JP4016987B2 - Fluorine-containing laminate, method for forming fluorine-containing laminate and coated article - Google Patents

Description

  The present invention relates to a fluorine-containing laminate, a method for forming a fluorine-containing laminate, and a coated article.

（式中、Ｒｆは、炭素数４〜２０のパーフルオロアルキル基を表し、Ｒ^１は、−Ｈ又は炭素数１〜１０のアルキル基を表し、Ｒ^２は、炭素数１〜１０のアルキレン基を表し、Ｒ^３は、−Ｈ又はメチル基を表し、Ｒ^４は、炭素数１〜１７のアルキル基を表し、ｒは、１〜１０の整数を表し、ｓは、０〜１０の整数を表す。）で表されるものである。
上記含フッ素重合体（ａ）は、上記不飽和単量体（ＩＶ）の単独重合体であってもよいし、また、上記不飽和単量体（ＩＶ）と上記不飽和単量体（ＩＶ）と共重合し得る単量体（Ｖ）との共重合体であってもよい。
上記単量体（Ｖ）としては特に限定されず、例えば、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジルエステル、ジ（メタ）アクリル酸ポリエチレングリコール、Ｎ−メチロールプロパンアクリルアミド、（メタ）アクリル酸アミド、アルキル基の炭素数が１〜２０である（メタ）アクリル酸のアルキルエステル等の（メタ）アクリル酸誘導体；エチレン、塩化ビニル、フッ化ビニル、スチレン、α−メチルスチレン、ｐ−メチルスチレン等の置換又は非置換エチレン；アルキル基の炭素数が１〜２０であるアルキルビニルエーテル、アルキル基の炭素数が１〜２０であるハロゲン化アルキルビニルエーテル等のビニルエーテル類；アルキル基の炭素数が１〜２０であるビニルアルキルケトン等のビニルケトン類；無水マレイン酸等の脂肪族不飽和ポリカルボン酸及びその誘導体；ブタジエン、イソプレン、クロロプレン等のポリエン等が挙げられる。
上記含フッ素重合体（ａ）は、例えば、乳化重合等の従来公知の重合方法等を用いることにより得ることができる。
上記含フッ素重合体（ａ）としては、得られる含フッ素積層体が耐食性及び耐水蒸気性に優れる点から、ＴＦＥホモポリマー、変性ＰＴＦＥ、上記ＴＦＥ系共重合体が好ましい。上記ＴＦＥ系共重合体としては、ＦＥＰ、ＰＦＡが好ましい。
上記含フッ素重合体（ａ）としては、ＴＦＥホモポリマー、変性ＰＴＦＥ、ＦＥＰ及び／又はＰＦＡがより好ましい。
上記含フッ素重合体（ａ）としては、得られるプライマー層（Ａ）と後述の含フッ素層（Ｂ）との密着性が優れる点から、ＴＦＥ系共重合体を含むものが更に好ましい。上記プライマー層（Ａ）と後述の含フッ素層（Ｂ）との密着性が優れる含フッ素積層体は、耐水蒸気性に優れるので、水蒸気の存在下にあってもブリスター等の塗膜欠陥の発生を抑制することができる。ＴＦＥ系共重合体を含む含フッ素重合体（ａ）としては、例えば、ＰＦＡ単独、ＴＦＥホモポリマーとＦＥＰとの混合物、ＴＦＥホモポリマーとＰＦＡとの混合物、変性ＰＴＦＥとＦＥＰとの混合物、変性ＰＴＦＥとＰＦＡとの混合物等が挙げられる。
プライマー層（Ａ）における含フッ素重合体（ａ）としては、得られる含フッ素積層体が耐食性及び耐水蒸気性に優れ、上記プライマー層（Ａ）が後述の含フッ素層（Ｂ）への密着性に優れる点から、ＰＦＡ単独、ＴＦＥホモポリマーとＰＦＡとの混合物、ＴＦＥホモポリマーとＦＥＰとの混合物が好ましく、ＴＦＥホモポリマーとＦＥＰとの混合物がより好ましい。
上記プライマー層（Ａ）は、上述の含フッ素重合体（ａ）とともに、耐熱性樹脂からなるものである。
上記耐熱性樹脂は、通常、耐熱性を有すると認識されている樹脂であればよく、連続使用可能温度が１５０℃以上の樹脂が好ましい。但し、上記耐熱性樹脂としては、上述の含フッ素重合体（ａ）を除く。
上記耐熱性樹脂としては特に限定されず、例えば、ポリアミドイミド樹脂、ポリイミド樹脂、ポリエーテルスルホン樹脂、ポリエーテルイミド樹脂、ポリエーテルエーテルケトン樹脂、芳香族ポリエステル樹脂、ポリアリレンサルファイド樹脂等が挙げられる。上記耐熱性樹脂としては、１種又は２種以上を用いることができる。
上記ポリアミドイミド樹脂〔ＰＡＩ〕は、分子構造中にアミド結合及びイミド結合を有する重合体からなる樹脂である。上記ＰＡＩとしては特に限定されず、例えば、アミド結合を分子内に有する芳香族ジアミンとピロメリット酸等の芳香族四価カルボン酸との反応；無水トリメリット酸等の芳香族三価カルボン酸と４，４−ジアミノフェニルエーテル等のジアミンやジフェニルメタンジイソシアネート等のジイソシアネートとの反応；芳香族イミド環を分子内に有する二塩基酸とジアミンとの反応等の各反応により得られる高分子量重合体からなる樹脂等が挙げられる。上記ＰＡＩとしては、耐熱性に優れる点から、主鎖中に芳香環を有する重合体からなるものが好ましい。
上記ポリイミド樹脂〔ＰＩ〕は、分子構造中にイミド結合を有する重合体からなる樹脂である。上記ＰＩとしては特に限定されず、例えば、無水ピロメリット酸等の芳香族四価カルボン酸無水物の反応等により得られる高分子量重合体からなる樹脂等が挙げられる。上記ＰＩとしては、耐熱性に優れる点から、主鎖中に芳香環を有する重合体からなるものが好ましい。
上記ポリエーテルスルホン樹脂〔ＰＥＳ〕は、下記一般式

で表される繰り返し単位を有する重合体からなる樹脂である。上記ＰＥＳとしては特に限定されず、例えば、ジクロロジフェニルスルホンとビスフェノールとの重縮合により得られる重合体からなる樹脂等が挙げられる。
上記耐熱性樹脂は、基材との密着性に優れ、含フッ素積層体を形成する際に行う焼成時の温度下でも充分な耐熱性を有し、得られる含フッ素積層体が耐食性及び耐水蒸気性に優れる点から、ＰＡＩ、ＰＩ及び／又はＰＥＳが好ましい。上記「ＰＡＩ、ＰＩ及び／又はＰＥＳ」とは、ＰＡＩ単独、ＰＩ単独、ＰＥＳ単独、ＰＡＩとＰＩとの混合物、ＰＥＳとＰＡＩとの混合物、ＰＥＳとＰＩとの混合物、ＰＥＳとＰＡＩとＰＩとの混合物を意味する。
ＰＡＩ、ＰＩ及びＰＥＳは、それぞれが１種又は２種以上からなるものであってよい。
上記耐熱性樹脂としては、基材との密着性及び耐熱性に優れる点から、ＰＡＩ及び／又はＰＩがより好ましい。上記「ＰＡＩ及び／又はＰＩ」とは、ＰＡＩ単独、ＰＩ単独、又は、ＰＡＩとＰＩとの混合物を意味する。
上記耐熱性樹脂としては、耐食性と耐水蒸気性に優れる点から、ＰＥＳ、並びに、ＰＡＩ及び／又はＰＩが更に好ましい。上記「ＰＥＳ、並びに、ＰＡＩ及び／又はＰＩ」とは、ＰＥＳとＰＡＩとの混合物、ＰＥＳとＰＩとの混合物、又は、ＰＥＳとＰＡＩとＰＩとの混合物を意味する。上記耐熱性樹脂は、上記ＰＥＳ及びＰＡＩの混合物であることが特に好ましい。
上記プライマー層（Ａ）において、上記ＰＥＳは、ＰＥＳ、並びに、ＰＡＩ及び／又はＰＩの合計量の６５〜８５質量％であることが好ましい。
上記プライマー層（Ａ）は、上記含フッ素重合体（ａ）と上記耐熱性樹脂とからなるものであるが、上記耐熱性樹脂は、上記耐熱性樹脂及び含フッ素重合体（ａ）の固形分合計量の１５〜５０質量％であることが好ましい。
上記プライマー層（Ａ）は、主として、重合体成分と後述の添加剤類とからなるものである。上記プライマー層（Ａ）は、重合体成分が含フッ素重合体（ａ）及び耐熱性樹脂であるものが好ましい。本明細書において、上記「プライマー層（Ａ）は、重合体成分が含フッ素重合体（ａ）及び耐熱性樹脂である」とは、プライマー層（Ａ）における重合体が含フッ素重合体（ａ）及び耐熱性樹脂のみであることを意味する。上記プライマー層（Ａ）は、その重合体成分が含フッ素重合体（ａ）及び耐熱性樹脂であることにより、基材及び後述の含フッ素層（Ｂ）の双方に対して優れた密着性を効率よく有するものである。
