WO2008061229A9 - Buffer layer for strings - Google Patents

Buffer layer for strings

Info

Publication number
WO2008061229A9
WO2008061229A9 PCT/US2007/084973 US2007084973W WO2008061229A9 WO 2008061229 A9 WO2008061229 A9 WO 2008061229A9 US 2007084973 W US2007084973 W US 2007084973W WO 2008061229 A9 WO2008061229 A9 WO 2008061229A9
Authority
WO
WIPO (PCT)
Prior art keywords
coating
nylon
buffer layer
filaments
gaps
Prior art date
Application number
PCT/US2007/084973
Other languages
French (fr)
Other versions
WO2008061229A1 (en
Inventor
Zvi Yaniv
Yunjun Li
Dongsheng Mao
Original Assignee
Nano Proprietary Inc
Zvi Yaniv
Yunjun Li
Dongsheng Mao
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nano Proprietary Inc, Zvi Yaniv, Yunjun Li, Dongsheng Mao filed Critical Nano Proprietary Inc
Priority to JP2009537390A priority Critical patent/JP2010510400A/en
Priority to AT07864530T priority patent/ATE530230T1/en
Priority to EP07864530A priority patent/EP2083928B1/en
Publication of WO2008061229A1 publication Critical patent/WO2008061229A1/en
Publication of WO2008061229A9 publication Critical patent/WO2008061229A9/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B51/00—Stringing tennis, badminton or like rackets; Strings therefor; Maintenance of racket strings
    • A63B51/02—Strings; String substitutes; Products applied on strings, e.g. for protection against humidity or wear
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • D07B1/162—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber enveloping sheathing
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • D07B1/165—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber inlay
    • G—PHYSICS
    • G10—MUSICAL INSTRUMENTS; ACOUSTICS
    • G10D—STRINGED MUSICAL INSTRUMENTS; WIND MUSICAL INSTRUMENTS; ACCORDIONS OR CONCERTINAS; PERCUSSION MUSICAL INSTRUMENTS; AEOLIAN HARPS; SINGING-FLAME MUSICAL INSTRUMENTS; MUSICAL INSTRUMENTS NOT OTHERWISE PROVIDED FOR
    • G10D3/00—Details of, or accessories for, stringed musical instruments, e.g. slide-bars
    • G10D3/10—Strings
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/10—Rope or cable structures
    • D07B2201/1028—Rope or cable structures characterised by the number of strands
    • D07B2201/1036—Rope or cable structures characterised by the number of strands nine or more strands respectively forming multiple layers
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2071—Spacers
    • D07B2201/2074—Spacers in radial direction
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2083—Jackets or coverings
    • D07B2201/2087—Jackets or coverings being of the coated type
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/10—Natural organic materials
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/20—Organic high polymers
    • D07B2205/2046—Polyamides, e.g. nylons
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/30—Inorganic materials
    • D07B2205/3007—Carbon
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2936—Wound or wrapped core or coating [i.e., spiral or helical]

