EP0049368A1 - Corde synthétique - Google Patents

Corde synthétique Download PDF

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Publication number
EP0049368A1
EP0049368A1 EP81106902A EP81106902A EP0049368A1 EP 0049368 A1 EP0049368 A1 EP 0049368A1 EP 81106902 A EP81106902 A EP 81106902A EP 81106902 A EP81106902 A EP 81106902A EP 0049368 A1 EP0049368 A1 EP 0049368A1
Authority
EP
European Patent Office
Prior art keywords
strings
monofilament
string
string according
acrylates
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.)
Granted
Application number
EP81106902A
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German (de)
English (en)
Other versions
EP0049368B1 (fr
Inventor
Günther Dr. Tappe
Bertram Gasper
Herbert Laubenberger
Richard Dr. Weiss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels Troisdorf AG
Dynamit Nobel AG
Original Assignee
Huels Troisdorf AG
Dynamit Nobel AG
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 Huels Troisdorf AG, Dynamit Nobel AG filed Critical Huels Troisdorf AG
Priority to AT81106902T priority Critical patent/ATE3948T1/de
Publication of EP0049368A1 publication Critical patent/EP0049368A1/fr
Application granted granted Critical
Publication of EP0049368B1 publication Critical patent/EP0049368B1/fr
Expired legal-status Critical Current

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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
    • 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