上記プライマー層（Ａ）は、基材及び後述の含フッ素層（Ｂ）の双方に対して優れた密着性を効率良く有する点から、重合体成分が含フッ素重合体（ａ）及び耐熱性樹脂であるものが好ましいが、含フッ素積層体の耐食性及び耐水蒸気性をより向上させることができる点から、含フッ素重合体（ａ）と耐熱性樹脂とともに、更に、その他の樹脂からなるものであってもよい。
上記その他の樹脂としては特に限定されず、例えば、フェノール樹脂、尿素樹脂、エポキシ樹脂、ウレタン樹脂、メラミン樹脂、ポリエステル樹脂、ポリエーテル樹脂、アクリル樹脂、アクリルシリコーン樹脂、シリコーン樹脂、シリコーンポリエステル樹脂等が挙げられる。上記その他の樹脂としては、本発明の含フッ素積層体が焼成することにより得られるものであることから、耐熱性であることが好ましい。
本発明の含フッ素積層体は、溶融加工性含フッ素重合体（ｂ）と充填材とからなる含フッ素層（Ｂ）を有するものである。
本発明の含フッ素積層体は、上記含フッ素層（Ｂ）が上記プライマー層（Ａ）上に形成されているものである。上記含フッ素層（Ｂ）は、その上に後述の含フッ素層（Ｃ）が積層されているものである。
上記溶融加工性含フッ素重合体（ｂ）は、主鎖又は側鎖を構成する炭素原子に直接結合しているフッ素原子を有する重合体のうち、溶融加工性を有するものである。
上記溶融加工性含フッ素重合体（ｂ）としては、上述の含フッ素重合体（ａ）のうち、溶融加工性を有するものを用いることができる。上記溶融加工性含フッ素重合体（ｂ）は、上記含フッ素層（Ｂ）が上述のプライマー層（Ａ）と後述の含フッ素層（Ｃ）との密着性に優れ、得られる含フッ素積層体が耐食性及び耐水蒸気性に優れる点から、１５０〜３５０℃の融点を有し、融点より５０℃高い温度における溶融粘度が１０^６（パスカル・秒）以下であるものが好ましく、上述のＴＦＥ系共重合体であることが好ましい。上記溶融加工性含フッ素重合体（ｂ）は、１種又は２種以上であってよい。上記溶融加工性含フッ素重合体（ｂ）は、ＰＦＡ及び／又はＦＥＰであることがより好ましい。上記「ＰＦＡ及び／又はＦＥＰである」とは、ＰＦＡ又はＦＥＰのそれぞれ単独であってもよいし、これらの混合物であってもよいことを意味する。上記溶融加工性含フッ素重合体（ｂ）は、耐熱性に優れる点から、ＰＦＡであることが更に好ましい。
上記含フッ素層（Ｂ）は、上記溶融加工性含フッ素重合体（ｂ）とともに、充填材からなるものである。
本明細書において、上記「充填材」とは、得られる含フッ素積層体に対する特性付与、物性向上、増量等を目的として用いるものであって、後述の充填材含有組成物における液状媒体に溶解しないものを意味する。上記特性や物性としては、強度、耐久性、耐侯性、難燃性等が挙げられる。
上記充填材としては特に限定されず、例えば、木粉、石英砂、カーボンブラック、クレー、タルク、体質顔料、光輝性偏平顔料、鱗片状顔料、ガラス、各種強化材、各種増量材、導電性フィラー等が挙げられる。上記充填材としては、本発明の含フッ素積層体が光輝感を有することを要求される場合、光輝性充填材が好ましい。上記「光輝性充填材」は、得られる含フッ素積層体に光輝感を付与することができる充填材である。
上記光輝性充填材としては、光輝性偏平顔料や鱗片状顔料に分類されるもの、ガラス等が挙げられ、これらは１種又は２種以上を用いることができる。上記光輝性偏平顔料や鱗片状顔料に分類されるものとしては特に限定されず、例えば、マイカ、金属粉末等が挙げられる。上記ガラスとしては特に限定されず、例えば、ガラスビーズ、ガラスバブル、ガラスフレーク、ガラス繊維等が挙げられる。上記光輝性偏平顔料や鱗片状顔料に分類されるもの及びガラスとしては、それぞれ１種又は２種以上を用いることができる。
上記充填材としては、マイカ、金属粉末及び／又はガラスビーズからなる光輝性充填材がより好ましい。このような光輝性充填材は、マイカ、金属粉末及び／又はガラスビーズを含むものであればよく、マイカ、金属粉末及び／又はガラスビーズのみであってもよいし、マイカ、金属粉末及び／又はガラスビーズと、含フッ素積層体に光輝感を付与することができるその他の充填材とであってもよい。上記「マイカ、金属粉末及び／又はガラスビーズ」とは、マイカ単独、金属粉末単独、ガラスビーズ単独、マイカと金属粉末との混合物、マイカとガラスビーズとの混合物等、又は、金属粉末とガラスビーズとの混合物を意味する。
マイカ、金属粉末及びガラスとしては、一般に、得られる含フッ素積層体に光輝感を付与することができないものもあり得るが、上記「マイカ、金属粉末及び／又はガラスビーズからなる光輝性充填材」におけるマイカ、金属粉末及び／又はガラスビーズは、光輝感を付与することができるものである。
上記金属粉末としては特に限定されず、例えば、アルミニウム、鉄、すず、亜鉛、銅等の金属単体の粉末；アルミニウム合金、ステンレス等の合金の粉末等が挙げられる。上記金属粉末の形状としては特に限定されず、例えば、粒子状、フレーク状等が挙げられるが、光輝感に優れる点からフレーク状が好ましい。
上記充填材は、光輝感及び経済性に優れる点から、マイカ及び／又はアルミニウム粉末からなる光輝性充填材が更に好ましい。このような光輝性充填材としては、マイカ単独、アルミニウム粉末単独、又は、マイカとアルミニウム粉末との混合物が挙げられる。上記アルミニウム粉末の形状としては、フレーク状が好ましい。上記充填材は、得られる含フッ素積層体が耐食性に優れる点から、マイカからなる光輝性充填材であることが特に好ましい。
上記含フッ素層（Ｂ）において、上記充填材は、溶融加工性含フッ素重合体（ｂ）の固形分に対して０．００１〜１０質量％であることが好ましい。０．００１質量％未満であると、上記含フッ素層（Ｂ）が光輝感を付与し得る充填材からなるものである場合、得られる含フッ素積層体の光輝感が充分ではなく、１０質量％を超えると、耐食性及び耐水蒸気性が低下するおそれがある。好ましい下限は、０．０１質量％であり、好ましい上限は、５質量％である。
上記含フッ素層（Ｂ）は、主として、重合体成分、充填材及び後述の添加剤類からなるものである。上記含フッ素層（Ｂ）は、重合体成分が溶融加工性含フッ素重合体（ｂ）であるものが好ましい。本明細書において、上記「含フッ素層（Ｂ）は、重合体成分が溶融加工性含フッ素重合体（ｂ）である」とは、含フッ素層（Ｂ）における重合体が溶融加工性含フッ素重合体（ｂ）のみであることを意味する。上記含フッ素層（Ｂ）は、その重合体成分が溶融加工性含フッ素重合体（ｂ）であることにより、上記プライマー層（Ａ）及び後述の含フッ素層（Ｃ）の双方に対して優れた密着性を効率よく有するものである。
本発明の含フッ素積層体は、溶融加工性含フッ素重合体（ｃ）からなる含フッ素層（Ｃ）を有するものである。
本発明の含フッ素積層体は、上述の含フッ素層（Ｂ）上に含フッ素層（Ｃ）が形成されているものである。上記含フッ素層（Ｃ）は、上記含フッ素層（Ｂ）上に形成されている塗膜であってもよいし、フィルム、シート等の成形物であってもよく、いずれの場合であっても、溶融加工性含フッ素重合体（ｃ）の融点以上の温度で焼成されたものである。上記含フッ素層（Ｃ）は、含フッ素層（Ｂ）との密着性に優れる点から、含フッ素層（Ｂ）上に形成された塗膜であることが好ましい。
上記溶融加工性含フッ素重合体（ｃ）は、主鎖又は側鎖を構成する炭素原子に直接結合しているフッ素原子を有する重合体のうち、溶融加工性を有するものである。
上記溶融加工性含フッ素重合体（ｃ）としては、上述の含フッ素重合体（ａ）のうち溶融加工性を有するものを用いることができる。上記溶融加工性含フッ素重合体（ｃ）は、上述の含フッ素重合体（ａ）のうち溶融加工性を有するものであるという点で上記溶融加工性含フッ素重合体（ｂ）と共通するものであるが、含フッ素層（Ｃ）におけるものであるという点で、含フッ素層（Ｂ）におけるものである上記溶融加工性含フッ素重合体（ｂ）と異なるものである。
