JP5071466B2 - 塗料組成物、含フッ素積層体及び樹脂組成物 - Google Patents
塗料組成物、含フッ素積層体及び樹脂組成物 Download PDFInfo
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- JP5071466B2 JP5071466B2 JP2009261791A JP2009261791A JP5071466B2 JP 5071466 B2 JP5071466 B2 JP 5071466B2 JP 2009261791 A JP2009261791 A JP 2009261791A JP 2009261791 A JP2009261791 A JP 2009261791A JP 5071466 B2 JP5071466 B2 JP 5071466B2
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- amide group
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- fluororesin
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- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
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- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D5/002—Priming paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
以下に本発明を詳細に説明する。
上記アミド基含有ポリマー(a1)は、ポリアミドイミド〔PAI〕、ポリアミド、及び/又は、ポリアミド酸(ポリアミック酸)であることが好ましい。
上記プライマー組成物は、上塗り塗料を塗装することに先立ち、被塗装物上に塗装する下塗り用塗料組成物である。本明細書において、プライマー組成物は、プライマーということがある。上記上塗り塗料は、塗装して得られる塗装物の用途にもよるが、耐蝕性、非粘着性等のフッ素樹脂の一般的な特性を付与し得る点で、フッ素樹脂(D)からなる塗料であることが好ましい。本明細書において、上記上塗り塗料として上記フッ素樹脂(D)からなる塗料を塗装して得られる塗膜をフッ素樹脂層ということがある。本発明の塗料組成物は、即ち、プライマー組成物であり、上記プライマー組成物が、フッ素樹脂(D)からなるフッ素樹脂層の下塗り用塗料組成物であるものが好ましい。上記フッ素樹脂(D)については、後述する。
本明細書において、上記「クロムフリープライマー」とは、6価クロムがバインダー成分の役割を果たさないプライマーを意味する。上記クロムフリープライマーは、従って、たとえ6価クロム単体又は6価クロムを有する化合物を含有するものであっても、6価クロム単体又は6価クロムを有する化合物がバインダー成分としての役割を果たさないプライマーであり、好ましくは、6価クロム単体又は6価クロムを有する化合物を含有しないプライマーである。
上記塗布の方法としては、本発明の塗料組成物が液状塗料タイプである場合、スプレー塗布、ローラーによる塗布等を用いることが好ましく、本発明の塗料組成物が粉体塗料タイプである場合、静電塗布、流動浸漬塗布又はロトライニング塗布を用いることが好ましい。
上記フッ素樹脂(D)としては、本発明の塗料組成物がフッ素樹脂(C)を含まないものである場合、フッ素樹脂(C)と同じものを用いてもよい。
本発明の塗料組成物がフッ素樹脂(C)を含むものである場合、上記塗料組成物を被塗装物上に塗装し形成される塗膜の表面には、フッ素樹脂(C)が多く含まれており、上記塗膜の表面との相溶性及び接着性を高める意味で、上記塗膜上に形成するフッ素樹脂層におけるフッ素樹脂(D)としては、フッ素樹脂(C)と同一又は類似の組成を有するフッ素樹脂を用いることが好ましい。
上記末端官能基を有するポリマーにおける官能基の量は、上記官能基を有するモノマーを重合することによって増やすことができる。
バルブシート、油圧用シール、バックアップリング、ピストンリング、ウェアバンド、ベーン、ボールベアリングリテーナー、ローラー、カム、ギア、ベアリング、ラビリンスシール、ポンプ部品、機械的リンク機構、ブッシング、ファスナ、スプラインライナー、ブラケット、油圧ピストン、ケミカルポンプケーシング、バルブ、弁、タワーパッキン、コイルボビン、パッキン、コネクター、ガスケット、バルブシール等の機械工業関連用途;
