nanotube nanocomposite can be used as the wear resistant coating 304. The nylon 6 nanocomposite produced by in-situ polymerization may contain an annual nano-clay crucible. Other nylon composites produced by the melt blending process can also be used in the wear resistant coating 304. In addition to clay, carbon nanotubes, ceramic particles (such as SiO 2 and Al 2 〇 3), or glass granules are also used to make nylon 6 nanocomposites. The nylon 6 nanocomposite is also modified with a rubber modifier to improve ductility and toughness. The abrasion resistant coating can range from 1 to 100 microns. Example 2: Coating System with Nylon 1 1 Buffer Layer Referring again to Figure 3A, the string used for coating was a monofilament core 301 wound with a smaller diameter 03. Pure nylon 1 1 is available from ARKEMA. Nylon 1 1 has very good meltability at temperatures above 22 (TC). Good impact strength and shear strength also make nylon 11 a good buffer layer material. In Figure 3B, buffer layer coating 3 03 is applied by an extrusion process of 190 ° C to 27 (temperature in the range of TC. The thickness of the buffer layer 303 may be from 10 to 100 μm. The coating by the tarragon will be between the gaps of the multifilaments 03. Fully squeezing. The squeezing can be multifilament pressure stroke 6/viscous material r 4% 6 na, neat can be used thickness of multifilament Inc. fused flow as good cause in pure Nepal 200840890 refer to Figure 3C, then by at 24 The abrasion resistant coating 304 is applied by an extrusion process at a temperature ranging from TC to 280 ° C. A nanocomposite of nylon 6 / clay or nylon 6 / carbon nanotubes may be used as the wear resistant coating material 304 . The nylon 6 nanocomposite produced by in-situ polymerization can contain 4% nano-clay crucible. Other nylon 6 nanocomposites produced by the melt blending procedure can also be used for wear-resistant coatings. 6 nanocomposites can also be modified with rubber modifiers to improve ductility and toughness. The thickness of the wear resistant coating 304 can be From 1 to 100 microns. In addition to the extrusion process used to deposit coatings on the strings, other methods such as spraying, dip coating, spin coating, brushing, painting, and immersion can be used on the surface of the string. Deposition coating. Nylon 6 nanocomposite can be melted and extruded at temperatures above 190 ° C to deposit a coating on the string. Nylon 6 nanocomposite can be dissolved in a solvent such as formic acid at room temperature or elevated temperature Spraying, dip coating, spin coating, brushing, painting, or immersion to deposit a coating on the string. The solvent can then be removed by subsequent procedures such as evaporation. Figure 4 shows another embodiment of the invention Basically, it is then coated with a smaller diameter multifilament 40 1 on the coated string structure of Figure 3 C. By applying a squeezing procedure at a temperature ranging from 190 ° C to 270 ° C Buffer layer coating 402, similar to coating 303. Buffer layer coating 402 can have a thickness from 10 to 100 microns. The gap between the multifilaments 410 is fully filled by pure nylon 1 1 coating. Then, an abrasion resistance is applied by an extrusion process at a temperature ranging from 240 ° C to 2 80 ° C. Layer 403. A nylon 6/clay or nylon 6/nano carbon nanotube nano composite may be used as the wear resistant coating material 403. The nylon 6 nano composite produced by in-situ polymerization may contain 4% nai 200840890 m. Clay enamel filling. Other nylon 6 nanocomposites produced by the melt blending procedure can also be used for wear resistant coatings 403. Nylon 6 nanocomposites can also be modified with rubber modifiers to improve ductility and toughness. The thickness of the wear resistant coating 403 can range from 1 to 1 micron. [Simplified Schematic] FIG. 1 shows an SEM image of a cross-sectional view of a nylon 6/clay nano composite coated on a wound wire. . Figure 2 shows an SEM image of the material cut from the wire and the coating after the high impact test of the string. Figure 3A shows a cross section of a core wire having a wound wire surrounding it; Figure 3B shows a buffer layer applied to the wound wire; Figure 3C shows a coating applied to the buffer layer; and Figure 4 shows Another specific example of the invention. [Main component symbol description] 30 1,401 : Monofilament core 3 02 : Multifilament 3 03, 402 : Buffer coating 3 04, 403 : Abrasion resistant coating