上記溶融加工性含フッ素重合体（ｃ）としては、造膜性に優れる点、含フッ素層（Ｃ）が上述の含フッ素層（Ｂ）への密着性に優れる点、並びに、得られる含フッ素積層体が耐食性及び耐水蒸気性に優れる点から、上記溶融加工性含フッ素重合体（ｂ）と同じもの等が挙げられ、なかでも１５０〜３５０℃の融点を有し、融点より５０℃高い温度における溶融粘度が１０^６（パスカル・秒）以下であるものが好ましく、このようなものとしては、ＴＦＥ系共重合体が挙げられる。上記溶融加工性含フッ素重合体（ｃ）としては、耐熱性、非粘着性及び造膜性が優れる点から、ＰＦＡ及び／又はＦＥＰが好ましい。上記「ＰＦＡ及び／又はＦＥＰ」とは、ＰＦＡ単独、ＦＥＰ単独、ＰＦＡとＦＥＰとの混合物を意味する。上記溶融加工性含フッ素重合体（ｃ）としては、耐熱性により優れる点から、ＰＦＡがより好ましい。
上記含フッ素層（Ｃ）は、得られる含フッ素積層体が光輝感等の意匠性を有することを要求される場合、透明な層であることが好ましい。上記含フッ素層（Ｃ）が透明な層であると、含フッ素層（Ｃ）を通して上記含フッ素層（Ｂ）中の充填材を視認することができるので、充填材として光輝感を有するものを用いた場合、本発明の含フッ素積層体は、良好な光輝感を有する。
また、上記含フッ素層（Ｃ）が透明な層であると、上記含フッ素層（Ｃ）は、耐食性を悪化させる原因と通常考えられている着色顔料を有していないので、得られる含フッ素積層体は、より優れた耐食性及び耐水蒸気性を有する。
上記含フッ素層（Ｃ）は、主として、重合体成分及び後述の添加剤類からなるものである。上記含フッ素層（Ｃ）は、重合体成分が溶融加工性含フッ素重合体（ｃ）であるものが好ましい。本明細書において、上記「含フッ素層（Ｃ）は、重合体成分が溶融加工性含フッ素重合体（ｃ）である」とは、含フッ素層（Ｃ）における重合体が溶融加工性含フッ素重合体（ｃ）のみであることを意味する。上記含フッ素層（Ｃ）は、その重合体成分が溶融加工性含フッ素重合体（ｃ）であることにより、上記含フッ素層（Ｂ）に対して優れた密着性を有するものである。
本発明の含フッ素積層体において、上記プライマー層（Ａ）は、膜厚が５〜３０μｍであるものが好ましい。５μｍ未満であると、ピンホールが発生し易く、含フッ素積層体の耐食性が低下するおそれがある。３０μｍを超えると、クラックが生じ易くなり、含フッ素積層体の耐水蒸気性が低下するおそれがある。上記プライマー層（Ａ）の膜厚の好ましい上限は、２０μｍである。
本発明の含フッ素積層体において、上記含フッ素層（Ｂ）は、膜厚が５〜３０μｍであるものが好ましい。５μｍ未満であると、含フッ素積層体に光輝感を付与するため光輝感を有する充填材を用いた場合、得られる含フッ素積層体の光輝感が充分ではない場合がある。３０μｍを超えると、含フッ素層（Ｂ）にクラックを生じ易くなり、含フッ素積層体の耐水蒸気性が低下するおそれがある。上記含フッ素層（Ｂ）の膜厚の好ましい下限は、１０μｍであり、好ましい上限は、２０μｍである。
本発明の含フッ素積層体において、含フッ素層（Ｃ）は、膜厚が１０〜９０μｍであるものが好ましい。１０μｍ未満であると、ピンホールが生じ易くなり、含フッ素積層体の耐食性や耐摩耗性が低下するおそれがある。９０μｍを超えると、含フッ素積層体が水蒸気の存在下にある場合、水蒸気が含フッ素積層体中に残存し易くなり、耐水蒸気性に劣る場合がある。上記含フッ素層（Ｃ）の膜厚の好ましい下限は、３０μｍであり、好ましい上限は、７０μｍである。
本発明の含フッ素積層体は、上記プライマー層（Ａ）、上記含フッ素層（Ｂ）及び上記含フッ素層（Ｃ）が、この順に積層されているものである。本発明の含フッ素積層体は、上記プライマー層（Ａ）、上記含フッ素層（Ｂ）及び上記含フッ素層（Ｃ）が、この順に積層されているものであれば、上記プライマー層（Ａ）の上面、及び／又は、上記含フッ素層（Ｂ）の上面に文字、図面等の印刷が施されているものであってもよい。
本発明の含フッ素積層体は、また、上述のように、上記プライマー層（Ａ）、上記含フッ素層（Ｂ）及び上記含フッ素層（Ｃ）を有するものであればよく、上記含フッ素層（Ｃ）上に更に層が設けられているものであってもよい。
本発明の含フッ素積層体は、上述のように、プライマー層（Ａ）上に形成されている含フッ素層（Ｂ）が溶融加工性含フッ素重合体（ｂ）と充填材とからなるものであり、含フッ素層（Ｂ）上に形成されている含フッ素層（Ｃ）が、溶融加工性含フッ素重合体（ｃ）からなるものである。
本発明の含フッ素積層体は、溶融加工性含フッ素重合体（ｂ）と溶融加工性含フッ素重合体（ｃ）とが、どちらも溶融加工性であるので、含フッ素層（Ｂ）と含フッ素層（Ｃ）との密着性が優れ、耐食性及び耐水蒸気性に優れたものである。従来の、プライマー層、ＴＦＥホモポリマーからなる中間層及びＰＦＡからなるトップコート層がこの順に積層している積層体は、耐水蒸気性に劣るという問題があったが、この問題は、プライマー層と中間層との間が剥離しやすいことによると考えられる。この剥離は、ＴＦＥホモポリマーとＰＦＡとの熱膨張率や熱による収縮率に差があることに起因して、中間層とトップコート層に内部応力（ひずみ）が残留したり、ピンホールが発生しやすくなるので、プライマー層と中間層との間で起こりやすくなると考えられる。
本発明の含フッ素積層体は、上述のように含フッ素層（Ｂ）と含フッ素層（Ｃ）との密着性が優れ、耐食性及び耐水蒸気性に優れたものであり、そして、耐摩耗性に優れたものともなる。
本発明の含フッ素積層体は、また、含フッ素層（Ｂ）中で上記充填材を均一に分散させることができるので、充填材として光輝感を有するものを用いた場合、光輝感に優れたものである。本発明の含フッ素積層体は、また、充填材が基材に接触していないので、充填材として上述の金属粉末を用いた場合であっても、耐食性に優れたものである。
本発明の含フッ素積層体形成方法は、上述の含フッ素積層体を形成するためのものであって、
基材上に含フッ素重合体（ａ）と耐熱性樹脂とからなるプライマー用被覆組成物を塗布することよりプライマー塗布膜（Ａｐ）を形成する工程（ｉ）、
上記プライマー塗布膜（Ａｐ）上に溶融加工性含フッ素重合体（ｂ）と充填材とからなる充填材含有組成物を塗布することより含フッ素塗布膜（Ｂｐ）を形成する工程（ｉｉ）、並びに、
上記含フッ素塗布膜（Ｂｐ）上に溶融加工性含フッ素重合体（ｃ）からなる溶融加工性含フッ素組成物を用いて含フッ素膜（Ｃｐ）を形成して、含フッ素積層体を形成する工程（ｉｉｉ）
を含むものである。
上記工程（ｉ）において、上記プライマー用被覆組成物は、含フッ素重合体（ａ）と耐熱性樹脂とからなるものである。上記プライマー用被覆組成物は、液状であってもよいし、粉体であってもよい。上記プライマー用被覆組成物は、液状である場合、含フッ素重合体（ａ）と耐熱性樹脂とともに、液状媒体からなるものである。上記液状媒体は、通常、水及び／又は有機液体からなるものである。本明細書において、上記「有機液体」とは、有機化合物であって、２０℃程度の常温において液体であるものを意味する。
上記プライマー用被覆組成物の液状媒体が主に有機液体からなるものである場合、上記耐熱性樹脂並びに含フッ素重合体（ａ）は、上記液状媒体に粒子として分散したもの、及び／又は、上記液状媒体に溶解したものである。上記有機液体としては特に限定されず、例えば、Ｎ−メチル−２−ピロリドン、２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド等の含窒素有機液体；トルエン、キシレン、トリメチルベンゼン、メチルエチルベンゼン、プロピルベンゼン、ブチルベンゼン等の芳香族炭化水素系溶剤；炭素数が６〜１２の飽和炭化水素系溶剤；γ−ブチロラクトン等のラクトン類；酢酸ブチル等の非環状エステル類；メチルイソブチルケトン、メチルエチルケトン等のケトン類；エチレングリコール、トリエチレングリコール、プロピレングリコール等のグリコール類；ブチルセロソルブ等のグリコールエーテル類；１−ブタノール、ジアセトンアルコール等のモノアルコール類等が挙げられる。