スラストワッシャ、シールリング、ギア、ベアリング、タペット、エンジン部品(ピストン、ピストンリング、バルブステア)、トランスミッション部品(スプール弁、ボール逆止弁、シーリング)、ロッカーアーム等の車両工業関連用途;
ジェットエンジン部品(ブッシング、ワッシャ、スペーサー、ナット)、パワーコントロールクラッチ、ドアヒンジ用ベアリング、コネクター、チューブクランプ、ブラケット、油圧部品、アンテナ、レドーム、フレーム、燃料系統部品、コンプレッサ部品、ロケットエンジン部品、ウェアストリップ、コネクタシェルフ、宇宙構造体等の航空、宇宙産業関連用途等が挙げられる。その他にも、製罐機ピンカバー、メッキ装置用部品、原子力関連部品、超音波トランデューサ、ポテンショメータシャフト、給水栓部品等の用途が挙げられる。
本発明の樹脂組成物は、上述のように耐熱性に優れるので、これらの特性が要求される塗膜や各種成形体の形成に好適に用いることができる。
以下に実験例を挙げて本発明を更に詳しく説明するが、本発明はこれら実験例のみに限定されるものではない。
ポリアミドイミド樹脂(商品名:HI−680、日立化成工業社製、30%N−メチル−2−ピロリドン溶液)〔PAI〕10.00g、テトラフルオロエチレン/パーフルオロ(アルキルビニル)エーテル共重合体〔PFA〕(融点:310℃、平均粒子径:25μm)6.66g、ポリフェニレンサルファイド樹脂〔PPS〕(商品名:ライトンV−1、フィリップス社製)0.33gをN−メチル−2−ピロリドン13.80g、メチルイソブチルケトン9.20gの混合溶剤に加え、ディスパー(商品名:スリーワンモーター、新東科学社製)を用いて溶解分散して本発明の塗料組成物を得た。
10mmの幅に切れ目を入れた試験片を350℃の電気炉に入れ、20時間又は50時間加熱した後、室温に戻し、テンシロン万能試験機を用いてJIS K 6854−1(1999年)に準拠して引っ張り速度50mm/分で試験片に対して90°方向に剥離接着強さを測定した。但し、上記加熱後に試験片の塗膜が剥離した場合、剥離接着強さは0kg/cmとした。
10mmの幅に切れ目を入れた試験片を90℃以上の熱水に24時間浸漬した後、室温に戻し、耐熱性試験と同様にして試験片に対して90°方向に剥離接着強さを測定した。
上記剥離接着強さの試験において、剥離状態を観察し以下のように評価した。
/A:被塗装物と塗料組成物の焼成塗膜との間での剥離〔基材剥離〕
/B:塗料組成物の焼成塗膜とPFA樹脂層との間での剥離〔層間剥離〕
/C:塗料組成物の焼成塗膜の破壊による剥離〔凝集破壊〕
実験例1のPFAを13.32gにする以外は実験例1と同様にして積層体Bを作製し実験例1と同様の評価を行った。
PAIを11.00g、PPSを0.03gにする以外は実験例1と同様にして積層体Cを作製し実験例1と同様の評価を行った。
PAIを11.00g、抗酸化性物質として亜鉛系酸化防止剤であるベンゾチアゾール系化合物(2−メルカプトベンゾチアゾール亜鉛塩)0.03gを用いた以外は実験例1と同様に積層体Dを作製し実験例1と同様の評価を行った。
PAIを8.88g、PPSを0.67gにする以外は実験例1と同様にして積層体Eを作製し実験例1と同様の評価を行った。
実験例1のPFAを1.67g用いた以外は実験例1と同様にして積層体Fを作製し実験例1と同様の評価を行った。
実験例1のPFAを23.31g用いた以外は実験例1と同様にして積層体Gを作製し実験例1と同様の評価を行った。
PFAを6.00g用い、PPSを添加しなかった以外は実験例1と同様にして積層体Hを作製し実験例1と同様の評価を行った。
PAIを5.55g、PPSを1.67g用いた以外は実験例1と同様にして積層体Iを作製し実験例1と同様の評価を行った。
PAIを7.77g、PPSを1.00g用いた以外は実験例1と同様にして積層体Jを作製し実験例1と同様の評価を行った。
実験例1で用いた鉄板に代えて実験例1で用いたものと同じアルミナ粉を用いてブラスト処理したステンレス鋼板(SUS304、縦100mm×横50mm×厚さ1.5mm、平均粗さ〔Ra〕=2〜3μm)を用いた以外は実験例1と同様にして積層体Kを作製し実験例1と同様の評価を行った。
抗酸化性物質としてPPS0.33gに代えてベンゾチアゾール系化合物(2−メルカプトベンゾチアゾール亜鉛塩)0.03gとPPS0.33gとのブレンドを用いた以外は実験例1と同様に塗料組成物を調製した。次に実験例1で用いた鉄板を実験例11で用いたステンレス鋼板にする以外は実験例1と同様にして積層体Lを作製し実験例1と同様の評価を行った。
