DE102011052630A1 - Polymer composition useful for producing string instrument bow for stringing string instrument, preferably violin, comprises polyamide-6, and mixture of ethylene, ethyl acrylate or 2-ethylhexyl acrylate and maleic anhydride terpolymer - Google Patents

Abstract

Polymer composition comprises (in wt.%): polyamide-6 (77.5-82.5); and a mixture (17.5-22.5) comprising ethylene (69), ethyl acrylate or 2-ethylhexyl acrylate (30) and maleic anhydride terpolymer (1). An independent claim is also included for a string instruments bow comprising the above polymer composition, as a bow covering.

Description

The invention relates to a polymer composition consisting of 77.5 to 82.5% by weight of polyamide-6 and 17.5 to 22.5% by weight of a mixture consisting of 69% by weight of ethylene, 30% by weight Ethyl acrylate or 2-ethylhexyl acrylate and 1 wt% maleic anhydride terpolymer. The invention moreover relates to the use for producing a stringed instrument bow for swiping a stringed instrument, the stringed instrument being a violin, and a stringed instrument bow containing the polymer composition as a bowed stringing.

To make bows from stringed instruments (i.e., bowed strings), horsehair (usually from molds) are standardly used as stringing. However, these have the disadvantage that they wear over time by abrasion on the sides of the instrument and also not resistant to moisture, especially against high humidity, and to temperature fluctuations.

The patent DD 36 347 describes a plastic bow hair for stringed musical instruments, wherein a single hair has a non-round cross-section and a permanent twist. The bow hair disclosed in this document consists of polyamide-6.10, polyamide-8 or polyamide-11.

However, the sheet coverings described in this document are not yet optimal in terms of wear resistance, sensitivity to humidity and temperature fluctuations and the sound volume produced when brushing stringed instruments.

Darstellunq the invention, task, solution, advantages

It is the object of the invention to provide a material for the stringing of stringed instrumental bows, which does not have the above-mentioned disadvantages of the prior art.

A solution of the object according to the invention is surprisingly achieved by the polymer composition according to claim 1. Accordingly, the invention relates to a polymer composition consisting of 77.5 to 82.5 wt .-% polyamide-6 and 17.5 to 22.5 wt .-% a mixture consisting of 69% by weight of ethylene, 30% by weight of ethyl acrylate or 2-ethylhexyl acrylate and 1% by weight of maleic anhydride terpolymer. This polymer material is resistant to moisture and temperature fluctuations and is not or only slightly abraded even when used over several years as a covering of string instrument bows. It is also inexpensive and suitable for large-scale production.

Also preferred is a polymer composition, wherein these from 77.5 to 82.5 wt .-% of nylon-6 and 17.5 to 22.5 wt .-% of a mixture consisting of 69 wt .-% of ethylene, 30 wt. % Ethyl acrylate and 1% by weight of maleic anhydride terpolymer. Particular preference is given to a polymer composition which comprises about 80% by weight of polyamide-6 and about 20% by weight of a mixture consisting of 69% by weight of ethylene, 30% by weight of ethyl acrylate and 1% by weight. % Maleic anhydride terpolymer. Such a material is optimal in terms of the above-mentioned advantages for a bowing.

According to the invention, polymer composition is understood to mean any composition which contains at least one type of polymer as an essential constituent. This typically means that the physical and chemical properties of the composition are largely or even exclusively determined by the properties of the polymers contained. Polymer is understood to mean any chemical compound of chain or branched molecules (i.e., macromolecules) composed of the same or at least similar units (i.e., monomers). Examples of polymers are homopolymers, i. H. Monomeric type polymers such as polyethylene, polypropylene, polyvinyl chloride or polyamide-6, copolymers, d. H. Polymers of a plurality of mutually different monomers, such as polyesters, polyurethanes and polyamide-66, and polymer alloys, d. H. Mixtures of different polymers and copolymers.

