JP6175665B2 - Racket gut - Google Patents
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- JP6175665B2 JP6175665B2 JP2013111565A JP2013111565A JP6175665B2 JP 6175665 B2 JP6175665 B2 JP 6175665B2 JP 2013111565 A JP2013111565 A JP 2013111565A JP 2013111565 A JP2013111565 A JP 2013111565A JP 6175665 B2 JP6175665 B2 JP 6175665B2
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- 239000010954 inorganic particle Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 27
- 229920001225 polyester resin Polymers 0.000 claims description 25
- 229920000728 polyester Polymers 0.000 claims description 14
- 239000011342 resin composition Substances 0.000 claims description 8
- 238000002074 melt spinning Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 210000001035 gastrointestinal tract Anatomy 0.000 description 53
- 239000004645 polyester resin Substances 0.000 description 23
- 238000005520 cutting process Methods 0.000 description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 description 14
- 239000005020 polyethylene terephthalate Substances 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 239000004594 Masterbatch (MB) Substances 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- -1 polyethylene terephthalate Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 208000012886 Vertigo Diseases 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 235000009854 Cucurbita moschata Nutrition 0.000 description 3
- 240000001980 Cucurbita pepo Species 0.000 description 3
- 235000009852 Cucurbita pepo Nutrition 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 235000020354 squash Nutrition 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
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- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、テニス、バドミントン、スカッシュ等に使用するラケット用ガットに関するものである。 The present invention relates to a racket gut used for tennis, badminton, squash and the like.
従来、テニスやバドミントン等のラケット用ガットには、牛や羊の腸等から作られた天然ガットや、ポリアミド繊維やポリエステル繊維等から作られた合成樹脂製ガットが提供されている。 Conventionally, for rackets such as tennis and badminton, natural gut made from the intestines of cattle and sheep, and synthetic resin gut made from polyamide fiber and polyester fiber have been provided.
天然ガットは、反発性、制球性、耐衝撃性等の打球性に優れているが、耐水性が悪いために、使用・保管環境によっては使用寿命が短くなりやすく、しかも非常に高価であるため、近年では耐久性、量産性、経済性等に優れた合成樹脂製ガットが数多く使用されている。 Natural gut is excellent in hitting properties such as resilience, ball control and impact resistance, but due to poor water resistance, its service life is likely to be shortened depending on the usage and storage environment, and it is very expensive. In recent years, many synthetic resin guts having excellent durability, mass productivity, economy and the like have been used.
合成樹脂製ガットとしては、ナイロン製繊維（マルチフィラメント／モノフィラメント）の芯糸の周囲にナイロンモノフィラメントの皮糸を編組／巻付けしたものや、ポリエステル系モノフィラメントを単糸で使用するものが代表的である。 Typical synthetic resin guts are nylon fiber (multifilament / monofilament) core yarn braided / wrapped with nylon monofilament yarn and polyester monofilament used as a single yarn. is there.
これらの中でも、ポリエステル系モノフィラメントを単糸で使用するガットは、ナイロン製ガットに比べて、繰り返しの打球によってガットが切断しにくい性質（以下、切断耐久性という）を持つため、プロ選手やプレー頻度の高い学生等の間で、需要が高まっている。ガットが切断しやすいと、ガット貼りの回数が増加してコストが掛かったり、複数の予備用ラケットを持ち歩かねばならなかったりするばかりか、試合中のガットの切断は動揺が大きくプレーにも影響を与えかねないため、さらなる切断耐久性の向上が求められている。 Of these, guts that use polyester monofilaments as single yarns are more difficult to cut by repeated hitting balls (hereinafter referred to as cutting durability) than nylon guts. Demand is increasing among high-school students. If the gut is easy to cut, the number of times of gut sticking will increase and it will cost more, and it will be necessary to carry multiple spare rackets, and cutting the gut during the game will be upset and will affect play Therefore, there is a demand for further improvement in cutting durability.
これまでに、ＰＥＴガットの耐久性の向上を目的として、ラケット用ガットの表面をフィルムで被覆したもの（例えば、特許文献１参照）、フッ素系樹脂を添加したもの（例えば、特許文献２参照）、シリコーンオイルを添加したもの（例えば、特許文献３参照）などが提案されている。 Up to now, for the purpose of improving the durability of PET gut, the surface of the racket gut is covered with a film (for example, see Patent Document 1), and the fluorine resin is added (for example, see Patent Document 2). In addition, a silicone oil added (for example, see Patent Document 3) has been proposed.
しかしながら、特許文献１〜３に記載されている技術はラケット用ガット表面の摩擦特性を変更することにより間接的に切断耐久性を向上させるものであり、一定の効果は得られるものの、十分満足のいくものではなかった。 However, the techniques described in Patent Documents 1 to 3 indirectly improve the cutting durability by changing the friction characteristics of the racket gut surface, and although a certain effect can be obtained, it is sufficiently satisfactory. It wasn't going.