上記芳香族炭化水素系溶剤としては、市販品であるソルベッソ１００、ソルベッソ１５０、ソルベッソ２００（何れも商品名、エクソン化学社製）等を用いてもよい。上記飽和炭化水素系溶剤としては、市販品であるミネラルスピリット（日本工業規格、工業ガソリン４号）等を用いてもよい。
上記有機液体は、単独で用いてもよいし、２種以上を併用してもよい。
上記プライマー用被覆組成物の液状媒体が主に水からなるものである場合、上記耐熱性樹脂は、上記液状媒体に粒子として分散したもの、又は、上記液状媒体に溶解したものであり、含フッ素重合体（ａ）は、上記液状媒体に粒子として分散したものである。
上記プライマー用被覆組成物は、上記液状媒体が主に水からなるものである場合、通常、含フッ素重合体（ａ）からなる粒子を分散安定化させることを目的として、界面活性剤を添加してなるものである。上記界面活性剤としては特に限定されず、例えば、含フッ素系非イオン性界面活性剤等の非イオン性界面活性剤；含フッ素系アニオン性界面活性剤等のアニオン性界面活性剤；含フッ素系カチオン性界面活性剤等のカチオン性界面活性剤等が挙げられる。上記プライマー用被覆組成物は、含フッ素重合体（ａ）からなる粒子を分散安定化させることを目的として、上記界面活性剤とともに、上記有機液体を併用することもできる。
上記プライマー用被覆組成物は、また、特公昭４９−１７０１７号公報に記載されている方法、即ち、分散質が上記含フッ素重合体（ａ）からなる粒子と耐熱性樹脂からなる粒子であり、分散媒が主に水からなるものである水性分散体に、転層液である有機溶剤及び転層剤を加え、上記含フッ素重合体（ａ）からなる粒子と耐熱性樹脂からなる粒子とを上記有機溶剤に転層する方法等により得られるオルガノゾルであってもよい。
上記プライマー用被覆組成物は、基材との密着性に優れる点から液状のものであることが好ましく、環境問題の点から上記液状媒体が主に水からなるものがより好ましい。
上記プライマー用被覆組成物が液状のものである場合、上記プライマー用被覆組成物の粘度は、０．１〜５００００ｍＰａ・ｓであることが好ましい。０．１ｍＰａ・ｓ未満であると、基材上への塗布時にタレ等を生じやすく、目的とする膜厚を得ることが困難となる場合があり、５００００ｍＰａ・ｓを超えると、塗装作業性が悪くなる場合があり、得られるプライマー塗布膜（Ａｐ）の膜厚が均一とならず、表面平滑性等に劣る場合がある。より好ましい下限は、１ｍＰａ・ｓであり、より好ましい上限は、３００００ｍＰａ・ｓである。
上記プライマー用被覆組成物において、上記含フッ素重合体（ａ）は、平均粒子径が０．０１〜５μｍであるものが好ましい。上記耐熱性樹脂は、上記プライマー用被覆組成物中に粒子として分散している場合、その平均粒子径が０．５〜８μｍであるものが好ましい。
上記プライマー用被覆組成物において、上記耐熱性樹脂としては、上記含フッ素積層体が有するプライマー層（Ａ）について上述したように、ＰＥＳ、ＰＡＩ及び／又はＰＩが好ましく、ＰＡＩ及び／又はＰＩがより好ましく、ＰＥＳ、並びに、ＰＡＩ及び／又はＰＩが更に好ましい。
上記プライマー用被覆組成物において、上記ＰＥＳは、ＰＥＳ、並びに、ＰＡＩ及び／又はＰＩの合計量の６５〜８５質量％であることが好ましい。６５質量％未満であると、得られる含フッ素積層体の耐水蒸気性が低下するおそれがあり、８５質量％を超えると、耐食性が低下するおそれがある。
上記ＰＥＳの比率は、上述の耐熱性樹脂が、通常、後述の含フッ素積層体の形成時に行う焼成においても分解しないので、含フッ素積層体が有するプライマー層（Ａ）においても実質的に同じ比率である。
上記プライマー用被覆組成物において、上記耐熱性樹脂は、上記耐熱性樹脂及び含フッ素重合体（ａ）の固形分合計量の１５〜５０質量％であることが好ましい。
本明細書において、上記「固形分」とは、２０℃において固体であるものを意味する。
本明細書において、上記「上記耐熱性樹脂及び含フッ素重合体（ａ）の固形分合計量」とは、プライマー用被覆組成物を基材上に塗布したのち８０〜１００℃以下の温度で乾燥し、３８０〜４００℃で４５分間焼成した後の残渣における上記耐熱性樹脂と含フッ素重合体（ａ）との合計質量を意味する。
上記耐熱性樹脂は、上記耐熱性樹脂及び含フッ素重合体（ａ）の固形分合計量の１５質量％未満であると、得られる含フッ素積層体におけるプライマー層（Ａ）と基材との密着力が充分ではない場合がある。５０質量％を超えると、得られる含フッ素積層体におけるプライマー層（Ａ）と含フッ素層（Ｂ）との密着性が充分ではない場合がある。より好ましい下限は、２０質量％であり、より好ましい上限は、４０質量％である。
上記プライマー用被覆組成物は、上記含フッ素重合体（ａ）と耐熱性樹脂とともに、塗装作業性や得られる含フッ素積層体の耐食性及び耐水蒸気性をより向上させることを目的として、更に、上述の含フッ素層（Ｂ）における充填材以外の添加剤類からなるものであってもよい。
上記添加剤類としては特に限定されず、例えば、レベリング剤、固体潤滑剤、沈降防止剤、水分吸収剤、表面調整剤、チキソトロピー性付与剤、粘度調節剤、ゲル化防止剤、紫外線吸収剤、光安定剤、可塑剤、色分かれ防止剤、皮張り防止剤、スリ傷防止剤、防カビ剤、抗菌剤、酸化防止剤、帯電防止剤、シランカップリング剤等が挙げられる。
上記工程（ｉ）は、基材上にプライマー用被覆組成物を塗布することよりプライマー塗布膜（Ａｐ）を形成するものである。
上記基材は、必要に応じ、脱脂処理、粗面化処理等の表面処理を行ったものであってもよい。上記粗面化処理の方法としては特に限定されず、例えば、酸又はアルカリによるケミカルエッチング、陽極酸化（アルマイト処理）、サンドブラスト等が挙げられる。上記表面処理は、上記プライマー用被覆組成物をハジキを生じず均一に塗布することができる点、及び、基材とプライマー塗布膜（Ａｐ）との密着性が向上する点から、行うことが好ましい。
上記塗布の方法としては特に限定されず、上記プライマー用被覆組成物が液状である場合、例えば、スプレー塗装、ロール塗装、ドクターブレードによる塗装、ディップ（浸漬）塗装、含浸塗装、スピンフロー塗装、カーテンフロー塗装等が挙げられ、なかでも、スプレー塗装が好ましい。上記プライマー用被覆組成物が粉体である場合、静電塗装、流動浸漬法、ロトライニング法等が挙げられ、なかでも、静電塗装が好ましい。
上記工程（ｉ）は、基材上に上記プライマー用被覆組成物を塗布することより上記プライマー塗布膜（Ａｐ）を形成するものであればよく、上記塗布の後、上述の工程（ｉｉ）を行う前に焼成するものであってもよいし、焼成しないものであってもよいし、また、上記プライマー用被覆組成物が液状である場合、更に、上記塗布の後、乾燥するものであってもよいし、乾燥しないものであってもよい。
上記乾燥は、７０〜３００℃の温度で５〜６０分間行うことが好ましい。上記焼成は、２６０〜４１０℃の温度で１０〜３０分間行うことが好ましい。
上記プライマー用被覆組成物は、液状である場合、基材上に塗布したのち、通常、乾燥を行うものであることが好ましく、後述の工程（ｉｉｉ）において塗布膜積層体の焼成を行うので、焼成を行わないものであることがより好ましい。
上記プライマー用被覆組成物は、粉体である場合、基材上に塗布したのち、通常、焼成を行うものであることが好ましい。
上記プライマー塗布膜（Ａｐ）は、基材上に上記プライマー用被覆組成物を塗布することより形成されるものである。上記プライマー塗布膜（Ａｐ）は、上記工程（ｉ）において、上記塗布のみにより形成されたものであってもよいし、上記塗布の後、乾燥することにより形成されたものであってもよいし、上記塗布の後、必要に応じて乾燥した後、焼成することにより形成されるものであってもよい。上記プライマー塗布膜（Ａｐ）は、得られる含フッ素積層体においてプライマー層（Ａ）となる。
上記工程（ｉ）は、以下、「工程（１）」ということがある。