According to the invention, polyamide (abbreviation PA) is understood as meaning any polymer whose repeating units have a functional amide group as a characteristic feature. This amide functional group may be generally understood as a condensation product of an organic carboxylic acid with an organic amine to form an amide bond. Preferably, the amide bond is hydrolytically cleavable. The polyamide belongs to the group of thermoplastics. According to the invention For example, the polyamide or the polymer can be selected from the group consisting of aliphatic polyamides, partly aromatic polyamides and aromatic polyamides (polyaramides).

According to the invention, aliphatic polyamides are understood as meaning polyamides whose monomers can be derived from aliphatic basic bodies. Examples of aliphatic polyamides are polyamide-6 and polyamide-66.

Polyamide-6 according to the invention is understood to mean an aliphatic polyamide which results from a condensation of ε-caprolactam. Alternative names for polyamide-6 are polycaprolactam or PA-6. Polyamide-6 has the advantage that it is available inexpensively in large quantities.

According to the invention, polyamide-66 is understood to mean an aliphatic polyamide which results from a condensation of hexamethylenediamine and adipic acid. An alternative designation for polyamide-66 is PA-66.

Partially aromatic polyamides are polyamides whose monomers are at least partially derived from aromatic starting materials. Examples of partially aromatic polyamides are polyamides of hexamethylenediamine and terephthalic acid (alternative name PA-6T).

Aromatic polyamides (polyaramides) are polyamides whose monomers are derived from exclusively aromatic starting materials. Examples of aromatic polyamides are para-phenylenediamine and terephthalic acid, such as aramid.

The polymer compositions according to the invention are optimal in view of the physical parameters required for use as a sheet covering, in particular the modulus of elasticity, the yield stress, the elongation at break, the tensile strength, the breaking stress and the elongation at break, as is also apparent from the attached experimental examples.

According to the invention, E modulus (modulus of elasticity, tensile modulus, coefficient of elasticity, E) is understood to mean the material characteristic value from materials engineering, which describes the relationship between mechanical stress σ and strain ε during the deformation of a solid body with linear elastic behavior.

The modulus of elasticity is the proportionality constant in Hooke's Law (see Eq.1) and has the unit of a mechanical stress. E = σ / ε = const. (Equation 1)

Typically, the modulus of elasticity is given in units of megapascals (MPa) or kN / mm ² . The amount of modulus of elasticity is greater, the more resistance a material is able to counteract a mechanical deformation. This means that a high modulus material has high rigidity and a low modulus material has high compliance.

The tensile strength σ _m is understood according to the invention to mean the stress σ which, in the tensile test, is calculated from the maximum tensile force achieved, based on the original cross-section of the sample. The tensile strength has the dimension force per surface and is typically given in megapascals (MPa) or kN / mm ² .

Under elongation at break (elongation at break) A according to the invention the material characteristic understood, indicating the permanent extension ΔL of a sample to be tested after the fraction based on the initial measuring length L ₀ in the tensile test. It results from the following equation (see equation 2). A = ΔL / L₀ × 100% (equation 2)

The permanent extension ΔL is the length after the break reduced by the initial measuring length L ₀ .

According to the invention, breaking stress σ _{B is} understood to mean the drop in force that occurs when the maximum force is exceeded at which the material just barely elastically deforms. The breaking stress is typically given in units of megapascals (MPa) or kN / mm ² .

The yield stress σ _Y in the stress-strain diagram is the first stress value at which an increase in elongation occurs without increasing the stress. At this point, the first derivative of stress versus strain is zero (see equation 3): ∂σ / ∂ε = 0 (equation 3)

Usually, the yield stress is given in the unit Megapascal (MPa) or kN / mm ² . The yield stress may be less than the fracture stress of a sample.

Stretch elongation is understood according to the invention to mean the elongation ε _Y at yield stress σ _Y.

According to the invention, it is advantageous if the polymer composition for use as a bowed covering complies with the parameter limits for the modulus of elasticity, the yield stress, the elongation at break, the tensile strength, the breaking stress and the elongation at break described in the application.

The polymer composition is also preferably a thermoplastic which can be extruded by melt extrusion in the form of a thread or yarn.