Claims

200840890 十、申請專利範圍 1 · 一種用於弦線之塗層，其包括：一核心絲’其經由具有比核心絲較小直徑的複數條纏繞絲予以纏繞；一緩衝層塗層’其塡充在介於纏繞絲之間及介於纏繞絲與核心絲間之間隙；及一外部塗層，其覆蓋該緩衝層塗層、纏繞絲及核心絲〇 2 ·如申請專利範圍第1項之塗層，其中該緩衝層塗層包含聚合物。 3 ·如申請專利範圍第1項之塗層，其中該緩衝層塗層包含尼龍（nylon )。 4.如申請專利範圍第3項之塗層，其中該緩衝層塗層包含尼龍6。 5 ·如申請專利範圍第3項之塗層，其中該緩衝層塗層包含尼龍1 1。 6·如申請專利範圍第3項之塗層，其中該外部塗層包含尼龍和黏土奈米粒之複合材料。 7·如申請專利範圍第3項之塗層，其中該外部塗層包含尼龍和奈米碳管之複合材料。 8·如申請專利範圍第6項之塗層，其中該外部塗層進一步包含一改質劑。 9· 一種用於塗覆弦線之方法，其包括：纒繞具有第一直徑之核心絲，其中係使用一或更多具 -1(K 200840890 有小於該第一直徑的第二直徑之纏繞絲；擠壓熔融尼龍至一或更多纒繞絲間之間隙及該纏繞絲與核心絲間之間隙中；擠壓一塗層於弦線的圓周之上使其覆蓋一或更多纏繞絲及在間隙內的熔融尼龍。 10·如申請專利範圍第9項之方法，其中該熔融尼龍包含尼龍6。 1 1 ·如申請專利範圍第9項之方法，其中該熔融尼龍包含尼龍1 1。 1 2.如申請專利範圍第9項之方法，其中該塗層包含尼龍與黏土奈米粒之複合材料。 1 3 ·如申請專利範圍第9項之方法，其中該塗層包含尼龍與奈米碳管之複合材料。 1 4 ·如申請專利範圍第9項之方法，其中該塗層包含尼龍與陶瓷粒之複合材料。 1 5 ·如申請專利範圍第9項之方法，其中該塗層包含尼龍與玻璃粒之複合材料。 1 6·如申請專利範圔第9項之方法，其中該塗層厚度爲介於1與100微米之間。 1 7 ·如申請專利範圓第1項之塗層，其進一步包含：另一複數纏繞絲，其纏繞該外部塗層；另一緩衝層塗層’其塡充在該另一複數纏繞絲間之間隙；及另一外部塗層，其覆蓋該另一緩衝層塗層。 -11 - 200840890 18. 如申請專利範圍第3項之塗層，其中該塗層包含尼龍和玻璃粒之複合材料。 19. 如申請專利範圍第3項之塗層，其中該塗層包含尼龍和陶瓷粒之複合材料。 -12-200840890 X. Patent Application No. 1 · A coating for a string comprising: a core filament 'wound through a plurality of winding filaments having a smaller diameter than the core filament; a buffer layer coating' a gap between the wound filaments and between the wound filaments and the core filaments; and an outer coating covering the buffer layer coating, the wound filaments, and the core filaments 2 as described in claim 1 a layer wherein the buffer layer coating comprises a polymer. 3. The coating of claim 1, wherein the buffer layer coating comprises nylon. 4. The coating of claim 3, wherein the buffer layer coating comprises nylon 6. 5. The coating of claim 3, wherein the buffer layer coating comprises nylon 11. 6. The coating of claim 3, wherein the outer coating comprises a composite of nylon and clay nanoparticle. 7. The coating of claim 3, wherein the outer coating comprises a composite of nylon and carbon nanotubes. 8. The coating of claim 6 wherein the outer coating further comprises a modifier. 9. A method for coating a string, comprising: winding a core wire having a first diameter, wherein one or more of -1 is used (K 200840890 has a second diameter less than the first diameter) a filament; extruding molten nylon to a gap between one or more twisted filaments and a gap between the wound filament and the core filament; extruding a coating over the circumference of the string to cover one or more winding filaments The method of claim 9, wherein the molten nylon comprises nylon 6. The method of claim 9, wherein the molten nylon comprises nylon 11. 1 2. The method of claim 9, wherein the coating comprises a composite of nylon and clay nanoparticle. The method of claim 9, wherein the coating comprises nylon and nanocarbon. The method of claim 9, wherein the coating comprises a composite of nylon and ceramic particles. The method of claim 9, wherein the coating comprises nylon. Compound with glass The method of claim 9, wherein the coating thickness is between 1 and 100 microns. 1 7 · The coating of claim 1, wherein the coating further comprises: Another plurality of winding wires wound around the outer coating; another buffer layer coating 'filling the gap between the other plurality of winding wires; and another outer coating covering the other buffer layer coating -11 - 200840890 18. The coating of claim 3, wherein the coating comprises a composite of nylon and glass granules. 19. The coating of claim 3, wherein the coating comprises nylon Composite with ceramic particles. -12-