上記工程（ｉｉ）は、上記プライマー塗布膜（Ａｐ）上に充填材含有組成物を塗布することより含フッ素塗布膜（Ｂｐ）を形成するものである。
上記充填材含有組成物は、溶融加工性含フッ素重合体（ｂ）と充填材とからなるものである。上記充填材含有組成物は、液状の充填材含有液状組成物であることが好ましく、溶融加工性含フッ素重合体（ｂ）と充填材と液状媒体とからなるものであることが好ましい。上記液状媒体は、通常、水及び／又は有機液体からなるものである。
上記充填材含有液状組成物の液状媒体が主に有機液体からなるものである場合、上記溶融加工性含フッ素重合体（ｂ）は、上記液状媒体に粒子として分散したもの、及び／又は、上記液状媒体に溶解したものであり、上記充填材は、上記液状媒体に粒子として分散したものである。上記有機液体としては特に限定されず、例えば、上記プライマー用被覆組成物の液状媒体として用い得る有機液体と同じもの等が挙げられる。
上記充填材含有液状組成物の液状媒体が主に水からなるものである場合、上記溶融加工性含フッ素重合体（ｂ）と充填材とは、液状媒体に粒子として分散したものである。上記充填材含有液状組成物としては、上記液状媒体が有機液体からなるものであってもよいが、環境問題の点から、上記液状媒体が主に水からなる充填材含有水性分散体であることが好ましい。上記充填材含有水性分散体において、上記液状媒体は、主として水からなるものであれば、低分子量のアルコール等の水溶性有機液体を含むものであってもよいが、水のみからなるものが好ましい。
上記充填材含有組成物は、上記液状媒体が主に水からなるものである場合、通常、上記溶融加工性含フッ素重合体（ｂ）からなる粒子を分散安定化させることを目的として、界面活性剤を添加してなるものである。上記界面活性剤としては特に限定されず、例えば、上記プライマー用被覆組成物に用い得る界面活性剤と同じもの等が挙げられる。
上記充填材含有組成物の粘度は、上記プライマー用被覆組成物が液状のものである場合と同様、０．１〜５００００ｍＰａ・ｓであることが好ましい。より好ましい下限は、１ｍＰａ・ｓであり、より好ましい上限は、３００００ｍＰａ・ｓである。
上記充填材含有組成物において、上記溶融加工性含フッ素重合体（ｂ）からなる粒子は、平均粒子径が０．０１〜５μｍであるものが好ましい。上記充填材は、平均粒子径が１〜１００μｍであるものが好ましい。
上記充填材含有組成物は、溶融加工性含フッ素重合体（ｂ）と充填材とともに、塗装作業性や得られる含フッ素積層体の耐食性及び耐水蒸気性をより向上させること、上記充填材を含フッ素層（Ｂ）中に均一に分散させること等を目的として、更に、上述のプライマー用被覆組成物に用い得る添加剤類と同様の添加剤類からなるものであってもよい。上記充填材含有組成物は、光輝性偏平顔料等の上記充填材を分散安定化させることを目的として、顔料分散剤を添加してなるものであることが好ましい。
上記工程（ｉｉ）は、上記プライマー塗布膜（Ａｐ）上に充填材含有組成物を塗布することより含フッ素塗布膜（Ｂｐ）を形成するものである。
上記塗布の方法としては特に限定されず、例えば、上記プライマー用被覆組成物が液状である場合の塗布の方法と同じ方法等が挙げられ、なかでも、スプレー塗装が好ましい。
上記工程（ｉｉ）は、上記プライマー塗布膜（Ａｐ）上に上記充填材含有組成物を塗布することより上記含フッ素塗布膜（Ｂｐ）を形成するものであればよく、上記塗布の後、上述の工程（ｉｉｉ）を行う前に乾燥するものであってもよいし、乾燥しないものであってもよいし、更に、焼成するものであってもよいし、焼成しないものであってもよい。
上記工程（ｉｉ）における乾燥は、上記工程（ｉ）における乾燥と同様、７０〜３００℃の温度で５〜６０分間行うことが好ましい。
上記工程（ｉｉ）における焼成は、上記工程（ｉ）における焼成と同様、２６０〜４１０℃の温度で１０〜３０分間行うことが好ましい。
上記充填材含有組成物は、上記プライマー塗布膜（Ａｐ）上に塗布したのち、通常、乾燥を行うものであることが好ましく、後述の工程（ｉｉｉ）において塗布膜積層体の焼成を行うので、焼成を行わないものであることがより好ましい。
含フッ素塗布膜（Ｂｐ）は、上記プライマー塗布膜（Ａｐ）上に上記充填材含有組成物を塗布することより形成されるものである。上記含フッ素塗布膜（Ｂｐ）は、上記工程（ｉｉ）において、上記塗布のみにより形成されたものであってもよいし、上記塗布の後、乾燥することにより形成されたものであってもよいし、上記塗布の後、必要に応じて乾燥した後、焼成することにより形成されるものであってもよい。上記含フッ素塗布膜（Ｂｐ）は、得られる含フッ素積層体において含フッ素層（Ｂ）となる。
上記工程（ｉｉ）において、上記充填材含有組成物は、液状である充填材含有液状組成物であることが好ましく、上記工程（ｉｉ）は、上記プライマー塗布膜（Ａｐ）上に上記充填材含有液状組成物を塗布することより上記含フッ素塗布膜（Ｂｐ）を形成する工程（以下、「工程（２）」ということがある。）であることが好ましい。
上記工程（ｉｉｉ）は、上記含フッ素塗布膜（Ｂｐ）上に溶融加工性溶融加工性含フッ素組成物を用いて含フッ素膜（Ｃｐ）を形成して、含フッ素積層体を形成するものである。
上記溶融加工性含フッ素組成物は、溶融加工性含フッ素重合体（ｃ）からなるものである。
上記溶融加工性含フッ素組成物は、フィルム状、シート状等の成形物であってもよいし、液状であってもよいし、粉体であってもよい。上記溶融加工性含フッ素組成物は、液状である場合、溶融加工性含フッ素重合体（ｃ）とともに、液状媒体からなるものである。上記液状媒体は、通常、水及び／又は有機液体からなるものである。
上記溶融加工性含フッ素組成物の液状媒体が主に有機液体からなるものである場合、上記溶融加工性含フッ素重合体（ｃ）は、上記液状媒体に粒子として分散したもの、及び／又は、上記液状媒体に溶解したものである。上記有機液体としては特に限定されず、例えば、上記プライマー用被覆組成物の液状媒体として用い得る有機液体と同じもの等が挙げられる。
上記溶融加工性含フッ素組成物の液状媒体が主に水からなるものである場合、上記溶融加工性含フッ素重合体（ｃ）は、上記液状媒体に粒子として分散したものである。上記溶融加工性含フッ素組成物は、上記液状媒体が主に水からなる水性分散体である場合、通常、上記溶融加工性含フッ素重合体（ｃ）からなる粒子を分散安定化させることを目的として、界面活性剤を添加してなるものである。上記界面活性剤としては特に限定されず、例えば、上述のプライマー用被覆組成物に用い得る界面活性剤と同じもの等が挙げられる。
上記溶融加工性含フッ素重合体（ｃ）は、上記液状媒体に粒子として分散したものである場合、平均粒子径が０．０１〜５μｍであるものが好ましく、上記溶融加工性含フッ素組成物が粉体である場合、平均粒子径が５〜５０μｍであるものが好ましい。上記溶融加工性含フッ素組成物が粉体である場合、上記溶融加工性含フッ素重合体（ｃ）からなる粒子の平均粒子径のより好ましい下限は、１０μｍであり、より好ましい上限は、３０μｍである。
上記溶融加工性含フッ素組成物は、少ない塗装回数で厚い塗布膜を得ることが容易であることから、粉体である含フッ素粉体であるものが好ましい。
上記溶融加工性含フッ素組成物は、溶融加工性含フッ素重合体（ｃ）とともに、更に、塗装作業性や得られる含フッ素積層体の耐食性及び耐水蒸気性をより向上させることを目的として、上述のプライマー用被覆組成物に用い得る添加剤類と同様の添加剤類からなるものであってもよい。
上記工程（ｉｉｉ）は、上記含フッ素塗布膜（Ｂｐ）上に上記溶融加工性含フッ素組成物を用いて含フッ素膜（Ｃｐ）を形成して、含フッ素積層体を形成するものである。
上記含フッ素膜（Ｃｐ）を形成する方法は、上記溶融加工性含フッ素組成物が粉体である場合、上記含フッ素塗布膜（Ｂｐ）上に上記溶融加工性含フッ素組成物を塗布することによりなるものである。上記溶融加工性含フッ素組成物が粉体である場合、上記塗布の方法としては特に限定されず、例えば、上述のプライマー用被覆組成物が粉体である場合の塗布の方法と同じ方法等が挙げられ、なかでも、静電塗装が好ましい。