According to the invention, dyes of any desired, invariable and / or abrasion-resistant dyeings can additionally be added to the polymer composition in the melt. For example, when a yellow dye is added to the polymer composition, a yarn may be obtained in the color of a horse bristle, which is also commonly used as a bowed garnish. In this way the impression of natural hair tension can be created. Preferably, dyes are used which have high stability to hue changes over time. Examples of such dyes are titanium dioxide, cadmium sulfide, cadmium selenide, carbon. Alternatively, finished yarns prepared from the polymer compositions may be dyed with disperse dyes. Such processes are already known in the production of textiles.

The present invention further relates to a use of the polymer composition according to the invention for producing a stringed instrument bow for swiping a stringed instrument, the stringed instrument being a violin.

For this purpose, it is particularly preferred that the polymer composition is brought into a cadenced structure by melt extrusion or by other suitable means known to those skilled in the art. Preferably, the polymer composition is melt-extruded in the form of a yarn having regular longitudinal cycling, the cycle length in the longitudinal direction d and the amplitude difference A2-A1 being substantially equal over the length of the extrusion (see 1 ). In this case, the extrudate can be produced by melt extrusion, in which case it can be used directly as a yarn, or in addition can have been drawn, resulting in a drawn yarn. For example, the cadenced structure can be achieved by stretching three times (150% of the full elasticity of the yarn is observed).

The yarn preferably has a diameter of 0.10 to 0.14 mm, in particular 0.12 mm, so that it is ideal as a covering of the string instrument bow.

In addition, the invention also relates to a stringed instrument bow comprising the polymer composition according to the invention as sheet covering. Compared to conventional bowing, such as conventional horsehair, the yarn of the invention is temperature resistant and insensitive to variations in humidity. In addition, the sheet covering polymer composition of the present invention provides better sound stability and sound volume when used in conjunction with a stringed instrument, and higher abrasion resistance even over several years, for example over more than 10 years of use by a professional prank player.

Further advantages and embodiments can be found in the following experiments, the figures and the dependent claims.

Examples

Hereinafter, the invention based on embodiments and with reference to the 1 explained in more detail.

The 1 Figure 11 is a sketch of the yarn made with the polymer composition for use as a string for a stringed instrument bow.

The embodiments and the figure are intended only for a general understanding of the invention and in particular are not to be interpreted as limiting the scope of the invention.

Example 1.

• – Polyamid-6 (PA-6 Ultramid^® B3, MFI = 20 (235°C), hergestellt durch die BASF AG);
• – Additiv 1 (Ethylen/Ethylacrylat/Maleinsäureanhydrid-Terpolymer mit einer Zusammensetzung von 69 Gew.-%/30 Gew.-%/1 Gew.-%, MFI = 6 (190°C));
• – Additiv 2 (Ethylen/2-Ethylhexylacrylat/Maleinsäureanhydrid-Terpolymer mit einer Zusammensetzung von 69 Gew.-%/30 Gew.-%/1 Gew.-%, MFI = 5,5 (190 00));
• – Additiv 3 (Ethylen/2-Ethylhexylacrylat/Maleinsäureanhydrid-Terpolymer mit einer Zusammensetzung von 67 Gew.-%/32 Gew.-%/1 Gew.-%, MFI = 6 (190°C));
• – Additiv 4 (Ethylen/2-Ethylhexylacrylat-Copolymer mit einer Zusammensetzung von 70 Gew.-%/30 Gew.-%, MFI = 2 (190°C));
• – Additiv 5 (Ethylen/Butylacrylat-Copolymer mit einer Zusammensetzung von 70 Gew.-%/30 Gew.-%, MFI = 2 (190°C)).