本発明の目的は、切断耐久性に極めて優れるポリエステル系ラケット用ガットを提供することである。 An object of the present invention is to provide a gut for a polyester racket that is extremely excellent in cutting durability.
上記目的を達成するために本発明によれば、ポリエステル系樹脂と無機粒子とを質量比９７．５：２．５〜９９．９５：０．０５の割合で含む樹脂組成物を溶融紡糸してなるポリエステルモノフィラメントからなり、無機粒子の平均粒子径が０．２〜１．０μｍであるラケット用ガットが提供される。 In order to achieve the above object, according to the present invention, a resin composition containing a polyester resin and inorganic particles in a mass ratio of 97.5: 2.5 to 99.95: 0.05 is melt-spun. There is provided a gut for a racket made of a polyester monofilament having an average particle size of inorganic particles of 0.2 to 1.0 μm.
なお、本発明のラケット用ガットにおいては、
前記無機粒子が金属酸化物粒子であること、
前記ポリエステルモノフィラメントの１．５ｃＮ／ｄｔｅｘ強力時の中間伸度（ＭＥ１．５）が２．０≦ＭＥ１．５［％］＜４．０、かつ２．０ｃＮ／ｄｔｅｘ強力時の中間伸度（ＭＥ２．０）が３．０≦ＭＥ２．０［％］≦８．０であること、および
前記ポリエステルモノフィラメントのＪＩＳ Ｌ１０１３：２０１０に準じて測定した引張破断強度が２．５〜６．０ｃＮ／ｄｔｅｘであること
が好ましい条件であり、これらの条件を適用した場合には、さらに優れた効果を得ることができる。
In the racket gut of the present invention,
The inorganic particles are metal oxide particles;
The intermediate elongation at 1.5 cN / dtex strength of the polyester monofilament is 2.0 ≦ ME 1.5 [%] <4.0 and 2.0 cN / dtex strength. (ME 2.0 ) is 3.0 ≦ ME 2.0 [%] ≦ 8.0, and the tensile strength at break of the polyester monofilament measured in accordance with JIS L1013: 2010 is 2.5 to 6. It is a preferable condition to be 0 cN / dtex, and when these conditions are applied, a further excellent effect can be obtained.
本発明によれば、切断耐久性の高いラケット用ガットを得ることができる。 According to the present invention, a racket gut having high cutting durability can be obtained.
本発明のラケット用ガットは、ポリエステル系樹脂と無機粒子とを特定の割合で含む樹脂組成物を溶融紡糸してなるポリエステルモノフィラメントからなる。 The racket gut of the present invention comprises a polyester monofilament formed by melt spinning a resin composition containing a polyester resin and inorganic particles in a specific ratio.
ここで、本発明におけるポリエステル系樹脂とはポリエチレンテレフタレート（以下ＰＥＴという）、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリプロピレンテレフタレート、ポリメチレンナフタレート、ポリブチレンナフタレート、ポリプロピレンナフタレートまたはそれらの２種類以上を共重合したものまたはブレンドしたもの等が挙げられるが、中でもＰＥＴを主成分として含むものが好ましく使用される。ここで主成分とは、ポリエステル系樹脂中に６０質量％以上含まれることをいい、８０質量％以上含まれることがより好ましい。さらには、ポリエステル系樹脂としてＰＥＴを用いることが特に好ましい。 Here, the polyester resin in the present invention is polyethylene terephthalate (hereinafter referred to as PET), polybutylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polymethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate or two or more of them. Copolymerized or blended ones can be mentioned, and among them, those containing PET as a main component are preferably used. Here, the main component means that 60% by mass or more is contained in the polyester resin, and more preferably 80% by mass or more. Furthermore, it is particularly preferable to use PET as the polyester resin.
ポリエステル系樹脂の固有粘度（以下、ＩＶと記す場合もある）は０．６５〜１．５が好ましく、さらに０．７〜１．２であればより好ましい。上記の範囲を外れると、ラケット用ガットとして用いるのに不十分な程度に破断強力が低下する場合がある。 The intrinsic viscosity (hereinafter sometimes referred to as IV) of the polyester resin is preferably 0.65 to 1.5, more preferably 0.7 to 1.2. If it is out of the above range, the breaking strength may be lowered to an extent insufficient for use as a racket gut.
本発明において用いられる樹脂組成物は、ポリエステル系樹脂と無機粒子とを質量比９７．５：２．５〜９９．９５：０．０５の範囲で含むものであり、９８．５：１．５〜９９．９２：０．０８の範囲であると好ましい。ポリエステル樹脂の質量比が上記範囲を上回る場合には無機粒子を添加することによる耐久性向上効果が得られず、一方、上記範囲を下回る場合にはラケット用ガットとして必要な強度が得られない。 The resin composition used in the present invention contains a polyester resin and inorganic particles in a mass ratio of 97.5: 2.5 to 99.95: 0.05, and 98.5: 1.5. It is preferable in the range of ˜99.92: 0.08. When the mass ratio of the polyester resin exceeds the above range, the effect of improving the durability by adding inorganic particles cannot be obtained. On the other hand, when the mass ratio is below the above range, the strength required for the racket gut cannot be obtained.