Definitions

  • the strings for sports equipment e.g., tennis raquets
  • musical instruments are usually coated with a thin layer at their outmost surface to improve their durability, spin, feeling, etc.
  • Nanocomposites such as clay and carbon nanotube reinforced nylon 6 nanocomposites, having better physical properties than neat nylon 6, are of a potential to be highly durable string coating materials with other functionalities.
  • the reinforcing polymeric composites using nano-sized clay particles with high aspect ratio have been investigated since the 1980's (see U.S. Patent No.
  • Strings are usually polymer materials with a multi-layer structure - core filament, wrapping filaments on the core filament, and coating.
  • coating materials are required to match the base materials and have good melt-flow properties (acceptable viscosity) at certain temperature to allow them to be penetrated into the gaps between the wrapping filaments.
  • Viscosity of a nanocomposite is usually higher than neat nylon 6 at the same temperature. Thus, the nanocomposite may not easily penetrate into the gaps between the wrapping filaments.
  • Figure 1 shows an SEM image of a cross-section view of a nylon 6/clay nanocomposite coated on a wrapping filament. It can be seen that the nanocomposite material did not successfully fill out the gaps.
  • Figure 1 shows an SEM image of a cross-section view of a nylon 6/clay nanocomposite coated on a wrapping filament
  • Figure 2 shows an SEM image of chipped materials from filaments and coatings after high impact tests on a string
  • Figure 3 A illustrates a cross-section of a core filament with wrapping filaments surrounding it
  • Figure 3B illustrates a buffer layer applied onto the wrapping filament
  • Figure 3 C illustrates a coating applied onto the buffer layer
  • FIG. 4 illustrates another embodiment of the present invention.
  • polymer nanocomposites have higher physical/mechanical properties than neat polymer materials, they normally have higher viscosity or melt- flow during an extrusion or coating process.
  • 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.
  • Example 1 A coating system with a nylon 6 buffer layer
  • Figure 3A illustrates a cross-section of a string for coating comprised of one monofilament core 301 wrapped with smaller-diameter multi-filaments 302.
  • Neat nylon 6 pellets as may be obtained from UBE Industries Inc. (product name: UBE SF 1018 A) are melted.
  • the buffer layer coating 303 is applied by an extrusion process at temperatures ranging from 22O 0 C to 27O 0 C.
  • the thickness of the buffer layer 303 may be from 10 to 100 micrometers.
  • the gaps between the multi-filaments 302 are fully filled by the neat nylon 6 coating.
  • a wear-resistant coating 304 is then coated (Figure 3C) by an extrusion process at temperatures ranging from 24O 0 C to 28O 0 C.
  • a nylon 6/clay or nylon 6/carbon nanotube nanocomposite may be employed as the wear-resistant coating material 304.
  • the nylon 6 nanocomposite produced by in-situ polymerization may contain 4% nano-clay filler.
  • Other nylon 6 nanocomposites produced by melt-compounded process may also be used for the wear- resistant coatings 304. Except for the clay, carbon nanotubes, ceramic particles such as SiO 2 and AI2O3, or glass particles may be used to make nylon ⁇ nanocomposites.
  • the Nylon 6 nanocomposites may also be modified by rubber modifiers to improve the ductility and toughness.
  • the thickness of the wear-resistant coating may be from 1 to 100 micrometers.
  • Example 2 A coating system with a nylon 11 buffer layer
  • the string for coating is one monofilament core 301 wrapped with smaller-diameter multi-filaments 302.
  • Neat nylon 11 may be obtained from ARKEMA Inc. Nylon 11 has a very good melt flow at temperatures over 22O 0 C. Good impact strength and shear strength also make nylon 11 a good buffer layer material.
  • the buffer layer coating 303 is applied by an extrusion process at temperatures ranging from 19O 0 C to 27O 0 C.
  • the thickness of the buffer layer 303 may be from 10 to 100 micrometers.
  • the gaps between the multi-filaments 302 are fully filled by the neat nylon 11 coating.
  • a wear-resistant coating 304 is then coated by an extrusion process at temperatures ranging from 24O 0 C to 28O 0 C.
  • Nylon 6/clay or a nylon 6/carbon nanotube nanocomposite may be employed as the wear-resistant coating material 304.
  • the nylon 6 nanocomposite produced by in-situ polymerization may contain 4% nano-clay filler.
  • Other nylon 6 nanocomposites produced by melt-compounded process may also be used for the wear-resistant coating 304.
  • the nylon 6 nanocomposites may also be modified by rubber modifiers to improve the ductility and toughness.
  • the thickness of the wear-resistant coating 304 may be from 1 to 100 micrometers.
  • Nylon 6 nanocomposites may be melted at higher than 19O 0 C and extruded to deposit a coating on the strings. Nylon 6 nanocomposites may be dissolved in a solvent such as formic acid and sprayed, dipped, spin coated, brushed, painted, or immersed to deposit a coating on the string at room temperature or elevated temperatures. The solvent may be then removed by a follow-up process such as an evaporation method.
  • Figure 4 illustrates another embodiment of the present invention.
  • the coated string structure of Figure 3 C is then coated again with smaller-diameter multi-filaments 401.
  • a buffer layer coating 402 similar to layer 303, is applied by an extrusion process at temperatures ranging from 19O 0 C to 27O 0 C.
  • the thickness of the buffer layer 402 may be from 10 to 100 micrometers.
  • the gaps between the multi-filaments 401 are fully filled by the neat nylon 11 coating.
  • a wear-resistant coating 403 is then coated by an extrusion process at temperatures ranging from 24O 0 C to 28O 0 C.
  • Nylon 6/clay or a nylon 6/carbon nanotube nanocomposite may be employed as the wear-resistant coating material 403.
  • the nylon 6 nanocomposite produced by in-situ polymerization may contain 4% nano-clay filler.
  • Other nylon 6 nanocomposites produced by melt-compounded process may also be used for the wear-resistant coating 403.
  • the nylon 6 nanocomposites may also be modified by rubber modifiers to improve the ductility and toughness.
  • the thickness of the wear-resistant coating 403 may be from 1 to 100 micrometers.