For compositions 1 to 7, the following starting materials are used:

• - polyamide-6 (PA-6 Ultramid ^® B3, MFI = 20 (235 ° C) manufactured by BASF AG);
• Additive 1 (ethylene / ethyl acrylate / maleic anhydride terpolymer having a composition of 69% by weight / 30% by weight / 1% by weight, MFI = 6 (190 ° C));
• Additive 2 (ethylene / 2-ethylhexyl acrylate / maleic anhydride terpolymer having a composition of 69% by weight / 30% by weight / 1% by weight, MFI = 5.5 (190 ° C));
• Additive 3 (ethylene / 2-ethylhexyl acrylate / maleic anhydride terpolymer having a composition of 67% by weight / 32% by weight / 1% by weight, MFI = 6 (190 ° C));
• Additive 4 (ethylene / 2-ethylhexyl acrylate copolymer having a composition of 70% by weight / 30% by weight, MFI = 2 (190 ° C));
• Additive 5 (ethylene / butyl acrylate copolymer having a composition of 70% by weight / 30% by weight, MFI = 2 (190 ° C)).

Preparation of the compositions 1 to 7 according to the invention is carried out by melting the individual components in the twin screw extruder or single-screw BUSS ^® -Cokneter by conventional methods.

The compositions 1 to 3 and 6 to 7 are first mixed in the single-screw BUSS ^® co-kneader, melted and then extruded in a post-treatment extruder. For this purpose, the starting materials, ie polyamide-6 and terpolymers, are introduced as granules in the mixer.

For compositions 4 and 5, a co-rotating 40 mm twin screw "Werner 40" extruder is used. Also for the preparation of these compositions, the starting materials are added as granules in the mixer.

The starting materials used can be taken from Table 1. Table 1: Starting materials of the polymer compositions used. Composition no. starting materials 1 2 3 4 5 6 7 PA 6 100 80 80 80 80 80 80 Additive 1 20 20 Additive 2 20 Additive 3 20 Additive 4 2 2 Additive 5 18 18

Example 2.

Tensile tests were carried out on compositions 1 to 7 (about 21 ° C., about 20% relative humidity).

The measuring instrument used was a tensile tester with mechanical long-distance transducers, T1-FR010TH.A50; Software TestXpert V11.02 manual, company Zwick GmbH & Co. KAG used. The average values of these parameters for the compositions 1 and 2 are shown in Table 2. Table 2: Results of tensile tests on the polymer composition. parameter Composition no. 1 2 Modulus of elasticity [MPa] 3264 6004 Tensile strength [MPa] 83 405 Breaking stress [MPa] 83 405 Elongation at break [%] 37 12 Yield stress [MPa] 81 57 Elongation at break [%] 3.5 1.5

Table 2 shows the mean value of the material properties from three measurements as well as the standard deviation from the measured values. In the yield stress and the elongation at break, the periodically occurring yield stress and yield strength are indicated (lowest measured values).

Compared to composition 1, composition 2 exhibits a higher modulus of elasticity, higher tensile strength, higher breaking stress, lower reeling strain, lower yield stress and lower elongation at break. Compositions 3 to 7 each showed similar results as composition 2.

Example 3.

For moisture absorption, the polymer composition 2 was stored for 36 h under the conditions given in Table 3 and then dried at 120 ° C to constant mass. Table 3: Moisture uptake results on the polymer composition. Storage of the composition at Measured value [%] 23 ° C, 30% rel. humidity 3.2 +/- 0.2 23 ° C, in water 9.4 +/- 0.3

Table 3 shows the mean of two measurements and the standard deviation.

Example 4.

• Messgerät: Seiko Exstar 6000 DSC 6000, Aluminiumpfännchen (d = 5 mm) Temperaturprogramm, Heizrate 10°C/min

• 1. 25 bis 200°C
• 2. 200 bis 25°C
• 3. 25 bis 350°C

Tabelle 4: Ergebnis der DSC Messung an der Polymerzusammensetzung. Messparameter Messwert Schmelztemperatur 216 bis 225°C Glasübergangstemperatur nicht detektiert To determine the thermal properties, a differential scanning calorimetry (DSC) measurement is carried out on the polymer composition 2 (without prior drying).

• Measuring device: Seiko Exstar 6000 DSC 6000, aluminum pans (d = 5 mm) Temperature program, heating rate 10 ° C / min

• 1. 25 to 200 ° C
• 2. 200 to 25 ° C
• 3. 25 to 350 ° C

Table 4: Result of DSC measurement on the polymer composition. measurement parameters reading melting temperature 216 to 225 ° C Glass transition temperature not detected

The second heating curve was evaluated in each case.