上記含フッ素膜（Ｃｐ）を形成する方法は、上記溶融加工性含フッ素組成物が液状である場合、上記含フッ素塗布膜（Ｂｐ）上に上記溶融加工性含フッ素組成物を塗布することよりなるものである。上記溶融加工性含フッ素組成物が液状である場合、上記塗布の方法としては特に限定されず、例えば、上記プライマー用被覆組成物が液状である場合の塗布の方法と同じ方法等が挙げられ、なかでも、スプレー塗装が好ましい。
上記含フッ素膜（Ｃｐ）を形成する方法は、上記溶融加工性含フッ素組成物が液状である場合、上記含フッ素塗布膜（Ｂｐ）上に上記溶融加工性含フッ素組成物を塗布するものであればよく、上記塗布の後、乾燥するものであってもよいし、乾燥していないものであってもよい。
上記乾燥は、上記工程（ｉ）及び上記工程（ｉｉ）における乾燥と同様、７０〜３００℃の温度で５〜６０分間行うことが好ましい。
上記含フッ素膜（Ｃｐ）を形成する方法は、溶融加工性含フッ素組成物がフィルム状等の成形物である場合、例えば、従来公知の方法等により予め成形したフィルム状等の成形物を上記含フッ素塗布膜（Ｂｐ）上に載置し、加熱圧着する等の従来公知の方法等が挙げられる。
上記含フッ素膜（Ｃｐ）は、上記含フッ素塗布膜（Ｂｐ）上に上記溶融加工性含フッ素組成物を用いることにより形成されるものである。上記含フッ素膜（Ｃｐ）は、上記工程（ｉｉｉ）において、上記溶融加工性含フッ素組成物が液状である場合、上記塗布ののち必要に応じて乾燥することにより形成されるものであってもよいし、上記溶融加工性含フッ素組成物が成形物である場合、加熱圧着することにより形成されるものであってもよい。上記含フッ素膜（Ｃｐ）は、得られる含フッ素積層体における含フッ素層（Ｃ）となる。
上記工程（ｉｉｉ）は、上記含フッ素塗布膜（Ｂｐ）上に含フッ素膜（Ｃｐ）を形成して、含フッ素積層体を形成するものである。
上記含フッ素積層体を形成する方法は、上記溶融加工性含フッ素組成物が粉体又は液状である場合、上記含フッ素塗布膜（Ｂｐ）上に上記溶融加工性含フッ素組成物を塗布することより、上記含フッ素膜（Ｃｐ）を形成したのち、上記プライマー塗布膜（Ａｐ）、上記含フッ素塗布膜（Ｂｐ）及び上記含フッ素膜（Ｃｐ）からなる塗布膜積層体を焼成する方法等が挙げられる。
上記焼成は、上記工程（ｉ）及び上記工程（ｉｉ）における焼成と同様、２６０〜４１０℃の温度で１０〜３０分間行うことが好ましい。
溶融加工性含フッ素組成物がフィルム状等の成形物である場合、上記工程（ｉｉｉ）は、上記含フッ素膜（Ｃｐ）を形成すると同時に、上記含フッ素積層体を得ることができる。
上記含フッ素積層体を形成する方法において、上記溶融加工性含フッ素組成物が成形物である場合、上記プライマー塗布膜（Ａｐ）及び上記含フッ素塗布膜（Ｂｐ）は、それぞれ次の工程を行う前に焼成することにより形成されるものであることが好ましい。
上記工程（ｉｉｉ）は、上記溶融加工性含フッ素組成物として粉体からなる含フッ素粉体を用いるものが好ましく、上記含フッ素塗布膜（Ｂｐ）上に上記含フッ素粉体を塗布することより上記含フッ素膜（Ｃｐ）を形成する工程（以下、「工程（３）」ということがある。）、並びに、上記プライマー塗布膜（Ａｐ）、上記含フッ素塗布膜（Ｂｐ）及び上記含フッ素膜（Ｃｐ）からなる塗布膜積層体を焼成することにより含フッ素積層体を形成する工程（以下、「工程（４）」ということがある。）であることが好ましい。
本発明の含フッ素積層体形成方法は、上記プライマー塗布膜（Ａｐ）を形成する工程（ｉ）の後、又は、上記含フッ素塗布膜（Ｂｐ）を形成する工程（ｉｉ）の後に、文字、図面等を印刷する工程を有するものであってもよい。上記文字、図面等は、例えば、後述の被覆物品が炊飯釜である場合、水の量を示す文字と線等である。
上記印刷の方法としては特に限定されず、例えば、パット転写印刷が挙げられる。上記印刷に用いる印刷インキとしては特に限定されず、例えば、ＰＥＳとＴＦＥホモポリマーと酸化チタンとからなる組成物が挙げられる。
本発明の含フッ素積層体形成方法は、上述の含フッ素積層体を形成するためのものであって、
基材上に含フッ素重合体（ａ）と耐熱性樹脂とからなるプライマー用被覆組成物を塗布することよりプライマー塗布膜（Ａｐ）を形成する工程（１）、
上記プライマー塗布膜（Ａｐ）上に溶融加工性含フッ素重合体（ｂ）と充填材とからなる充填材含有液状組成物を塗布することより含フッ素塗布膜（Ｂｐ）を形成する工程（２）、
上記含フッ素塗布膜（Ｂｐ）上に溶融加工性含フッ素重合体（ｃ）からなる含フッ素粉体を塗布することにより含フッ素膜（Ｃｐ）を形成する工程（３）、並びに、
上記プライマー塗布膜（Ａｐ）、上記含フッ素塗布膜（Ｂｐ）及び上記含フッ素膜（Ｃｐ）からなる塗布膜積層体を焼成することにより上記含フッ素積層体を形成する工程（４）
を含むものであることが好ましい。
本発明の含フッ素積層体形成方法は、溶融加工性含フッ素重合体（ｃ）からなる含フッ素粉体を塗布することにより、少ない塗装回数で、含フッ素積層体における上記含フッ素層（Ｃ）を上述のような厚い膜とすることができる。本発明の含フッ素積層体形成方法により得られる含フッ素積層体は、上述したように含フッ素層（Ｂ）と含フッ素層（Ｃ）との密着性が優れ、耐食性及び耐水蒸気性に優れたものであると同時に、上記含フッ素層（Ｃ）が、上述のような厚い膜であるので、特に耐摩耗性に優れたものである。
本発明の含フッ素積層体形成方法は、また、充填材含有液状組成物において充填材の分散がよいので、得られる含フッ素積層体の含フッ素層（Ｂ）において充填材が均一に分散し、充填材が有する光輝感等の特性を安定して発現することができる。
本発明の含フッ素積層体形成方法は、上述の構成からなるものであるので、基材上に含フッ素積層体を形成する方法として好適である。
本発明の被覆物品は、基材と、上述の含フッ素積層体とからなるものである。上記基材としては特に限定されず、例えば、鉄、アルミニウム、銅等の金属単体及びこれらの合金類等の金属；ホーロー、ガラス、セラミックス等の非金属無機材料等が挙げられる。上記合金類としては、ステンレス等が挙げられる。上記基材としては、金属が好ましく、アルミニウム及びステンレスがより好ましい。
本発明の被覆物品としては特に限定されず、含フッ素重合体が有する非粘着性、耐熱性、滑り性等を利用した用途に使用することができ、例えば、非粘着性を利用したものとして、フライパン、圧力鍋、鍋、グリル鍋、炊飯釜、オーブン、ホットプレート、パン焼き型、包丁、ガステーブル等の調理器具；電気ポット、製氷トレー、金型、レンジフード等の厨房用品等が挙げられ、滑り性を利用したものとして、のこぎり、やすり等の工具；アイロン等の家庭用品；金属箔等が挙げられる。なかでも、耐食性と耐水蒸気性が要求される炊飯釜、圧力鍋及びグリル鍋であることが好ましく、意匠性が要求される炊飯釜であることがより好ましい。  Fluorine-containing polymers such as tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer [PFA] have a low coefficient of friction and are excellent in properties such as non-adhesiveness, chemical resistance, and heat resistance. It is widely used for surface processing of food industry supplies, kitchen utensils such as frying pans and pans, household items such as irons, electrical industry supplies, and machine industry supplies.