本発明に用いる無機粒子としては、酸化チタン、酸化ケイ素、炭酸カルシウム、チッ化ケイ素、クレー、タルク、カオリン、ジルコニウム酸等が例示でき、これらの中でも酸化チタン、酸化ケイ素、酸化アルミニウム、ジルコニウムなどに代表される金属酸化物が好ましい。さらに、ポリエステル系樹脂中への分散性の点から、酸化チタン、酸化ケイ素が特に好ましく用いられる。 Examples of the inorganic particles used in the present invention include titanium oxide, silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin, zirconium acid, and the like. Among these, titanium oxide, silicon oxide, aluminum oxide, zirconium, etc. Representative metal oxides are preferred. Furthermore, titanium oxide and silicon oxide are particularly preferably used from the viewpoint of dispersibility in the polyester resin.
本発明に用いる無機粒子は、その数平均粒子径が０．２〜１．０μｍであり、特に０．３〜０．７μｍが好ましい。無機粒子の平均粒子径が上記範囲を上回ると、無機粒子の異物効果が大きくなり、ラケット用ガットとして必要な引張強度が得られなくなる一方、上記範囲を下回ると無機粒子を添加することによる耐久性向上効果が得られない。 The number average particle diameter of the inorganic particles used in the present invention is 0.2 to 1.0 μm, and 0.3 to 0.7 μm is particularly preferable. When the average particle diameter of the inorganic particles exceeds the above range, the foreign matter effect of the inorganic particles becomes large, and the tensile strength required as a racket gut cannot be obtained. On the other hand, if the average particle size is below the above range, durability by adding inorganic particles Improvement effect cannot be obtained.
また、本発明に用いる無機粒子は粒子径５．０〜１０μｍの粒子が１％以下、１０μｍを超える粒子が０．５％以下であることが好ましい。上記範囲を超えると、ラケット用ガット中で粒子が異物として働き、強度低下や、ラケットへの張設時／使用中の切断の原因となりやすいためである。 Moreover, it is preferable that the inorganic particle used for this invention is 1% or less of particles having a particle diameter of 5.0 to 10 μm and 0.5% or less of particles exceeding 10 μm. When the above range is exceeded, the particles act as a foreign substance in the racket gut, which is likely to cause a reduction in strength and a cutting during stretching / use on the racket.
従来のラケット用ガットにはポリマ中に無機粒子を加えたモノフィラメントを使用することは敬遠されており（例えば、特開１０−２２５５３６号公報 段落［００３９］参照）、積極的に無機粒子を添加したモノフィラメントを用いたラケット用ガットは提案されていなかった。これは、ラケット用ガットに使用する繊維に高強度が求められていたためであり、無機粒子を添加すると、製造中の延伸切れの原因となり高倍率延伸が困難になったり、無機粒子とポリマとの界面に欠陥が生じてしまうと強度低下の原因となったりすることが懸念されていたためと考えられる。 In conventional racket guts, the use of monofilaments in which inorganic particles are added to a polymer has been avoided (see, for example, paragraph [0039] of JP-A-10-225536), and inorganic particles were actively added. A racket gut using monofilament has not been proposed. This is because the fiber used in the racket gut has been required to have high strength, and when inorganic particles are added, it becomes difficult to stretch at a high magnification due to stretching during production, or between inorganic particles and polymer. This is probably because there was a concern that a defect would occur at the interface, causing a decrease in strength.
これに対し、本発明者らは、特定の粒子径の無機粒子を適量添加することによって、高強度を維持したまま切断耐久性をも向上できることを見出し本発明に想到したものである。 On the other hand, the present inventors have found that the cutting durability can be improved while maintaining high strength by adding an appropriate amount of inorganic particles having a specific particle diameter, and the present inventors have conceived the present invention.
本発明において、ポリエステル系樹脂に特定の粒子径の無機粒子を添加することによって、ラケット用ガットの切断耐久性が向上するメカニズムについて明らかではないが、ラケット用ガットの表面に無機粒子が存在することによって、摩擦抵抗が低下することに加え、延伸によってポリエステル系樹脂と無機粒子との界面に繊維軸方向に微細なボイドが発生し、このボイドが打球の衝撃を吸収する役割を果していると推定している。すなわち無機粒子として特定の粒子径のものを適用したことにより、微細なボイドの大きさを制御することができ、ラケット用ガットに必要な強度を維持できたものと考えている。 In the present invention, it is not clear about the mechanism by which the cutting durability of the racket gut is improved by adding inorganic particles having a specific particle size to the polyester resin, but there are inorganic particles on the surface of the racket gut. In addition to lowering frictional resistance, it is estimated that fine voids are generated in the fiber axis direction at the interface between the polyester resin and the inorganic particles due to stretching, and these voids play a role of absorbing the impact of the hit ball. ing. That is, by applying inorganic particles having a specific particle size, the size of fine voids can be controlled, and the strength required for the racket gut can be maintained.