Abstract

A thin buffer layer (303) is used to coat on the multi-filament (401) 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

BUFFER LAYER FOR STRINGS
This application claims priority to U.S. Provisional Application Serial No. 60/866,199, which is hereby incorporated by reference hereby.
BACKGROUND
The strings for sports equipment (e.g., tennis raquets) or musical instruments are usually coated with a thin layer at their outmost surface to improve their durability, spin, feeling, etc.
Polyamide (nylon), polyester, and other polymers have been used to coat on strings. Nanocomposites, such as clay and carbon nanotube reinforced nylon 6 nanocomposites, having better physical properties than neat nylon 6, are of a potential to be highly durable string coating materials with other functionalities. The reinforcing polymeric composites using nano-sized clay particles with high aspect ratio have been investigated since the 1980's (see U.S. Patent No.
4,739,007). Strings are usually polymer materials with a multi-layer structure - core filament, wrapping filaments on the core filament, and coating. For the strings with multi-layer structures, coating materials are required to match the base materials and have good melt-flow properties (acceptable viscosity) at certain temperature to allow them to be penetrated into the gaps between the wrapping filaments. Viscosity of a nanocomposite is usually higher than neat nylon 6 at the same temperature. Thus, the nanocomposite may not easily penetrate into the gaps between the wrapping filaments. Figure 1 shows an SEM image of a cross-section view of a nylon 6/clay nanocomposite coated on a wrapping filament. It can be seen that the nanocomposite material did not successfully fill out the gaps. Many defects were left in the string which will result in unacceptable durability of the strings. The gaps will result in chipping-off or unacceptable durability of coatings during high impact hitting of balls. More over, due to creation of the gaps, coatings also fail to a fix the filaments on the core materials of the string. Figure 2 shows the chipped materials from filaments and coatings after high impact tests on the strings. BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows an SEM image of a cross-section view of a nylon 6/clay nanocomposite coated on a wrapping filament; Figure 2 shows an SEM image of chipped materials from filaments and coatings after high impact tests on a string;
Figure 3 A illustrates a cross-section of a core filament with wrapping filaments surrounding it;
Figure 3B illustrates a buffer layer applied onto the wrapping filament; Figure 3 C illustrates a coating applied onto the buffer layer; and
Figure 4 illustrates another embodiment of the present invention.
DETAILED DESCRIPTION
Although polymer nanocomposites have higher physical/mechanical properties than neat polymer materials, they normally have higher viscosity or melt- flow during an extrusion or coating process. To solve this problem, 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.
Example 1 : A coating system with a nylon 6 buffer layer
Figure 3A illustrates a cross-section of a string for coating comprised of one monofilament core 301 wrapped with smaller-diameter multi-filaments 302. Neat nylon 6 pellets as may be obtained from UBE Industries Inc. (product name: UBE SF 1018 A) are melted. The buffer layer coating 303 is applied by an extrusion process at temperatures ranging from 22O0C to 27O0C. The thickness of the buffer layer 303 may be from 10 to 100 micrometers. The gaps between the multi-filaments 302 are fully filled by the neat nylon 6 coating.
A wear-resistant coating 304 is then coated (Figure 3C) by an extrusion process at temperatures ranging from 24O0C to 28O0C. A nylon 6/clay or nylon 6/carbon nanotube nanocomposite may be employed as the wear-resistant coating material 304. The nylon 6 nanocomposite produced by in-situ polymerization may contain 4% nano-clay filler. Other nylon 6 nanocomposites produced by melt-compounded process may also be used for the wear- resistant coatings 304. Except for the clay, carbon nanotubes, ceramic particles such as SiO2 and AI2O3, or glass particles may be used to make nylonβ nanocomposites. The Nylon 6 nanocomposites may also be modified by rubber modifiers to improve the ductility and toughness. The thickness of the wear-resistant coating may be from 1 to 100 micrometers.
Example 2: A coating system with a nylon 11 buffer layer
Again referring to Figure 3 A, the string for coating is one monofilament core 301 wrapped with smaller-diameter multi-filaments 302. Neat nylon 11 may be obtained from ARKEMA Inc. Nylon 11 has a very good melt flow at temperatures over 22O0C. Good impact strength and shear strength also make nylon 11 a good buffer layer material. In Figure 3B, the buffer layer coating 303 is applied by an extrusion process at temperatures ranging from 19O0C to 27O0C.
The thickness of the buffer layer 303 may be from 10 to 100 micrometers. The gaps between the multi-filaments 302 are fully filled by the neat nylon 11 coating.
Referring to Figure 3C, a wear-resistant coating 304 is then coated by an extrusion process at temperatures ranging from 24O0C to 28O0C. Nylon 6/clay or a nylon 6/carbon nanotube nanocomposite may be employed as the wear-resistant coating material 304. The nylon 6 nanocomposite produced by in-situ polymerization may contain 4% nano-clay filler. Other nylon 6 nanocomposites produced by melt-compounded process may also be used for the wear-resistant coating 304. The nylon 6 nanocomposites may also be modified by rubber modifiers to improve the ductility and toughness. The thickness of the wear-resistant coating 304 may be from 1 to 100 micrometers.
Except for the extrusion process to deposit a coating on the string, other methods such as spraying, dipping, spin coating, brushing, painting, and immersing processes can be used to deposit a coating on the surface of strings. Nylon 6 nanocomposites may be melted at higher than 19O0C and extruded to deposit a coating on the strings. Nylon 6 nanocomposites may be dissolved in a solvent such as formic acid and sprayed, dipped, spin coated, brushed, painted, or immersed to deposit a coating on the string at room temperature or elevated temperatures. The solvent may be then removed by a follow-up process such as an evaporation method. Figure 4 illustrates another embodiment of the present invention. Essentially, the coated string structure of Figure 3 C is then coated again with smaller-diameter multi-filaments 401. A buffer layer coating 402, similar to layer 303, is applied by an extrusion process at temperatures ranging from 19O0C to 27O0C. The thickness of the buffer layer 402 may be from 10 to 100 micrometers. The gaps between the multi-filaments 401 are fully filled by the neat nylon 11 coating. A wear-resistant coating 403 is then coated by an extrusion process at temperatures ranging from 24O0C to 28O0C. Nylon 6/clay or a nylon 6/carbon nanotube nanocomposite may be employed as the wear-resistant coating material 403. The nylon 6 nanocomposite produced by in-situ polymerization may contain 4% nano-clay filler. Other nylon 6 nanocomposites produced by melt-compounded process may also be used for the wear-resistant coating 403.
The nylon 6 nanocomposites may also be modified by rubber modifiers to improve the ductility and toughness. The thickness of the wear-resistant coating 403 may be from 1 to 100 micrometers.

