JP2019058647A - 熱可塑性ポリウレタンカバーを具備するゴルフボールにポリウレタンコーティングを塗布する方法 - Google Patents
熱可塑性ポリウレタンカバーを具備するゴルフボールにポリウレタンコーティングを塗布する方法 Download PDFInfo
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- JP2019058647A JP2019058647A JP2018132831A JP2018132831A JP2019058647A JP 2019058647 A JP2019058647 A JP 2019058647A JP 2018132831 A JP2018132831 A JP 2018132831A JP 2018132831 A JP2018132831 A JP 2018132831A JP 2019058647 A JP2019058647 A JP 2019058647A
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- Prior art keywords
- golf ball
- diisocyanate
- polyurethane
- core
- outer cover
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Classifications
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Abstract
Description
ゴルフボールは、単層または多層のコアを含んで良い。 好ましい一実施例では、コア層の少なくとも1つは、ポリブタジエンゴム材料を含むゴム組成物から形成される。より具体的には、1つのバージョンにおいて、ボールは、ポリブタジエンゴム組成物で形成された単一の内側コアを含む。第2のバージョンでは、ボールは、内側コア(センタ)とその周囲の外側コア層とを含むデュアルコアを含む。
この発明のゴルフボールは、熱可塑性ポリウレタン組成物からなる外側カバー層をさらに含む。一般に、ポリウレタンは、イソシアネート基(−N=C=O)をヒドロキシル基(OH)と反応させることによって形成されるウレタン結合を含む。ポリウレタンは、触媒および他の添加剤の存在下で多官能性イソシアネート(NCO−R−NCO)と末端ヒドロキシル基(OHーーーOH)を有する長鎖ポリオールとの反応により製造される。ポリウレタンプレポリマーの鎖長は、それを短鎖ジオール(OH−R’−OH)と反応させることによって伸長される。得られるポリウレタンは、共有結合により共に結合された「硬質」および「軟質」セグメントのためにエラストマー特性を有する。この相分離は、主として非極性の低融点軟質セグメントが極性の高い融点の硬質セグメントと相溶性がないために生じる。ジイソシアネートと低分子量鎖延長ジオールとの反応によって形成される硬質セグメントは、比較的堅く不動である。ジイソシアネートと長鎖ジオールとの反応によって形成される軟質セグメントは、比較的柔軟で可動性がある。硬質セグメントは軟質セグメントに共有結合しているので、ポリマー鎖の塑性流動を阻害し、エラストマー弾性を作り出す。
好ましい一実施例では、中間層が、単一層または多層のコアと周囲のカバー層との間に配置される。これらの中間層は、ケーシング層または内側カバー層と呼ぶこともできる。中間層は、熱可塑性材料および熱硬化性材料を含む当技術分野で公知の任意の材料から形成することができるが、好ましくは、少なくとも部分的に中和された酸基を含むエチレン酸コポリマーを含むアイオノマー組成物から形成される。中間層を形成するのに用いることができる適切なエチレン酸コポリマーは、一般に、エチレンのコポリマー;C3〜C8エチレン性不飽和モノまたはジカルボン酸;および任意の軟化性モノマーを含む。これらのエチレン酸コポリマーアイオノマーは、また、上述のように内側コア層および外側コア層を形成するために使用することができる。