Definitions

  • the invention relates to a string made of at least one monofilament plastic.
  • Strings that are at least partially made of plastic are known, see, for example, DE-OS 27 28 339 and DE-OS 17 03 132. They are used for various purposes, in particular as strings for musical instruments, and for stringing rackets, in particular tennis , Squash, badminton rackets, etc., and also as tendons for bows and crossbows, the above list only giving examples.
  • the strings, tendons or the like have certain properties in terms of tensile force and elongation under short-term and repeated loads. After such a load, the strings or the like. quickly and completely return to their initial length. In the end the strings or the like.
  • Gut strings have long been used for musical instruments and for stringing high-quality tennis rackets.
  • the recoverability of these gut strings ie their ability to quickly and completely return to their original length after a short or multiple loading, is excellent.
  • the increase in length or elongation is linear as a function of the tensile force exerted and practically does not change from one load cycle to the next, which is an indication of low flow. All tensile force curves, however, have steps or jumps, which result from the scribing of certain individual fibers or the dissolution or unraveling of turns of the strings provided with a twist. The phenomena described above accordingly shorten the life of gut strings.
  • gut strings For gut strings, the lifespan is clearly proportional to the diameter of the same; on the other hand, however, it is not readily possible to simply increase this diameter, since this leads to various disadvantages, in particular with regard to the elasticity of the string under tension.
  • gut strings are not of constant quality either, because this quality depends on the ones used Intestines (sheep, beef, pig intestine) depends on the storage conditions for the strings and on the moisture conditions prevailing at the time the strings are used. Since the natural gut strings show a high level of moisture absorption, as a result of which dimensional changes occur, ie elongation of the string, the elastic behavior changes very significantly and to the disadvantage of the players. In addition, gut strings are extremely expensive to manufacture.
  • the known strings in which at least one process step for extruding thermoplastic materials takes place, in particular to carry out a monofilament core or an impregnation of a band of multifilaments, can be produced continuously and quickly very economically; on the other hand, the quality of the artificially produced strings is not competitive compared to the gut strings, primarily because of the special properties, in particular the insufficient resilience of the thermoplastic materials used and the insufficient elasticity.
  • the multifilament synthetic strings as tennis racket strings are inferior to the high-quality natural gut strings in terms of their playing properties and at most comparable to the lower qualities of the natural gut strings.
  • the pure plastic monofilaments on the other hand, have the worst playing characteristics, which is primarily due to insufficient elasticity.
  • polyamide 6 and 6.6 and, to a small extent, polyethylene terephthalate are preferably used.
  • strings made of polyamide arises from the fact that with a moisture content of the polyamide of approx. 3%, which arises at atmospheric humidity of 50% relative humidity, the glass transition area of the polyamide 6 and 6.6 is already at approx. 20 ° C. lies. Therefore, these strings have a high damping, they reset less due to the internal friction. In addition, these polyamide strings undergo major changes in elasticity with changes in temperature.
  • the elasticity of the polyvinylidene fluoride monofilament is equal to that of a natural gut string when the string is pretensioned in the range between 170 to 320 N.
  • This elasticity of the polyvinylidene fluoride monofilament can be set for the thicknesses in question, so that the same playing properties can be achieved regardless of the thickness.
  • Another essential property is that the relaxation of the polyvinylidene fluoride monofilament is equal to or less than that of natural gut strings, with a comparatively applied pretensioning force of 200 N.
  • strings formed from polyvinylidene fluoride monofilaments are characterized by high elasticity with little relaxation.
  • the elasticity for the string made of polyvinylidene fluoride monofilaments with a pretensioning force of 200 N is preferably between 2.0 and 5.0 ⁇ 10 -4 N -1 approximately 3.3 x 10 -4 N -1 can be achieved.
  • the ratio between the high elasticity of the monofilaments and the low relaxation thereof required for a string, in particular also for covering ball game rackets, is achieved in the case of polyvinylidene fluoride monofilaments in that the polyvinylidene fluoride monofilament in a ratio between 1: 3 to 1:10, preferably 1: 4 to 1: 5 is axially stretched.
  • the stretching temperature, the stretching ratio and the residence time the elasticity can be greatly changed above an elongation of 7 to 8%. So you can produce strings with the desired elasticity during hot stretching. If one stretches these strings for a long time, however, one finds that on the one hand the tension drops, but on the other hand also the elasticity.
  • pre-stretching is carried out at higher temperatures, so that the strings have an elasticity which is about 40 to 70% higher than desired and the elasticity on the strands by at least one cold post-stretching brings the desired value.
  • the length of the linear force expansion range can be determined by the level of the applied voltage.
  • a preferred area of application for monofilaments made of polyvinylidene fluoride is covering of ball game rackets, in particular tennis rackets.
  • the advantage of high weather resistance and moisture independence is fully exploited here.
  • monofilament strings made of polyvinylidene fluoride have high-quality natural gut strings that have approximate playing properties with a corresponding elasticity and relaxation behavior.
  • monofilaments made of polyvinylidene fluoride in the temperature range from -20 ° C to 30 ° C have a low attenuation measured at a measuring frequency of approximately 1 Hz.