Claims

1. A coating for a string, comprising: a core filament wrapped with a plurality of wrapping filaments of a smaller diameter than the core filament; a buffer layer coating filling in gaps between the wrapping filaments and between the wrapping filaments and the core filament; and an outer coating covering over the buffer layer coating, wrapping filaments and core filament.
2. The coating of claim 1 , 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 nanoparticles.
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: wrapping a core filament having a first diameter with one or more wrapping filaments having a second diameter that is less than the first diameter; extruding a melted nylon into gaps between the one or more wrapping filaments and into gaps between the wrapping filaments and the core filament; extruding a coating on a circumference of the string so that it covers the one or more wrapping filaments and the melted nylon in the gaps.
10. The method of claim 9, wherein the melted nylon comprises nylon 6.
11. The method of claim 9, wherein the melted nylon comprises nylon 11.
12. The method of claim 9, wherein the coating comprises a composite of nylon and clay nanoparticles.
13. The method of claim 9, wherein the coating comprises a composite of nylon and carbon nanotubes.
14. The method of claim 9, wherein the coating comprises a composite of nylon and ceramic particles.
15. The method of claim 9, wherein the coating comprises a composite of nylon and glass particles.
16. The method of claim 9, wherein the coating is between 1 and 100 micrometers thick.
17. The coating of claim 1, further comprising:
another plurality of wrapping filaments wrapped around the outer coating; another buffer layer coating filling in gaps between the another plurality of wrapping filaments; and another outer coating covering over the another buffer layer coating.
18. The coating of claim 3, wherein the coating comprises a composite of nylon and glass particles.
19. The coating of claim 3, wherein the coating comprises a composite of nylon and ceramic particles.
PCT/US2007/084973 2006-11-16 2007-11-16 Buffer layer for strings WO2008061229A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2009537390A JP2010510400A (en) 2006-11-16 2007-11-16 Buffer layer for strings
AT07864530T ATE530230T1 (en) 2006-11-16 2007-11-16 BUFFER LAYER FOR STRINGS
EP07864530A EP2083928B1 (en) 2006-11-16 2007-11-16 Buffer layer for strings

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86619906P 2006-11-16 2006-11-16
US60/866,199 2006-11-16

Publications (2)

Publication Number Publication Date
WO2008061229A1 WO2008061229A1 (en) 2008-05-22
WO2008061229A9 true WO2008061229A9 (en) 2008-08-21

Family

ID=39186839

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2007/084973 WO2008061229A1 (en) 2006-11-16 2007-11-16 Buffer layer for strings

Country Status (7)

Country Link
US (1) US20080124546A1 (en)
EP (1) EP2083928B1 (en)
JP (1) JP2010510400A (en)
CN (1) CN101534909A (en)
AT (1) ATE530230T1 (en)
TW (1) TW200840890A (en)
WO (1) WO2008061229A1 (en)

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EP2083928A1 (en) 2009-08-05
US20080124546A1 (en) 2008-05-29
WO2008061229A1 (en) 2008-05-22
TW200840890A (en) 2008-10-16
CN101534909A (en) 2009-09-16
ATE530230T1 (en) 2011-11-15
JP2010510400A (en) 2010-04-02
EP2083928B1 (en) 2011-10-26

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