次に、本発明のラケット用ガットは、１．５ｃＮ／ｄｔｅｘ強力時の中間伸度（ＭＥ１．５）が２．０≦ＭＥ１．５［％］＜４．０、かつ２．０ｃＮ／ｄｔｅｘ強力時の中間伸度（ＭＥ２．０）が３．０≦ＭＥ２．０［％］≦８．０であることが好ましい。 Next, the racket gut of the present invention has an intermediate elongation (ME 1.5 ) of 2.0 ≦ ME 1.5 [%] <4.0 and 2.0 cN / d at 1.5 cN / dtex strength. The intermediate elongation (ME 2.0 ) at dtex strength is preferably 3.0 ≦ ME 2.0 [%] ≦ 8.0.
ここで、中間伸度は、ＪＩＳ Ｌ１０１３：２０１０に準じて、試料長２５ｃｍ、引張り速度３０ｃｍ／分の条件でＳ−Ｓ曲線を求め、このＳ−Ｓ曲線から各値を読取る。 Here, as for the intermediate elongation, an SS curve is obtained under the conditions of a sample length of 25 cm and a tensile speed of 30 cm / min in accordance with JIS L1013: 2010, and each value is read from the SS curve.
各中間伸度が上記範囲内であれば、Ｓ−Ｓ曲線の初期直線部分が長く、弾性変形域が広くなるため、このラケット用ガットをラケットに張設した後、さらには球を打った時に塑性ひずみが小さくなることから、結果としてラケット用ガットの緩みが起こりにくく、テンション・ロスが抑制される傾向となるものと考えられる。 If each intermediate elongation is within the above range, the initial straight line portion of the SS curve is long and the elastic deformation range is widened. Therefore, after the racket gut is stretched on the racket and then a ball is hit. Since the plastic strain becomes small, it is considered that as a result, the racket gut is hardly loosened, and the tension loss tends to be suppressed.
本発明のラケット用ガットは、上記中間伸度と同様に測定した引張破断強度が２．５〜６．０ｃＮ／ｄｔｅｘであることが好ましく、さらに３．０〜６．０ｃＮ／ｄｔｅｘがより好ましい。 The racket gut of the present invention preferably has a tensile strength at break of 2.5 to 6.0 cN / dtex, more preferably 3.0 to 6.0 cN / dtex, as measured in the same manner as the intermediate elongation.
引張破断強度が上記範囲未満では、ラケットに張設する際に切断（いわゆる張り切れ）を生じやすい傾向となり、上記範囲を超えるポリエステルモノフィラメントを得ることは現在の技術では困難である。 If the tensile strength at break is less than the above range, cutting (so-called tearing) tends to occur when the racket is stretched, and it is difficult to obtain a polyester monofilament exceeding the above range with the current technology.
本発明のラケット用ガットは必要に応じて、着色がされていてもよく、モノフィラメントの紡糸段階で着色剤を直接添加する方法や、着色剤を予め高濃度でポリエステル系樹脂に混練したマスターバッチを添加する方法等を用いて着色することができる。 The racket gut of the present invention may be colored as required, and a method of directly adding a colorant at the spinning stage of a monofilament or a master batch in which a colorant is previously kneaded with a polyester resin at a high concentration. It can color using the method of adding.
さらに、ラケット用ガットの直径について制限は無く、テニス用、バドミントン用、スカッシュ用等の用途に合わせて適宜変更でき、０．０５〜２．０ｍｍの範囲を例示できる。また、丸、三角、四角、多角形等の如何なる断面形状のものであってもよい。 Furthermore, there is no restriction | limiting about the diameter of the racket gut, It can change suitably according to uses, such as for tennis, badminton, and squash, The range of 0.05-2.0 mm can be illustrated. Further, it may have any cross-sectional shape such as a circle, a triangle, a square, or a polygon.
次に、本発明のラケット用ガットの製造方法について、その一例を説明するが、かかる例に限定されるものではない。 Next, although an example is demonstrated about the manufacturing method of the racket gut of this invention, it is not limited to this example.
本発明のラケット用ガットを構成するポリエステル系モノフィラメントを製造するにあたり、ポリエステル系樹脂と無機粒子とを事前に所望の割合で溶融混練した原料チップを用いることが好ましい。これにより、原料の取り扱いが容易になるとともに、無機粒子の分散状態を安定させることができる。このような原料チップの作成方法は、ポリエステル系樹脂の重合開始段階で無機粒子を添加しても良いし、重合・ペレット化されたポリエステル系樹脂を粉砕して無機粒子と共に２軸エクストルーダー型混練押出機に供給していわゆるマスターバッチを作成しても良い。 In producing the polyester monofilament constituting the racket gut of the present invention, it is preferable to use a raw material chip in which a polyester resin and inorganic particles are previously melt-kneaded at a desired ratio. Thereby, handling of the raw material becomes easy and the dispersed state of the inorganic particles can be stabilized. Such a raw material chip can be prepared by adding inorganic particles at the start of polymerization of the polyester resin, or crushing the polymerized and pelletized polyester resin and mixing with inorganic particles in a biaxial extruder type kneading method. A so-called master batch may be prepared by feeding to an extruder.