実験例1と同様にブラスト処理した処理済み鉄板(縦100mm×横10mm×厚さ1.5mm)を2枚用意し、そのうちの1枚の縦半分の面積に、実験例1のPFAを用いない以外は実験例1と同様にして調製した塗料組成物を乾燥膜厚が30μmになるように塗布し、塗布した部分にもう1枚の処理済み鉄板を張り合わせた後、350℃で1時間焼成して試験片を作製した。その後、上記試験片に対して、実験例1に従って耐熱性試験及び耐熱水処理試験を行った。また、上記耐熱性試験及び上記耐熱水処理試験の前後でJIS K 6850(1999年)に準拠して引張剪断接着強さを測定した。
PFAのみならずPPSも用いない塗料組成物を用いた以外は実験例11と同様にして試験片を作製し実験例13と同様の評価を行った。
結果を表2に示す。なお、表中、/A、/B、及び、/Cは上述の剥離状態評価である。
実験例1と同様の条件で、本発明の塗料組成物を得た。得られた塗料組成物を実験例1で用いたブラスト処理した鉄板上に乾燥膜厚が30μmになるようにスプレー塗装し、120℃で30分間乾燥し、350℃で1時間焼成して、被塗装物と塗膜(測定用塗膜)とからなる積層体Mを得た。
350℃で30時間加熱したものについても剥離接着強さを測定したこと以外は実験例1と同様にした。結果を表3のa)に示す。
90℃以上の水にそれぞれ72時間、120時間浸漬したものについても剥離接着強さを測定したこと以外は実験例1と同様にした。結果を表3のb)に示す。
10cmの幅に切れ目を入れた試験片について、350℃に20時間又は30時間おく熱処理を行った後、90℃以上の水に24時間浸漬する熱水処理を行い、次いで室温に戻し、実験例1の耐熱性試験と同様にして試験片に対して90℃方向に剥離接着強さを測定した。結果を表4に示す。
塗料組成物の作製においてPPSを添加しなかった以外は実験例15と同様にして、比較用積層体を得、評価した。結果を表3及び表4に示す。
本発明の塗料組成物の代わりにリン酸クロム系プライマー(商品名:850−314/VM7799=100/35、DuPont社製)を塗装に供した以外は実験例15と同様にして比較用積層体を得、評価した。結果を表3及び表4に示す。
本発明の塗料組成物の代わりに比較用クロムフリープライマー(商品名:420−703、DuPont社製)を塗装に供した以外は実験例15と同様にして比較例用積層体を得、評価した。結果を表3及び表4に示す。
ポリアミドイミド樹脂(商品名:トーロン4000T−40、ソルベイアドバンストポリマーズ社製)〔PAI〕を粉砕機(商品名:アトマイザー、ダルトン社製)にて粉砕し平均粒子径が50μmのPAI粒子粉砕品を得た。得られたPAI粒子粉砕品90g、テトラフルオロエチレン/パーフルオロ(アルキルビニル)エーテル共重合体〔PFA〕(融点:310℃、平均粒子径:25μm)400g、ポリフェニレンサルファイド樹脂〔PPS〕(商品名:ライトンV−1、フィリップス社製)10gを混合機(商品名:V型ブレンダー、ダルトン社製)にて均一分散し本発明の塗料組成物を得た。
PPSを30g、PAIを70g用いた以外は実験例16と同様にして積層体Pを得、評価した。結果を表5に示す。
PPSを40g、PAIを60g用いた以外は実験例16と同様にして積層体Qを得、評価した。結果を表5に示す。
PPSを50g、PAIを50g用いた以外は実験例16と同様にして比較用積層体を得、評価した。結果を表5に示す。
PPSを用いず、PAIを100g用いた以外は実験例16と同様にして比較用積層体を得、評価した。結果を表5に示す。
Claims (3)
- アミド基を含有しているか又はアミド基を含有することとなるアミド基含有性高分子化合物(A)と、ポリアリレンサルファイドと、フッ素樹脂とからなる樹脂組成物であって、
粉体塗料であり、
前記アミド基含有性高分子化合物(A)は、アミド基と芳香環とを有しているアミド基含有ポリマー(a1)、及び/又は、前記塗料組成物を塗装する際の焼成により前記アミド基含有ポリマー(a1)に変化するアミド基含有ポリマー前駆体(a2)であり、
前記ポリアリレンサルファイドは、前記アミド基含有性高分子化合物(A)と前記ポリアリレンサルファイドとの合計の1〜40質量%であり、
前記フッ素樹脂は、前記アミド基含有性高分子化合物(A)とポリアリレンサルファイドと前記フッ素樹脂との合計の50〜90質量%である
ことを特徴とする樹脂組成物。 - ポリアリレンサルファイドは、アミド基含有性高分子化合物(A)とポリアリレンサルファイドとの合計の10〜40質量%である請求項1記載の樹脂組成物。
- アミド基含有ポリマー(a1)は、ポリアミドイミドである請求項1又は2記載の樹脂組成物。
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