この発明のゴルフボールのためのソリッドコアは、例えば圧縮または射出成形のような任意の適切な従来技術を用いて製造することができる。典型的には、コアは、未硬化または軽く硬化したゴムのスラグ材料を球状構造にする。カバー層を形成する前に、コア構造体を表面処理して、その外面と隣接する層との間の接着性を高めて良い。そのような表面処理は、コアの外面を機械的または化学的に研磨することを含んで良い。例えば、コアは、コロナ放電、プラズマ処理、シラン浸漬、または当業者に公知の他の処理方法に供されて良い。カバー層は、以下にさらに記載されるような任意の適切な方法を使用して、コアまたはボールサブアセンブリ(コア構造およびコアの周りに配置される任意の中間層)上に形成される。カバー層を形成する前に、ボールサブアセンブリを表面処理して、上述した技術を用いて、その外面と上にあるカバー材料との間の接着性を高めて良い。
一般に、ポリウレタンコーティング材料は、二液型コーティングシステムであって良い。好ましいコーティング系は、(1)活性水素原子を含有するポリオールまたは他の化合物を有する第1の部分、および(2)少なくとも2つの−N=C=O基を有するポリイソシアネート(またはポリイソシアヌレート)を有する第2の部分を含む。
いくつかの実施例において、架橋は、カバー層およびコーティング層中のイソシアネート官能基の相対的な割合の結果として起こって良いる。一般に知られているように、ポリウレタン(熱可塑性であろうと熱硬化性であろうと)は、ポリイソシアネート上のイソシアネート官能基とポリオール上のヒドロキシル官能基との間の反応によって重合される。これらの官能基のそれぞれの化学量論的な量の相対量は、ポリウレタン系の「イソシアネートインデックス」として表される。すなわち、イソシアネートインデックスは、ポリウレタン系中に存在するイソシアネート基の数とヒドロキシル基の数との比で表すことができる。あるいは、言い換えれば、イソシアネートインデックスは、ポリウレタン系中に存在するイソシアネート基の実際の数の、ポリウレタン系中に存在するすべてのヒドロキシル基と完全に反応するのに必要なイソシアネート官能基の仮想的な数に対する非として表して良い。
この発明のゴルフボールは、以下にさらに検討するように、様々な有利な機械的特性および演奏性能特性をボールに提供する。一般に、異なるボール層の硬度、直径および厚さは、所望のボール構造に応じて変化して良い。ボールが中間層または内側カバー層を含む場合、硬度(材料)は約50ショアD以上、より好ましくは約55ショアD以上、最も好ましくは約60ショアD以上である。一実施例では、内側カバーのショアD硬度は約62〜約90ショアDである.1つの例では、内側カバーの硬度は約68ショアD以上である。さらに、内側カバー層の厚さは、好ましくは約0.015インチ〜約0.100インチ、より好ましくは約0.020インチ〜約0.080インチ、最も好ましくは約0.030インチ〜約0.050インチである。
硬度
コアの中心硬度は以下の手順に従って得られる。コアは、コアの直径より近似的に若干小さな内部直径の半球ホルダーに静かに押し込まれる、この際、コアは半球ホルダー中に配置され、同時にコアの幾何中心面が露出されるようにする。コアは摩擦でホルダー内に固着され、切断および削り取りステップにおいて移動しないようにし、それでいて、摩擦は、コアの自然な形状が乱されないよう過剰なものでない。コアは、コアの分離線がホルダーの頂部とおおよそ平行になるように取り付けられる。コアの直径は、取り付けに先立って、この方位と80度の角度で測定される。さらに、ホルダーの底からコアの頂部までの測定もなされ、これは将来の計算の基準点を実現する。また、ホルダーの底からコアの頂部までの距離を測定して将来の較正のための基準点を得る。コアの露出された幾何中心の若干上で、コアがこのステップ中にホルダー内で動かないようにしながら、帯ノコまたは他の適切な切断ツールを用いて、大まかに切断する。ホルダー内に依然として保持されているコアの残りの部分が表面研磨機のベース板に固定される。露出されている「粗い」コア表面が平滑で平坦な表面に研磨され、コアの幾何中心が現れるようにし、この幾何中心はホルダーの底からコアの露出表面までの高さを測定して検証できる。これによりコアのオリジナルの高さのちょうど半分が、0.004インチの範囲内で除去されたことを確実にする。コアをホルダー内に保持して、コアの中心を芯出し定規で見いだし、注意して印付けし、この中心印で硬度をASTM−D2240に従って測定する。コアの中心から任意の距離での硬度測定を、中心マークから径方向外側に伸びる線を引き、中心から典型的には2mmの増分の距離位置で硬度を測定することにより行う。中心からの具体的な距離における硬度は、180°または90°それぞれ離れる、少なくとも2つ、好ましくは4つ半径の線分に知って測定すべきであり、その後平均がとられる。幾何中心を通る面の上ですべての硬度測定が実行されても、コアは依然としてホルダーの中にあり、その配位が乱されないようにし、測定面がホルダーの底に常に平行になるようにし、また、それゆえに、デュロメータの足に正確に整合するようにする。