原料チップは、必要に応じて真空乾燥され、必要に応じて着色剤等と共に、公知の溶融紡糸機に供給され溶融混練の後、紡糸口金孔から押し出される。 The raw material chips are vacuum-dried as necessary, and are supplied to a known melt spinning machine together with a colorant and the like as necessary. After melt-kneading, the raw material chips are extruded from the spinneret hole.
押し出された溶融物は、引き続き冷却媒体中に導かれて冷却固化される。なお、冷却媒体としては、例えば水やポリエチレングリコール等挙げることができるが、モノフィラメントの表面から容易に除去でき、化学的、物理的に本質的な変化を与えないものであれば特に限定されない。 The extruded melt is subsequently introduced into the cooling medium and cooled and solidified. Examples of the cooling medium include water and polyethylene glycol. However, the cooling medium is not particularly limited as long as it can be easily removed from the surface of the monofilament and does not change chemically or physically.
そして、冷却固化された未延伸糸は、モノフィラメントとして必要な強度を得るために、加熱１段延伸又は多段延伸および熱処理されるが、本発明においては、全延伸倍率が４．２〜５．０倍であり、このうち１段目の延伸配分比を８０〜１００％とした１段又は多段延伸を行った後、０．９５〜１．００倍の熱処理を行うことが好ましい。ここで、全延伸倍率とは延伸過程における延伸倍率の積をいい、熱処理工程での弛緩倍率を含まない。 The unstretched yarn that has been cooled and solidified is subjected to one-stage heating or multi-stage drawing and heat treatment in order to obtain the necessary strength as a monofilament. In the present invention, the total draw ratio is 4.2 to 5.0. It is preferable to perform heat treatment of 0.95 to 1.00 times after performing one-stage or multi-stage drawing in which the first-stage drawing distribution ratio is 80 to 100%. Here, the total draw ratio refers to the product of the draw ratio in the drawing process, and does not include the relaxation ratio in the heat treatment step.
なお、加熱延伸や熱処理の際に使用される熱媒体についても、空気、温水、蒸気、ポリエチレングリコール、グリセリンおよびシリコーンオイル等が挙げられるが、モノフィラメントの表面から容易に除去でき、化学的、物理的に本質的な変化を与えないものであれば特に限定されるものではない。 In addition, as for the heat medium used in the heat drawing and heat treatment, air, hot water, steam, polyethylene glycol, glycerin, silicone oil, and the like can be mentioned, but they can be easily removed from the surface of the monofilament, chemically, physically There is no particular limitation as long as it does not give an essential change to the above.
また、熱媒体の種類によって、延伸温度は９０〜２００℃、熱処理温度は１５０〜２５０℃を適用でき、中でも１段目の延伸に９０〜１００℃の温水浴、２段目の延伸に１１０〜１５０℃の乾熱浴を適用し、その後の熱処理として１５０〜２５０℃の乾熱浴を適用するのが好ましい。 Depending on the type of heat medium, a stretching temperature of 90 to 200 ° C. and a heat treatment temperature of 150 to 250 ° C. can be applied. Among them, a 90 to 100 ° C. hot water bath is used for the first stage stretching, and 110 to 110 for the second stage stretching. It is preferable to apply a 150 ° C. dry heat bath and then apply a 150 to 250 ° C. dry heat bath as a subsequent heat treatment.
このようにして得られたモノフィラメントには、必要に応じて、仕上げ油剤を付与したり、樹脂コーティングをしたり、印字したりすることができる。 The monofilament thus obtained can be provided with a finishing oil, coated with a resin, or printed as necessary.
以下に、本発明のラケット用ガットを実施例に基づいてさらに詳しく説明する。なお、実施例におけるラケット用ガットの評価は以下の方法で行った。特に断らない限り測定ｎ数は１として測定を行った。 Hereinafter, the racket gut of the present invention will be described in more detail based on examples. Note that the racket gut in the examples was evaluated by the following method. Unless otherwise specified, the measurement was performed assuming that the number of n was 1.
（１）無機粒子の粒子径分布
ラケット用ガット１．０ｇを２０ｍＬのオルトクロロフェノールに浸漬し、完全に溶解させた。この溶液をレーザー回折／散乱式粒度分布計測装置（堀場製作所製ＬＡ−７００）のバッチセルへ充填して、数平均粒子径、粒子径分布を測定した。また、粒子径分布から粗大粒子（粒子径：５〜１０μｍ及び１０μｍ超）の存在度［％］を求めた。
(1) Particle size distribution of inorganic particles 1.0 g of racket gut was immersed in 20 mL of orthochlorophenol and completely dissolved. This solution was filled into a batch cell of a laser diffraction / scattering particle size distribution measuring apparatus (LA-700 manufactured by Horiba, Ltd.), and the number average particle size and particle size distribution were measured. Further, the abundance [%] of coarse particles (particle size: 5 to 10 μm and more than 10 μm) was determined from the particle size distribution.