  • This object is achieved in a string made of at least one monofilament made of plastic in that plastics consisting of 99 to 86 wt .-% polyvinylidene fluoride and 1 to 14 wt .-% acrylates are used.
  • plastics consisting of 99 to 86 wt .-% polyvinylidene fluoride and 1 to 14 wt .-% acrylates are used.
  • polymethyl methacrylate, polymethyl acrylate, polyethyl acrylate or polypropyl acrylate or mixtures of these acrylates are preferably provided as acrylates.
  • the acrylate is a copolymer of vinylidene fluoride monomer with at least one acrylate monomer, preferably selected from the group of alkyl acrylates or alkyl methacrylates, the alkyl groups preferably being lower alkyl groups having 1 to 4 carbon atoms, where the acrylate content is calculated from the acrylate content of the copolymers.
  • copolymers of vinylidene fluoride monomers with at least one acrylate monomer are copolymers which contain 10 to 30% by weight of the stated acrylate monomer.
  • the copolymer with such a composition may be of a type which can be obtained by suspension polymerization, emulsion polymerization, graft polymerization or by any other suitable polymerization process is prepared.
  • a preferred blend for producing the monofilaments contains up to 8% by weight of acrylates and up to 25% by weight of polyvinylidene fluoride-acrylate polymers.
  • a weight ratio is preferred in which polyvinylidene fluoride makes up 90 to 95% by weight and contains 10 to 5% by weight of acrylate.
  • the invention has a particularly advantageous effect when the string is formed from at least one monofilament, it has proven itself fully in the economically most interesting monofilament string and combines the advantages of natural gut strings with the previously known advantages of plastic strings.
  • the string can also consist of several monofilaments made of polyvinylidene fluoride mixed with acrylates, which are twisted, intertwined, twisted or similarly connected to one another. This also includes completely assembled strings, which in addition to plastic monofilaments also have other components.
  • the string according to the invention is essentially characterized by its elasticity behavior. This is essentially dependent on the properties of the polyvinylidene fluoride in the monofilament.
  • polyvinylidene fluoride As with other macromolecular substances, some of the properties of polyvinylidene fluoride, especially the degree of crystallinity, depend on the thermal history of the material. While rapid cooling after processing results in a largely amorphous material with good flexibility, slow cooling or tempering at approx. 135 ° C lead to highly crystalline parts that have a higher tensile and bending modulus at higher densities and have improved creep resistance.
  • the method for producing a string according to the invention provides that a strand of polyvinylidene fluoride and acrylates extrudes at a melting temperature of the polyvinylidene fluoride between 250 and 350 ° C, preferably between 260 ° C and 280 ° C and to a temperature between 60 and 150 ° C, preferably 130 to 145 ° C and axially stretched at this temperature, then the monofilament thus obtained is cooled to room temperature (about 20 ° C) and then cold stretched.
  • the inventive combination of the process steps of warm stretching with a cold but relatively low post-stretching of the monofilaments achieves the excellent properties required for a string, namely an elastic behavior approximating the natural gut strings over long periods of time and a reduction in de
  • the cold stretching of the monofilament is preferably carried out to such an extent that the monofilament is elongated by 1 to 3%. This amount of cold stretching is sufficient to achieve the desired relaxation reduction. With cold post-stretching, the knot tensile strength and the elongation at break are practically hardly changed, while the elasticity increases somewhat. The achievable elasticity, knot tensile strength and elongation at break of the monofilament also depend on the temperature at which the hot stretching is carried out.
  • the temperature for the thermal stretching and also the stretching ratio which is preferably chosen between 1: 3 to 1:10, preferably 1: 4 to 1: 5, also depend on the required final thickness or diameter of the monofilament string.
  • the thickness of the strand to be stretched at a stretching ratio of 1: 5 must be between 2.7 to 3.4 mm and with a stretching ratio e.g. from 1: 8 between 3.4 and 4.2 mm.
  • the desired cold drawing is achieved, for example, according to the invention in that the monofilament is wound up with a uniform tension force of at least 200 N, preferably 230 to 280 N and remains wound under tension for at least five minutes, preferably up to one hour or possibly more, until after its relaxation is used for its intended purpose.
  • the string according to the invention As covering for ball game rackets, in particular tennis rackets, monofilaments are used with an elasticity of 2.7 to 3.6 x 10 -4 N -1 with a pretensioning force of 200 N, an elongation at break of 16 to 30 $ , a tensile strength between 300 to 500 N / mm 2 with a diameter of 1.2 to 1.5 mm.
  • the invention is explained in more detail below using an exemplary embodiment as a tennis racket string.
  • the properties which are important for the practical use of the string of polyvinylidene fluoride and acrylates according to the invention for covering tennis rackets are briefly described below.
  • tennis racket strings are stretched with a pretensioning force between 150 N and 300 N, preferably about 200 N, depending on the type of player. The following requirements result:
  • This force is added to the pretensioning force of a string from 160 to 300 N, with which a string is pretensioned during tensioning.
  • the tennis racket strings are tensioned with 160 to 300 N, mainly with 200 N when stringing, depending on the player and type of game. With increasing tension, the deformation path is reduced and the contact time between the ball and the covering is reduced, so that in general the ball guidance is poorer and a high speed of the tennis racket is necessary for the acceleration of the ball.
  • the tension of the strings should change as little as possible over time, i.e. the tension relaxation should be low. Furthermore, the clamping force should change as little as possible through the action of temperature and moisture.