Jeff Dalton’s Compression by Any Other Name、Science and Golf IV、Proceeding of World Science Congress of Golf(Eric Thain ed.,Routledge、2002)(「J.Dalton」)に開示されるように、いくつかの異なる手法が圧縮を測定するのに用いられ、その中に、Atti圧縮、Riehle圧縮、種々の固定荷重およびオフセットでの荷重/偏向測定、種々の固定荷重およびオフセットでの荷重/偏向の測定、および実効弾性係数が含まれる。この発明の目的に関しては、「圧縮」はソフトセンタ偏向指数(Soft Center Deflection Index、「SCDI」)を指す。SCDIは、コアの直径の10%を偏向させるのに必要なポンドを決定することを可能にする動的圧縮機械(Dynamic Compression Machine、「DCM」)に対するプログラム変更である。DCMは、コアまたはボールに荷重を印加して測定荷重においてコアまたはボールが変更したインチ数を測定する装置である。Atti圧縮を表示する数値をもたらすAtti圧縮スケールに合致する、未処理の荷重/変更の曲線が生成される。DCMは、これを荷重セルにより実行し、この荷重セルは静止状態のコアに向けて固定速度(典型的には1.0ft/s)で空気圧でトリガーされる油圧シリンダの底部に取り付けられる。シリンダにはLVDTが取り付けられ、これは、シリンダが試験時間枠の間に進行した距離を測定する。ソフトウェアベースの対数アルゴリズムによって、確実に、試験の初期段階では、少なくとも荷重が連続して5だけ増分するのが検出されるまで、測定が行われないようにする。SCDIはこの設定のわずかなバリエーションである。ハードウェアは同じであるけれども、ソフトウェアおよび出力が変更されている。SCDIでは、大きさは、コアの屈曲させるのに必要な力のポンド数×インチ数である。コアの撓み量は、コア直径の10%である。DCMがトリガされ、シリンダが直径の10%だけコアを変形させ、DCMは必要な力のポンドを(取り付けられたロードセルから測定して)戻し、その量でコアを偏向させる。表示される値は、1ポンド単位の単一の数である。
CORは既知の手順で決定され、ここで、ゴルフボールまたはゴルフボール部分組立体(例えば、ゴルフボールコア)を空気砲から2つの所定の速度で打ち出し、125ft/sの速度でのCORを計算することにより決定される。複数の弾道光スクリーンがボール速度を測定するために固定距離で空気砲およびスチール板の間に配置される。ボールがスチール板へ移動するときに、各光スクリーンが活性化され、各光スクリーンにおける時間を測定する。これにより、ボールの入射速度に反比例した入射移行時間が得られる。ボールはスチール板と衝突して複数の光スクリーンを通り抜けてリバウンドし、これが光スクリーン間を移行するのに要する時間間隔を測定する。これにより、ボールの飛び出し速度に反比例した飛び出し移行時間が得られる。CORは飛び出し移行時間間隔の入射移行時間間隔に対する比、COR=Vout/Vin=Tin/Toutとして計算される。
12 ディンプル
16 コア
18 外側カバー層
以下、ここで説明した技術的特徴を列挙する。
[技術的特徴1]
コーティングされたゴルフボールを形成する方法において、
熱可塑性ポリウレタン組成物から形成される少なくとも1つのコア層および外側カバー層を含むゴルフボールを提供するステップと、
未反応イソシアネート基を含み、少なくとも約115のイソシアネートインデックスを有する第1のポリウレタンコーティングを上記外側カバー層に塗布するステップと、
上記ゴルフボールを熱で処理するステップと、