（２）モノフィラメントの引張試験（中間伸度および引張破断強度）
ＪＩＳ Ｌ１０１３：２０１０ ８．５．１に準じて、島津製作所製のオートグラフＡＧ−１０００Ｇにキャプスタン型チャックを取り付けて用い、試料長２５ｃｍ、引張り速度３０ｃｍ／分の条件でｎ＝５の引張試験を行った。この時の荷重−伸び曲線を求め、この荷重−伸び曲線から１．５ｃＮ／ｄｔｅｘ強力時の中間伸度（ＭＥ１．５）および２．０ｃＮ／ｄｔｅｘ強力時の中間伸度（ＭＥ２．０）を読取った。また、引張試験の最大強力を繊度で割ったものを引張破断強度として求めた。
(2) Tensile test of monofilament (intermediate elongation and tensile strength at break)
In accordance with JIS L1013: 2010 8.5.1, a capstan-type chuck is attached to an autograph AG-1000G manufactured by Shimadzu Corporation, and a tensile test with n = 5 under conditions of a sample length of 25 cm and a pulling speed of 30 cm / min. Went. The load-elongation curve at this time was determined, and from this load-elongation curve, the intermediate elongation at 1.5 cN / dtex strength (ME 1.5 ) and the intermediate elongation at 2.0 cN / dtex strength (ME 2.0). ) Was read. Further, the tensile strength at break was obtained by dividing the maximum strength of the tensile test by the fineness.
（３）切断耐久性
ラケット用ガットを５０Ｌｂの張力でフェース面積１１５平方インチのテニスラケットに張設し、このテニスラケットの中心部分に、テニスボールを時速１２０ｋｍ、打ち出し間隔１０回／分、打ち出し距離５０ｃｍ、打ち出し角度４０度で打撃し、ラケット用ガットが切断するまでの打ち出し回数で評価した。
(3) Cutting durability A racket gut is stretched over a tennis racket with a face area of 115 square inches with a tension of 50 Lb, and a tennis ball is placed at the center of this tennis racket at a speed of 120 km / h, a launch interval of 10 times / minute, and a launch distance The ball was hit at 50 cm and a launch angle of 40 degrees, and the number of shots until the racket gut was cut was evaluated.
（４）面圧保持率
ラケット用ガットを５０Ｌｂの張力でフェース面積１１５平方インチのテニスラケットに張設し、張設直後の面圧をゴーセン製テニスコンピューターＧＡ５３によって測定した。そのラケットを標準状態（温度２０℃、湿度６５％）の環境に置き、２４時間後に再度測定し、面圧保持率［％］を求めた。
(4) Surface pressure retention rate The racket gut was stretched to a tennis racket having a face area of 115 square inches with a tension of 50 Lb, and the surface pressure immediately after the tension was measured with a Goensen tennis computer GA53. The racket was placed in an environment of a standard state (temperature 20 ° C., humidity 65%), measured again after 24 hours, and the surface pressure retention [%] was determined.
面圧保持率［％］＝２４時間後の面圧／張設直後の面圧×１００。 Surface pressure retention [%] = surface pressure after 24 hours / surface pressure immediately after tension × 100.
（５）試打評価
ラケット用ガットを５０Ｌｂの張力でテニス用ラケットに張設し、テニス経験が１０年以上のアマチュアプレーヤー１０人に、使用してもらい、比較例１のラケット用ガットを基準として切断耐久性を評価してもらった。
(5) Test hit evaluation A racket gut is stretched on a tennis racket with a tension of 50 Lb, and is used by 10 amateur players with tennis experience of 10 years or more, and the racket gut of Comparative Example 1 is cut as a reference. We had you evaluate durability.
○・・・７人以上が、切断耐久性の向上が認められると評価した、
△・・・５人または６人が、切断耐久性の向上が認められると評価した、
×・・・切断耐久性の向上が認められると評価したのは４人以下であった。
○ ... 7 or more people evaluated that improvement in cutting durability was recognized,
Δ: Five or six people evaluated that an improvement in cutting durability was observed.
X: Four or less evaluated that improvement in cutting durability was observed.
［実施例１］
ＰＥＴ（三井化学製Ｊ１５５，ＩＶ＝０．９７）に、平均粒子径０．３μｍの酸化チタン（ＴｉＯ２）を５．０質量％練りこんだマスターバッチＡを作成した。ＰＥＴ（三井化学製Ｊ１５５）とマスターバッチとをそれぞれ真空乾燥し、ＰＥＴ９９．９質量％、酸化チタン０．１質量％となるように計量、混合し樹脂組成物を得た。
[Example 1]
A master batch A was prepared by kneading 5.0% by mass of titanium oxide (TiO 2 ) having an average particle size of 0.3 μm into PET (J155, manufactured by Mitsui Chemicals, IV = 0.97). PET (Mitsui Chemicals J155) and the master batch were each vacuum-dried, and weighed and mixed so that it might become PET 99.9 mass% and titanium oxide 0.1 mass%, and the resin composition was obtained.