  • the strings must have sufficient knot tensile strength, but by repeatedly deflecting the string when stringing, the force acting on the knot can be reduced.
  • a deformation path that is too large results in a ball acceleration that is too small and a deformation path that is too small results in poor ball guidance.
  • the natural gut strings have an elasticity behavior that ensures both good ball guidance and acceleration.
  • the string should quickly return to its original state after a short load. This means that the internal friction of the material used should be small. However, if the internal friction is too low, undesirable reverberation occurs, for example, with ball game racket strings. The damping is a measure of the internal friction.
  • the wear behavior is caused on the one hand by rubbing two strings at the crossing points of a covering, but on the other hand by dust and dirt.
  • a monofilament string made from a polyvinylidene fluoride modified according to the invention which is to be used as a tennis racket string, are described below and their properties investigated and compared with a multifilament high-quality plastic string made of polyamide of the type Rucanor GmbH, Cologne and a natural gut string of the Victor Imperial type from Hoffmann von Gramm KG, Unteraching and a monofilament string made of pure polyvinylidene fluoride.
  • the monofilament according to the invention consists of 79% by weight polyvinylidene fluoride and 3.5% by weight PMMA and 17.5% by weight .-% vinylidene fluoride ethyl acrylate graft polymer with 20 wt .-% ethyl acrylate.
  • Fig. 1 shows the compilation of the comparison of the mechanical properties in tabular form for the monofilament strings mentioned here.
  • Fig.2 shows the force-strain diagram.
  • Fig.3 represents the elasticity
  • Fig. 4 shows the dependence of the thrust modulus and damping on the temperature as a function of the pre-tensioning force.
  • Fig. 1 and Fig. 3 specified elasticity a is defined as the ratio of the change in elongation ⁇ ⁇ with a change in force ⁇ ⁇ for a reversible deformation.
  • the tensile strength was determined according to DIN 53 455.
  • a knot was made in the thread to be tested and the tensile strength of the thread was then measured in a tensile test in accordance with DIN 53 455.
  • the property values are shown in Figure 1.
  • the abrasion resistance was determined using a special testing device. Two strings are clamped crosswise, each with a pretensioning force of 200 N. The tension clamps for one string are fixed, the tension clamps for the other string are movable. The movable string is pulled from above under the fixed string and continued upwards. With a speed of 100 cycles per minute, this string is moved back and forth. The crossing point of both strings can move about 10 mm back and forth during the test.
  • the abrasion resistance determined with this device is most favorable for tennis racket strings made of polyamide.
  • the natural gut strings differ greatly in abrasion resistance. There are strings that break after 600 cycles, others, however, only after 2000 cycles.
  • PVDF monofilaments have an abrasion resistance that is slightly worse than that of natural gut strings.
  • PVDF monofils or modified PVDF monofilaments according to the invention have their surface, for example with Teflon (R) abrasion resistance, which is much better than that of natural gut strings, see Fig. 1.
  • the force expansion diagram acc. Fig. 2 shows the characteristic differences between natural gut and synthetic strings. What is particularly noticeable here is that the polyamide strings show a high increase in force at higher elongations.
  • the elasticity can be calculated from the force expansion diagrams according to Fig. 2. of the formula given above, and it is shown as a function of preload in Fig. 3 for the different strings. From this it can be seen that monofilaments based on polyvinylidene fluoride with prestressing. Forces from about 150 N to 350 N have about the same elasticity as high-quality natural gut strings. In contrast, the polyamide plastic strings have a much lower elasticity with a pre-tensioning force of 200 N.
  • Fig. 4 are the temperature curves of the shear modulus and the damping, measured in the torsional vibration test acc. Reproduced DIN 53 445.
  • the strings made of natural gut and based on polyvinylidene fluoride change the shear modulus only slightly in the temperature range up to +20 0 0.
  • plastic strings based on polyamide change very strongly in this temperature range, which is due to the fact that the glass transition temperature of the polyamide is due to the relative moisture content is reduced, the moisture saturation at 23 ° C and 50% RH means a glass transition temperature of 20 ° C.
  • the comparison of the damping curves of natural gut, polyamide, pure PVFD monofilament and, according to the invention, modified PVDF monofilament according to Fig. 4 shows that the highest damping in the temperature range in question at 23 ° C and 50% relative humidity has the saturated polyamide string.
  • a completely dry polyamide string on the other hand, has very little damping.
  • the natural gut string saturated with moisture at 23 ° C and 50% relative humidity has a significantly lower damping.
  • the pure PVDF string has the lowest damping.
  • Such low damping means that such strings resonate longer, which causes a longer vibration of a ball game racket.
  • the acrylate-modified PVDF string according to the invention shows, in the temperature range in question, a desired damping behavior approximating to the natural gut string.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Acoustics & Sound (AREA)
  • Multimedia (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Braiding, Manufacturing Of Bobbin-Net Or Lace, And Manufacturing Of Nets By Knotting (AREA)
  • Decoration Of Textiles (AREA)
EP81106902A 1980-10-03 1981-09-03 Corde synthétique Expired EP0049368B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81106902T ATE3948T1 (de) 1980-10-03 1981-09-03 Saite aus kunststoff.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3037457A DE3037457C2 (de) 1980-10-03 1980-10-03 Saite aus Kunststoff
DE3037457 1980-10-03