  Surface processing is performed by forming a layer made of a fluorine-containing polymer on a substrate. If the fluorine-containing polymer to be used is melt-processable such as PFA, a thick layer is produced by a general industrial production method. The surface of the resulting article can easily exhibit various properties of the fluorine-containing polymer.
  Fluorine-containing polymers, however, have poor adhesion to the substrate due to their non-stick properties. For the purpose of improving the adhesion, a primer layer obtained by preliminarily applying a primer containing a binder resin such as a heat-resistant resin and a fluorine-containing polymer as an undercoat, and a primer layer obtained and a layer comprising a fluorine-containing polymer A laminate having
  In such a laminate, a filler may be added at the time of formation for the purpose of imparting design properties, improving strength, and the like.For example, when a glitter feeling is required as a design property, a glitter filler is added. Yes.
  As a laminate having a glitter feeling, there is a laminate having a two-layer structure of a primer layer to which mica is added as a glitter filler and a topcoat layer made of PFA formed thereon. However, this laminate has a problem in that mica tends to settle in the primer layer and the glitter is not sufficient.
  In order to solve this problem, it has been proposed to use aluminum powder instead of mica as a glitter filler, but aluminum powder is more likely to settle than mica, and when produced in mass production, the resulting laminate has a glitter feeling. In addition to being unstable, there was a problem of having an adverse effect on corrosion resistance.
  As a laminate having a stable glitter and excellent corrosion resistance, a layer composed of polytetrafluoroethylene [PTFE] and mica is used as an intermediate layer, and a primer layer composed of a binder resin and a fluorine-containing polymer thereunder And a laminate having a three-layer structure in which a topcoat layer is formed using a powder paint made of PFA (for example, Japanese Patent Application Laid-Open No. 7-11946 (page 1-3) and Japanese Patent No. 25933043). (See page 1-3).)
  This laminate is stable in glitter even when mass-produced. However, when the article comprising the laminate and the substrate is used for a kitchen appliance such as a pan, the steam resistance is not sufficient, and there is a possibility that blisters are generated by the steam.
  Among the laminates to which a filler is added at the time of formation, a primer layer using aluminum oxide as a filler is formed on a base material as having excellent scratch resistance, and PFA or the like is formed on the primer layer. An intermediate layer made of a melt-processable fluorine-containing polymer, PTFE and aluminum oxide is formed, and a top coat layer made of PTFE is formed on the intermediate layer (for example, Japanese Patent No. 2644380 (No. (See page 1-4).)
  However, this laminate has an adverse effect on the corrosion resistance of the base material because aluminum oxide may settle in the primer layer, and the topcoat layer is made of PTFE. It was not easy to obtain a thick layer, and there was a problem that durability such as wear resistance was inferior.
Summary of invention
  An object of the present invention is to provide a fluorine-containing laminate that is excellent in corrosion resistance, water vapor resistance, and abrasion resistance in view of the above-described situation, and that can stably exhibit the properties of a filler such as glitter even in mass production and its formation. It is to provide a method and a coated article.
  The present invention includes a primer layer (A) composed of a fluoropolymer (a) and a heat-resistant resin, a fluorine-containing layer (B) composed of a melt-processable fluoropolymer (b) and a filler, and a melt A fluorine-containing laminate having a fluorine-containing layer (C) made of a workable fluorine-containing polymer (c), wherein the primer layer (A), the fluorine-containing layer (B), and the fluorine-containing layer (C) are These are fluorine-containing laminates laminated in this order.
  The present invention is a fluorine-containing laminate forming method for forming the fluorine-containing laminate,
A step (1) of forming a primer coating film (Ap) by applying a primer coating composition comprising a fluoropolymer (a) and a heat-resistant resin on a substrate;
Step (2) of forming a fluorine-containing coating film (Bp) by applying a filler-containing liquid composition comprising a melt-processable fluorine-containing polymer (b) and a filler on the primer coating film (Ap). ,
A step (3) of forming a fluorine-containing film (Cp) by applying a fluorine-containing powder comprising a melt-processable fluorine-containing polymer (c) on the fluorine-containing coating film (Bp), and
Step (4) of forming the fluorine-containing laminate by firing the coating film laminate comprising the primer coating film (Ap), the fluorine-containing coating film (Bp), and the fluorine-containing film (Cp).
It is a fluorine-containing laminated body formation method characterized by having.
Detailed Disclosure of the Invention
  The present invention is described in detail below.
  The fluorine-containing laminate of the present invention comprises a primer layer (A) comprising a fluorine-containing polymer (a) and a heat-resistant resin, and a fluorine-containing layer (B) comprising a melt-processable fluorine-containing polymer (b) and a filler. ), And a fluorine-containing layer (C) made of a melt-processable fluorine-containing polymer (c), the primer layer (A), the fluorine-containing layer (B), and the fluorine-containing layer (C) ) Are stacked in this order.
  The fluorine-containing laminate of the present invention does not contain a substrate described later.
  The said primer layer (A) in the fluorine-containing laminated body of this invention is suitable for forming on a base material. The primer layer (A) is obtained by applying a primer coating composition comprising a fluoropolymer (a) and a heat-resistant resin, which will be described later, onto a substrate, drying as necessary, and then firing. It is what The primer layer (A) has a difference in surface tension between the fluoropolymer (a) and the heat-resistant resin, so that the fluoropolymer (a) floats during firing and is far from the substrate. The fluoropolymer (a) is mainly arranged on the surface side at a distance, and the heat-resistant resin is mainly arranged on the substrate side.
  Since the said heat resistant resin has adhesiveness with a base material, the said primer layer (A) is excellent in the adhesiveness with respect to a base material. The primer layer (A) has an affinity for the fluorine-containing layer (B) described later because the fluorine-containing polymer (a) has an affinity for the melt-processable fluorine-containing polymer (b) described later. Is excellent. Thus, the said primer layer (A) has the outstanding adhesiveness with respect to both a base material and a fluorine-containing layer (B).
  The primer layer (A) is composed of a fluoropolymer (a) and a heat resistant resin.
  The fluoropolymer (a) is a polymer having a fluorine atom that is directly bonded to the carbon atom constituting the main chain or side chain. The fluoropolymer (a) may be non-melt processable or melt processable.
  The fluorine-containing polymer (a) is obtained by polymerizing a fluorine-containing monoethylenically unsaturated hydrocarbon (I).
  The above-mentioned “fluorinated monoethylenically unsaturated hydrocarbon (I)” (hereinafter referred to as “unsaturated hydrocarbon (I)”) is a vinyl group in which part or all of the hydrogen atoms are substituted by fluorine atoms. Is an unsaturated hydrocarbon having one in the molecule.