この樹脂組成物をエクストルーダー型紡糸機へ供給し、紡糸温度２９０℃で溶融混練した後、ギヤポンプを経て、紡糸パック内の濾過層を通過して円形断面糸用紡糸ノズルから紡出し、ただちに７５℃の温水浴中で冷却固化させ、未延伸糸を得た。引き続き、得られた未延伸糸を９０℃の温水浴で４．６倍に１段目延伸し、次いで１２０℃の乾熱浴で１．０倍に２段目延伸を行って全延伸倍率４．６倍とし、さらに、２００℃の乾熱浴中、１．０倍で熱処理することにより、直径１．２０ｍｍのポリエステル系樹脂モノフィラメントを製造した。 This resin composition is supplied to an extruder-type spinning machine, melted and kneaded at a spinning temperature of 290 ° C., passed through a filtration layer in a spinning pack through a gear pump, and spun from a spinning nozzle for circular cross-sectional yarn, and immediately 75 By cooling and solidifying in a warm water bath at 0 ° C., an undrawn yarn was obtained. Subsequently, the obtained undrawn yarn was stretched 4.6 times in a hot water bath at 90 ° C. to the first stage, then stretched in the second stage to 1.0 times in a 120 ° C. dry heat bath to obtain a total draw ratio of 4 The polyester resin monofilament having a diameter of 1.20 mm was manufactured by heat treatment at a magnification of 1.0 and a heat treatment of 1.0 times in a 200 ° C. dry heat bath.
このモノフィラメントを、そのまま単糸でラケット用ガットとして用いた。 This monofilament was used as a racket gut with a single yarn as it was.
［実施例２、３］
樹脂組成物中のＰＥＴと酸化チタンの割合を表１に示すとおりに変更し、１段目の延伸倍率をそれぞれ４．４倍、４．８倍とした以外は、実施例１と同様に、直径１．２０ｍｍのポリエステル系樹脂モノフィラメントを製造し、そのまま単糸でラケット用ガットとして用いた。
[Examples 2 and 3]
As in Example 1, except that the ratio of PET and titanium oxide in the resin composition was changed as shown in Table 1, and the first stage draw ratios were 4.4 times and 4.8 times, respectively. A polyester resin monofilament having a diameter of 1.20 mm was produced and used as a gut for a racket with a single yarn as it was.
［実施例４］
マスターバッチとして、ＰＥＴ（三井化学製Ｊ１５５）に平均粒子径０．６μｍの酸化チタンを５．０質量％練りこんだマスターバッチＢを使用した以外は、実施例１と同様に、直径１．２０ｍｍのポリエステル系樹脂モノフィラメントを製造し、そのまま単糸でラケット用ガットとして用いた。
[Example 4]
As in Example 1, the diameter of 1.20 mm was the same as in Example 1 except that Master Batch B in which 5.0% by mass of titanium oxide having an average particle diameter of 0.6 μm was kneaded into PET (J155 manufactured by Mitsui Chemicals) was used as the master batch. A polyester resin monofilament was manufactured and used as a racket gut with a single yarn.
［実施例５］
マスターバッチとしてＰＥＴ（三井化学製Ｊ１５５）に平均粒子径０．５μｍの酸化アルミニウムを５．０質量％練りこんだマスターバッチＣを使用した以外は、実施例１と同様に、直径１．２０ｍｍのポリエステル系樹脂モノフィラメントを製造し、そのまま単糸でラケット用ガットとして用いた。
[Example 5]
As in Example 1, a master batch C having a diameter of 1.20 mm was used except that master batch C in which 5.0 mass% of aluminum oxide having an average particle size of 0.5 μm was kneaded into PET (J155 manufactured by Mitsui Chemicals) as a master batch. A polyester resin monofilament was produced and used as a gut for a racket with a single yarn as it was.
［比較例１］
酸化チタン入りマスターバッチを使用せず、ＰＥＴ（三井化学製Ｊ１５５）のみを原料とした以外は、実施例１と同様に、直径１．２０ｍｍのポリエステル系樹脂モノフィラメントを製造し、そのまま単糸でラケット用ガットとして用いた。
[Comparative Example 1]
A polyester-based resin monofilament with a diameter of 1.20 mm was produced in the same manner as in Example 1 except that a masterbatch containing titanium oxide was not used and only PET (J155, manufactured by Mitsui Chemicals) was used as a raw material, and the racquet was made of a single yarn Used as a gut.