Publications (2)

Publication Number Publication Date
EP0049368A1 true EP0049368A1 (fr) 1982-04-14
EP0049368B1 EP0049368B1 (fr) 1983-06-29

Family

ID=6113564

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81106902A Expired EP0049368B1 (fr) 1980-10-03 1981-09-03 Corde synthétique

Country Status (5)

Country Link
EP (1) EP0049368B1 (fr)
JP (1) JPS5789611A (fr)
AT (1) ATE3948T1 (fr)
DE (2) DE3037457C2 (fr)
SU (1) SU1082312A3 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997040228A1 (fr) * 1996-04-22 1997-10-30 Luethy Helmut Agent de revetement pour raquette a tension du cordage
GB2303730B (en) * 1995-07-18 2000-01-26 Zyex Limited Musical instrument strings
EP1081270A1 (fr) * 1999-08-24 2001-03-07 E.I. Du Pont De Nemours And Company Modification de cordes pour équipement à cordes et instruments de musique à l'aide d'un polymère fluoré

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60209009A (ja) * 1984-03-30 1985-10-21 Toray Ind Inc 高結節強度ポリフツ化ビニリデンモノフイラメントの製造法
JPS60209008A (ja) * 1984-03-30 1985-10-21 Toray Ind Inc 高結節強度ポリフツ化ビニリデンモノフイラメントの製造方法
JPS60215810A (ja) * 1984-04-11 1985-10-29 Unitika Ltd ポリ弗化ビニリデン系モノフイラメントとその製造法
JPS616307A (ja) * 1984-06-18 1986-01-13 Unitika Ltd ポリ弗化ビニリデン系モノフイラメント
DE3709636A1 (de) * 1986-03-24 1987-11-12 Kureha Chemical Ind Co Ltd Saite fuer ein musikinstrument
DE102007030159B4 (de) 2007-06-27 2015-08-06 Perlon Nextrusion Monofil GmbH Mechanisch strukturierte PET-Monofilamente, insbesondere daraus bestehende Saiten für Ballspielschläger
DE102007062238A1 (de) 2007-12-21 2009-06-25 Teijin Monofilament Germany Gmbh Monofilamente mit strukturiertem Querschnitt auf der Basis einer Mischung aus Polyester und Polyolefinen

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2380119A1 (fr) * 1977-02-10 1978-09-08 Fischer Gmbh Procede de fabrication de cordes de matiere plastique pour raquettes et en particulier pour raquettes de tennis

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2380119A1 (fr) * 1977-02-10 1978-09-08 Fischer Gmbh Procede de fabrication de cordes de matiere plastique pour raquettes et en particulier pour raquettes de tennis

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2303730B (en) * 1995-07-18 2000-01-26 Zyex Limited Musical instrument strings
WO1997040228A1 (fr) * 1996-04-22 1997-10-30 Luethy Helmut Agent de revetement pour raquette a tension du cordage
EP1081270A1 (fr) * 1999-08-24 2001-03-07 E.I. Du Pont De Nemours And Company Modification de cordes pour équipement à cordes et instruments de musique à l'aide d'un polymère fluoré

Also Published As

Publication number Publication date
EP0049368B1 (fr) 1983-06-29
DE3160535D1 (en) 1983-08-04
SU1082312A3 (ru) 1984-03-23
ATE3948T1 (de) 1983-07-15
DE3037457C2 (de) 1982-08-05
JPS5789611A (en) 1982-06-04
DE3037457A1 (de) 1982-04-15

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