第2のポリウレタンコーティングを上記ゴルフボールの上記外側カバーに塗布してコーティングされたゴルフボールを形成するステップとを有することを特徴とする、上記方法。
[技術的特徴2]
上記第1および第2のポリウレタンコーティングの少なくとも1つが触媒をさらに有する、技術的特徴1記載の方法。
[技術的特徴3]
上記熱可塑性ポリウレタン組成物が触媒をさらに有する、技術的特徴1記載の方法。
[技術的特徴4]
上記外側カバー層は、約0.010〜約0.050インチの範囲の厚さを有する、技術的特徴1記載の方法。
[技術的特徴5]
上記外側カバー層が、約20〜約59ショアDの範囲の硬度を有する、技術的特徴1記載の方法。
[技術的特徴6]
上記ゴルフボールが、内側コアおよび外側コア層を有する、技術的特徴1記載の方法。
[技術的特徴7]
上記ゴルフボールは、内側カバー層をさらに有する、技術的特徴1記載の方法。
[技術的特徴8]
上記第1および第2のポリウレタンコーティングがスプレイコーティングによって塗布される、技術的特徴1記載の方法。
[技術的特徴9]
上記ゴルフボールの上記外面が、赤外線熱源で加熱される、技術的特徴1記載の方法。
[技術的特徴10]
上記ゴルフボールの外面が、約120°〜約150°Fの表面温度に加熱される、技術的特徴9記載の方法。
[技術的特徴11]
上記第2のポリウレタンコーティングが96未満のイソシアネートインデックスを有する、技術的特徴1記載の方法。
[技術的特徴12]
技術的特徴1記載の方法によって形成された被覆されたゴルフボール。
[技術的特徴13]
コーティングされたゴルフボールを形成する方法において、少なくとも1つのコア層と外側カバー層と有し、上記外側コア層が熱可塑性ポリウレタン組成物から形成されるゴルフボールを提供するステップと、
多官能性イソシアネートおよび溶媒を含む混合物を上記外側カバー層に塗布するステップと、
未反応イソシアネート基を有し、少なくとも約115のイソシアネート指数を有する第1のポリウレタンコーティングを上記外側カバー層に塗布するステップと、
上記ゴルフボールを熱で処理するステップと、第2のポリウレタンコーティングをゴルフボールの上記外側カバーに塗布して上記コーティングされたゴルフボールを形成するステップとを有することを特徴とする、上記方法。
[技術的特徴14]
上記イソシアネートが、トルエン2,4−ジイソシアネート(TDI)、トルエン2,6−ジイソシアネート(TDI)、4,4'−メチレンジフェニルジイソシアネート(MDI)、2,4(MDI)、高分子メチレンジフェニルジイソシアネート(PMDI)、p−フェニレンジイソシアネート(PPDI)、m−フェニレンジイソシアネート(PDI)、ナフタレン1,5−ジイソシアネート(NDI)、ナフタレン2,4−ジイソシアネート(NDI)、3,3'−ビトルルレン−4,4'−ジイソシアネート(TODI)、p−キシレンジイソシアネート(XDI)、イソホロンジイソシアネート(IPDI)、1,6−ヘキサメチレンジイソシアネート(HDI)、4,4'−ジシクロヘキシルメタンジイソシアネート(H 12 MDI)、水添キシリレンジイソシアネート(H6XDI)、メタ−テトラメチルキシリレンジイソシアネート(TMXDI)、トランス−シクロヘキサンジイソシアネート(CHDI)、およびノルボルネンジイソシアネート(NBDI)、ならびにこれらのホモポリマーおよびコポリマーおよびブレンドからなるグループから選択される技術的特徴13記載の方法。
[技術的特徴15]
上記イソシアネートが、4,4'−メチレンジフェニルジイソシアネート(MDI)、2,4'−メチレンジフェニルジイソシアネート(MDI)、トルエン2,4−ジイソシアネート(TDI)、トルエン2,6−ジイソシアネート(TDI)、4,4'−ジシクロヘキシルメタンジイソシアネート(H 12 MDI)、p−フェニレンジイソシアネート(PPDI)およびイソホロンジイソシアネート(IPDI)、および、これらのホモポリマーおよびコポリマーおよびブレンドからなるグループから選択される、技術的特徴14記載の方法。
[技術的特徴16]
上記溶媒が、ケトン、アセテート、およびそれらの混合物からなるグループから選択される、技術的特徴13記載の方法。
[技術的特徴17]
上記混合物が紫外線(UV)光安定剤をさらに有する、技術的特徴13記載の方法。
[技術的特徴18]