［比較例２］
樹脂組成物中のＰＥＴと酸化チタンの割合を表２に示すとおりに変更した以外は、実施例１と同様に、直径１．２０ｍｍのポリエステル系樹脂モノフィラメントを製造し、そのまま単糸でラケット用ガットとして用いた。
[Comparative Example 2]
A polyester resin monofilament having a diameter of 1.20 mm was produced in the same manner as in Example 1 except that the ratio of PET and titanium oxide in the resin composition was changed as shown in Table 2. Used as.
［比較例３］
マスターバッチとして、ＰＥＴ（三井化学製Ｊ１５５）に平均粒子径３．０μｍの酸化チタンを５．０質量％練りこんだマスターバッチＤを使用した以外は、実施例１と同様に、直径１．２０ｍｍのポリエステル系樹脂モノフィラメントを製造し、そのまま単糸でラケット用ガットとして用いた。
[Comparative Example 3]
The diameter of 1.20 mm was the same as in Example 1 except that Masterbatch D, in which 5.0% by mass of titanium oxide having an average particle size of 3.0 μm was kneaded into PET (J155 manufactured by Mitsui Chemicals), was used as the masterbatch. A polyester resin monofilament was manufactured and used as a racket gut with a single yarn.
［比較例４］
融点１２０℃、平均粒子径２μｍ、共重合ポリエステル固体粒子の濃度を３０質量％に調製した水系懸濁液（エムスケミー・ジャパン製 Ｇｒｉｌｔｅｘ ９Ｅ Ｓｕｓｐｅｎｓｉｏｎ）中に、平均粒子径０．３μｍの酸化チタン（ＴｉＯ２）を共重合ポリエステル固体粒子に対して０．１質量％となるように添加し、分散させた。この混合懸濁液を比較例１で得られたポリエステル系樹脂モノフィラメントに、ディップ法により塗布し、１６０℃の熱風浴内で熱処理することにより、ポリエステル系樹脂モノフィラメントの表面に酸化チタンを含むコーティング層を形成し、そのまま単糸でラケット用ガットとして用いた。なお、コーティング層中の酸化チタン濃度は０．１％、コーティング層の厚みは１５μｍであった。
[Comparative Example 4]
In an aqueous suspension (Griltex 9E Suspension manufactured by Emschemie Japan) having a melting point of 120 ° C., an average particle size of 2 μm, and a concentration of copolymerized polyester solid particles of 30% by mass, titanium oxide (TiO 2) 2 ) was added and dispersed so as to be 0.1% by mass with respect to the copolyester solid particles. The mixed suspension is applied to the polyester resin monofilament obtained in Comparative Example 1 by the dipping method, and is heat-treated in a hot air bath at 160 ° C., whereby the surface of the polyester resin monofilament contains titanium oxide. And used as a racket gut with a single yarn as it was. The titanium oxide concentration in the coating layer was 0.1%, and the thickness of the coating layer was 15 μm.
ラケット用ガットの組成、評価結果を表１、２に示す。 Tables 1 and 2 show the composition and evaluation results of the racket gut.
表１、２から明らかなように、本発明のラケット用ガット（実施例１〜５）は、切断耐久性に極めて優れるものである。 As is clear from Tables 1 and 2, the racket guts (Examples 1 to 5) of the present invention are extremely excellent in cutting durability.
これに対し、無機粒子を含まないラケット用ガット（比較例１）は、切断耐久性が不十分であった。無機粒子を本発明の条件以上に含むラケット用ガット（比較例２）や無機粒子の平均粒子径が本発明の条件を満たさないラケット用ガット（比較例３）は、切断耐久性に劣るばかりか、引張破断強度にも劣り、使用に不適なものであった。また、モノフィラメントの表面に無機粒子を含むコーティング層を形成したラケット用ガット（比較例４）は、わずかな切断耐久性の改善しか見られず、効果が不十分であった。 On the other hand, the racket gut containing no inorganic particles (Comparative Example 1) had insufficient cutting durability. A racket gut that contains inorganic particles in excess of the conditions of the present invention (Comparative Example 2) and a racket gut that does not satisfy the conditions of the present invention (Comparative Example 3) does not have poor cutting durability. Also, the tensile strength at break was inferior and unsuitable for use. Further, the racket gut (Comparative Example 4) in which the coating layer containing inorganic particles was formed on the surface of the monofilament showed only a slight improvement in cutting durability, and the effect was insufficient.
本発明のラケット用ガットは、切断耐久性に極めて優れるため、テニス、バドミントン、スカッシュ等のラケットスポーツ用具として最適に利用することができる。 Since the racket gut of the present invention is extremely excellent in cutting durability, it can be optimally used as a racket sports equipment for tennis, badminton, squash and the like.
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| JP2008266873A (en) * | 2007-03-29 | 2008-11-06 | Toray Ind Inc | Polyester monofilament and woven fabric |
| JP4924495B2 (en) * | 2008-03-14 | 2012-04-25 | 東レ株式会社 | Screen filament monofilament |
| JP2011078581A (en) * | 2009-10-07 | 2011-04-21 | Toray Monofilament Co Ltd | String for racket and method for manufacturing the same |
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