Example 5.

According to the method in Example 1 are further polymer compositions 8, 9 and 10 made, which in turn ^® initially in the single-screw BUSS -Cokneter mixed, melted and then extruded in an aftertreatment extruder. Table 5: Starting materials used in the polymer compositions. Composition no. starting material 1 2 8th 9 10 PA-6 100 80 95 90 85 Additive 1 20 5 10 15

The polymer compositions 1, 2, 8, 9 and 10 are melt-extruded in the form of a yarn by conventional methods. The yarns prepared from the compositions have a diameter of 0.12 mm.

The yarns thus produced all have a regular clocking in the longitudinal direction which can be detected under the light microscope, the cycle length in the longitudinal direction d and the amplitude difference A2-A1 remaining essentially unchanged over the length of the extrusion. In analogy to Example 2, the E-moduli of the polymer compositions 1, 2, 8, 9 and 10 are also determined. The cycle lengths in the longitudinal direction d and the E-modules are given in Table 6. Table 6: E-Modules of Polymer Compositions. Composition no. 1 2 8th 9 10 Modulus of elasticity [MPa] 3264 6004 3971 4686 5591 Cycle length in the longitudinal direction d [mm] irregular 1.2 63 43 6

The yarns of polymer compositions 1, 2, 8, 9 and 10 are clamped between the head and the adjustable turnbuckle of a bow customary for use with stringed musical instruments and used by professional stringed instrument players to coat various stringed instruments. The sound stability when brushing over a period of 3 hours is estimated by the professional string instrument players (5 each per musical instrument).

The result is the result of the estimation shown in Table 7. Table 7: Assessment of sound stability. instrument empty strings Frequency of the fundamental tones [Hz] Composition no. 1 2 8th 9 10 violin g - d ¹ - a ¹ - e ² 196 to 659 - ++ - + + viola c - g - d '- a' 130 to 440 - + + + ++ violoncello C - G - d - a 65 to 220 - + + ++ + double bass Contra - C, E, A - D - G 41 to 98 - - ++ + -

In Table 7, a "-" predicts that the sound stability is considered "rather poor", "+" means that the sound stability was rated as "rather good" and "++" means that the sound stability is "very good "Was estimated.

The sound volume was rated "good" to "very good" when using all bows in conjunction with all musical instruments.

All sheet coverings from the polymer compositions 2, 8, 9 and 10 showed no visible surface wear even after a period of 3 to 6 hours under the microscope. The sound stability also did not change when the room temperature varied and the humidity changed.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DD 36347 [0003]

Claims (6)

Polymer composition consisting of 77.5 to 82.5% by weight of polyamide-6 and 17.5 to 22.5% by weight of a mixture consisting of 69% by weight of ethylene, 30% by weight of ethyl acrylate or 2% by weight Ethylhexyl acrylate and 1 wt .-% maleic anhydride terpolymer. A polymer composition according to claim 1, wherein it comprises from 77.5 to 82.5% by weight of polyamide-6 and from 17.5 to 22.5% by weight of a mixture consisting of 69% by weight of ethylene, 30% by weight of polymer. % Ethyl acrylate and 1 wt% maleic anhydride terpolymer. A polymer composition according to claim 1 or 2, wherein it consists of about 80% by weight of polyamide-6 and about 20% by weight of a mixture consisting of 69% by weight of ethylene, 30% by weight of ethyl acrylate and 1% by weight. % Maleic anhydride terpolymer. Use of the polymer composition of any of claims 1 to 3 for making a stringed instrument bow for swipe of a stringed instrument, the stringed instrument being a violin. String bow comprising the polymer composition according to any one of claims 1 to 3 as a bowing. String of bowed instruments according to claim 5, suitable for stroking a stringed instrument, the strings of the stringed instrument being tuned at the fifth pitch, the pitches of the blank strings being g - d1 - a1 - e2.

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