上記第1および第2のポリウレタンコーティングの少なくとも1つが触媒をさらに有する、技術的特徴13記載の方法。
[技術的特徴19]
上記熱可塑性ポリウレタン組成物が触媒をさらに有する、技術的特徴13記載の方法。
[技術的特徴20]
上記触媒が、ジブチルスズジラウレート、ジブチルスズアセチルアセトネート、ジブチルスズジブトキシド、ジブチルスズスルフィド、ジブチルスズジ−2−エチルヘキサノエート、ジブチルスズ(IV)ジアセテート、ジアルキルスズ(IV))オキサイド、ジブチルスズジクロライド、有機鉛、テトラブチルチタネート、第3級アミン、メルカプチド、オクタン酸第一錫、オクタン酸カリウム、オクタン酸亜鉛、ジアザ化合物および酢酸カリウム、ならびに混合物からなるグループから選択される、技術的特徴19記載の方法。
[技術的特徴21]
技術的特徴13記載の方法によって形成されたコーティングされたゴルフボール。
[技術的特徴22]
コーティングされたゴルフボールを形成する方法において、
少なくとも1つのコア層と外側カバー層とを有し、上記外側カバー層が熱可塑性ポリウレタン組成物から形成されるゴルフボールを提供するステップと、
上記外側カバーに、第1のコーティングを塗布するステップであって、上記コーティングは1,6−ヘキサメチレンジイソシアネート(HDI);4,4'−ジシクロヘキシルメタンジイソシアネート(H 12 MDI);および4,4'−メチレンジフェニルジイソシアネート(MDI)の混合物と、溶媒とを有し、上記コーティングは未反応イソシアネート基を有し、少なくとも約115のイソシアネートインデックスを有する、上記ステップと、
上記ゴルフボールを熱で処理するステップと、
第2のポリウレタンコーティングを上記ゴルフボールの上記外側カバーに塗布して上記コーティングされたゴルフボールを形成するステップとを有することを特徴とする、上記方法。
[技術的特徴23]
上記溶媒が、ケトン、アセテート、およびそれらの混合物からなるグループから選択される、技術的特徴22記載の方法。
[技術的特徴24]
技術的特徴22記載の方法によって形成されたコーティングされたゴルフボール。
Claims (24)
- コーティングされたゴルフボールを形成する方法において、
熱可塑性ポリウレタン組成物から形成される少なくとも1つのコア層および外側カバー層を含むゴルフボールを提供するステップと、
未反応イソシアネート基を含み、少なくとも約115のイソシアネートインデックスを有する第1のポリウレタンコーティングを上記外側カバー層に塗布するステップと、
上記ゴルフボールを熱で処理するステップと、
第2のポリウレタンコーティングを上記ゴルフボールの上記外側カバーに塗布してコーティングされたゴルフボールを形成するステップとを有することを特徴とする、上記方法。 - 上記第1および第2のポリウレタンコーティングの少なくとも1つが触媒をさらに有する、請求項1記載の方法。
- 上記熱可塑性ポリウレタン組成物が触媒をさらに有する、請求項1記載の方法。
- 上記外側カバー層は、約0.010〜約0.050インチの範囲の厚さを有する、請求項1記載の方法。
- 上記外側カバー層が、約20〜約59ショアDの範囲の硬度を有する、請求項1記載の方法。
- 上記ゴルフボールが、内側コアおよび外側コア層を有する、請求項1記載の方法。
- 上記ゴルフボールは、内側カバー層をさらに有する、請求項1記載の方法。
- 上記第1および第2のポリウレタンコーティングがスプレイコーティングによって塗布される、請求項1記載の方法。
- 上記ゴルフボールの上記外面が、赤外線熱源で加熱される、請求項1記載の方法。
- 上記ゴルフボールの外面が、約120°〜約150°Fの表面温度に加熱される、請求項9記載の方法。
- 上記第2のポリウレタンコーティングが96未満のイソシアネートインデックスを有する、請求項1記載の方法。
- 請求項1記載の方法によって形成された被覆されたゴルフボール。
- コーティングされたゴルフボールを形成する方法において、少なくとも1つのコア層と外側カバー層と有し、上記外側コア層が熱可塑性ポリウレタン組成物から形成されるゴルフボールを提供するステップと、
多官能性イソシアネートおよび溶媒を含む混合物を上記外側カバー層に塗布するステップと、
未反応イソシアネート基を有し、少なくとも約115のイソシアネート指数を有する第1のポリウレタンコーティングを上記外側カバー層に塗布するステップと、
上記ゴルフボールを熱で処理するステップと、第2のポリウレタンコーティングをゴルフボールの上記外側カバーに塗布して上記コーティングされたゴルフボールを形成するステップとを有することを特徴とする、上記方法。 - 上記イソシアネートが、トルエン2,4−ジイソシアネート(TDI)、トルエン2,6−ジイソシアネート(TDI)、4,4’−メチレンジフェニルジイソシアネート(MDI)、2,4(MDI)、高分子メチレンジフェニルジイソシアネート(PMDI)、p−フェニレンジイソシアネート(PPDI)、m−フェニレンジイソシアネート(PDI)、ナフタレン1,5−ジイソシアネート(NDI)、ナフタレン2,4−ジイソシアネート(NDI)、3,3’−ビトルルレン−4,4’−ジイソシアネート(TODI)、p−キシレンジイソシアネート(XDI)、イソホロンジイソシアネート(IPDI)、1,6−ヘキサメチレンジイソシアネート(HDI)、4,4’−ジシクロヘキシルメタンジイソシアネート(H12MDI)、水添キシリレンジイソシアネート(H6XDI)、メタ−テトラメチルキシリレンジイソシアネート(TMXDI)、トランス−シクロヘキサンジイソシアネート(CHDI)、およびノルボルネンジイソシアネート(NBDI)、ならびにこれらのホモポリマーおよびコポリマーおよびブレンドからなるグループから選択される請求項13記載の方法。
- 上記イソシアネートが、4,4’−メチレンジフェニルジイソシアネート(MDI)、2,4’−メチレンジフェニルジイソシアネート(MDI)、トルエン2,4−ジイソシアネート(TDI)、トルエン2,6−ジイソシアネート(TDI)、4,4’−ジシクロヘキシルメタンジイソシアネート(H12MDI)、p−フェニレンジイソシアネート(PPDI)およびイソホロンジイソシアネート(IPDI)、および、これらのホモポリマーおよびコポリマーおよびブレンドからなるグループから選択される、請求項14記載の方法。
- 上記溶媒が、ケトン、アセテート、およびそれらの混合物からなるグループから選択される、請求項13記載の方法。
- 上記混合物が紫外線(UV)光安定剤をさらに有する、請求項13記載の方法。
- 上記第1および第2のポリウレタンコーティングの少なくとも1つが触媒をさらに有する、請求項13記載の方法。
- 上記熱可塑性ポリウレタン組成物が触媒をさらに有する、請求項13記載の方法。
- 上記触媒が、ジブチルスズジラウレート、ジブチルスズアセチルアセトネート、ジブチルスズジブトキシド、ジブチルスズスルフィド、ジブチルスズジ−2−エチルヘキサノエート、ジブチルスズ(IV)ジアセテート、ジアルキルスズ(IV))オキサイド、ジブチルスズジクロライド、有機鉛、テトラブチルチタネート、第3級アミン、メルカプチド、オクタン酸第一錫、オクタン酸カリウム、オクタン酸亜鉛、ジアザ化合物および酢酸カリウム、ならびに混合物からなるグループから選択される、請求項19記載の方法。
- 請求項13記載の方法によって形成されたコーティングされたゴルフボール。
- コーティングされたゴルフボールを形成する方法において、
少なくとも1つのコア層と外側カバー層とを有し、上記外側カバー層が熱可塑性ポリウレタン組成物から形成されるゴルフボールを提供するステップと、
上記外側カバーに、第1のコーティングを塗布するステップであって、上記コーティングは1,6−ヘキサメチレンジイソシアネート(HDI);4,4’−ジシクロヘキシルメタンジイソシアネート(H12MDI);および4,4’−メチレンジフェニルジイソシアネート(MDI)の混合物と、溶媒とを有し、上記コーティングは未反応イソシアネート基を有し、少なくとも約115のイソシアネートインデックスを有する、上記ステップと、
上記ゴルフボールを熱で処理するステップと、
第2のポリウレタンコーティングを上記ゴルフボールの上記外側カバーに塗布して上記コーティングされたゴルフボールを形成するステップとを有することを特徴とする、上記方法。 - 上記溶媒が、ケトン、アセテート、およびそれらの混合物からなるグループから選択される、請求項22記載の方法。
- 請求項22記載の方法によって形成されたコーティングされたゴルフボール。
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