  In the unsaturated hydrocarbon (I), a part or all of hydrogen atoms not substituted by fluorine atoms are halogen atoms other than fluorine atoms such as chlorine atoms and / or fluoroalkyl groups such as trifluoromethyl groups. It may be substituted by. However, the unsaturated hydrocarbon (I) excludes trifluoroethylene described later.
  The unsaturated hydrocarbon (I) is not particularly limited, and examples thereof include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinylidene fluoride [VdF], and vinyl fluoride [ VF] and the like, and one or more of these can be used.
  The fluoropolymer (a) may be a homopolymer of the unsaturated hydrocarbon (I). Examples of the homopolymer of the unsaturated hydrocarbon (I) include, for example, tetrafluoroethylene homopolymer [TFE homopolymer], polychlorotrifluoroethylene [PCTFE], polyvinylidene fluoride [PVdF], polyvinyl fluoride [PVF]. ] Etc. are mentioned.
  The fluoropolymer (a) is also a copolymer of at least one kind of the unsaturated hydrocarbon (I) and an unsaturated compound (II) that can be copolymerized with the unsaturated hydrocarbon (I). It may be.
  The unsaturated compound (II) does not use a polymer obtained by polymerizing only one or more unsaturated compounds (II) as the fluoropolymer (a). A polymer obtained by polymerizing only one or two or more of the unsaturated hydrocarbons (I) as the unsaturated hydrocarbon (I) can be used as the fluoropolymer (a). Is different from the unsaturated hydrocarbon (I).
  The unsaturated compound (II) is not particularly limited, and examples thereof include trifluoroethylene [3FH]; monoethylenically unsaturated hydrocarbon having no halogen atom such as ethylene [Et] and propylene [Pr]. . These can use 1 type (s) or 2 or more types.
  The fluoropolymer (a) may be a copolymer of two or more unsaturated hydrocarbons (I). The copolymer of the two or more unsaturated hydrocarbons (I) and the copolymer of the at least one unsaturated hydrocarbon (I) and the unsaturated compound (II) are not particularly limited. Examples thereof include binary copolymers and ternary copolymers.
  The binary copolymer is not particularly limited, and examples thereof include a VdF / HFP copolymer, an Et / CTFE copolymer [ECTFE], an Et / HFP copolymer, and the like. The binary copolymer is also a TFE / HFP copolymer [FEP], a TFE / CTFE copolymer, a TFE / VdF copolymer, a TFE / 3FH copolymer, an Et / TFE copolymer [ETFE]. TFE copolymers such as TFE / Pr copolymer may be used. In the present specification, the “TFE copolymer” means a copolymer obtained by copolymerizing TFE and one or more monomers other than TFE. In the TFE copolymer, the proportion of other monomers other than TFE added to the TFE copolymer is usually 1 mass of the total mass of the TFE and the other monomers. % Is preferably exceeded.
  Examples of the ternary copolymer include VdF / TFE / HFP copolymer.
  The other monomer other than the TFE in the TFE copolymer may be another monomer (III) that can be copolymerized with the following TFE. The other monomer (III) has the following general formula
X (CF₂)_mO_nCF = CF₂
(Wherein X represents —H, —Cl or —F, m represents an integer of 1 to 6, and n represents an integer of 0 or 1) (however, HFP Except the following general formula:
C₃F₇O [CF (CF₃CF₂O]_p-CF = CF₂
(Wherein p represents an integer of 1 or 2), or the following general formula
X (CF₂)_qCY = CH₂
(Wherein X is the same as above, Y represents —H or —F, and q represents an integer of 1 to 6). These can use 1 type (s) or 2 or more types.
  Examples of such a TFE copolymer include TFE / perfluoro (alkyl vinyl ether) [PAVE] copolymer [PFA].
  The fluoropolymer (a) may also be modified polytetrafluoroethylene [modified PTFE]. In the present specification, the “modified PTFE” means a product obtained by copolymerizing a small amount of a comonomer with TFE so as not to impart melt processability to the obtained copolymer. The small amount of the comonomer is not particularly limited, and examples thereof include HFP and CTFE among the unsaturated hydrocarbons (I), and 3FH among the unsaturated compounds (II). Among other monomers (III), PAVE, perfluoro (alkoxy vinyl ether), (perfluoroalkyl) ethylene and the like can be mentioned. One kind or two or more kinds of the small amount of comonomer can be used.
  The ratio in which the small amount of the comonomer is added to the modified PTFE varies depending on the type thereof. For example, when PAVE, perfluoro (alkoxy vinyl ether) or the like is used, the TFE and the small amount of the comonomer are usually used. It is preferable that it is 0.001-1 mass% of the total mass with a weight body.
  The fluoropolymer (a) may be one type or two or more types, and is a copolymer of one type of the unsaturated hydrocarbon (I) and the unsaturated hydrocarbon (I). Or a mixture of two or more of the above unsaturated hydrocarbon (I) copolymers.
  Examples of the mixture include a mixture of a TFE homopolymer and the TFE copolymer, a mixture of two or more types of copolymers belonging to the TFE copolymer, and the like. Examples thereof include a mixture of TFE homopolymer and PFA, a mixture of TFE homopolymer and FEP, a mixture of TFE homopolymer, PFA and FEP, a mixture of PFA and FEP, and the like.
  The fluoropolymer (a) also contains a perfluoroalkyl group-containing ethylenically unsaturated monomer (IV) having a perfluoroalkyl group (hereinafter referred to as “unsaturated monomer (IV)”). It may be obtained by polymerization. The unsaturated monomer (IV) has the following general formula

  (In the formula, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms;¹Represents —H or an alkyl group having 1 to 10 carbon atoms;²Represents an alkylene group having 1 to 10 carbon atoms, and R³Represents —H or a methyl group, R⁴Represents an alkyl group having 1 to 17 carbon atoms, r represents an integer of 1 to 10, and s represents an integer of 0 to 10. ).
  The fluoropolymer (a) may be a homopolymer of the unsaturated monomer (IV), or the unsaturated monomer (IV) and the unsaturated monomer (IV). ) And a copolymer with the monomer (V) that can be copolymerized.
  The monomer (V) is not particularly limited, and examples thereof include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol di (meth) acrylate, N-methylolpropane acrylamide, and (meth) acryl. (Meth) acrylic acid derivatives such as acid amides and alkyl esters of (meth) acrylic acid having an alkyl group having 1 to 20 carbon atoms; ethylene, vinyl chloride, vinyl fluoride, styrene, α-methylstyrene, p-methyl Substituted or unsubstituted ethylene such as styrene; alkyl vinyl ethers having 1 to 20 carbon atoms in the alkyl group; vinyl ethers such as halogenated alkyl vinyl ethers having 1 to 20 carbon atoms in the alkyl group; Vinyl ketones such as vinyl alkyl ketones of ˜20; Aliphatic unsaturated polycarboxylic acids and derivatives thereof such as phosphate; butadiene, isoprene, polyenes such as chloroprene.
  The fluoropolymer (a) can be obtained, for example, by using a conventionally known polymerization method such as emulsion polymerization.
  As the fluorine-containing polymer (a), a TFE homopolymer, a modified PTFE, and the TFE copolymer are preferable because the resulting fluorine-containing laminate is excellent in corrosion resistance and water vapor resistance. As the TFE copolymer, FEP and PFA are preferable.
  As the fluoropolymer (a), TFE homopolymer, modified PTFE, FEP and / or PFA are more preferable.
  As the fluoropolymer (a), those containing a TFE copolymer are more preferred from the viewpoint of excellent adhesion between the resulting primer layer (A) and a fluorolayer (B) described later. Since the fluorine-containing laminate having excellent adhesion between the primer layer (A) and the fluorine-containing layer (B) described below is excellent in water vapor resistance, coating defects such as blisters are generated even in the presence of water vapor. Can be suppressed. Examples of the fluoropolymer (a) containing a TFE copolymer include PFA alone, a mixture of TFE homopolymer and FEP, a mixture of TFE homopolymer and PFA, a mixture of modified PTFE and FEP, and modified PTFE. And a mixture of PFA and the like.
  As the fluorine-containing polymer (a) in the primer layer (A), the resulting fluorine-containing laminate is excellent in corrosion resistance and water vapor resistance, and the primer layer (A) has adhesion to the fluorine-containing layer (B) described later. From the viewpoint of superiority, PFA alone, a mixture of TFE homopolymer and PFA, a mixture of TFE homopolymer and FEP are preferred, and a mixture of TFE homopolymer and FEP is more preferred.
  The said primer layer (A) consists of a heat resistant resin with the above-mentioned fluoropolymer (a).
  The heat-resistant resin may be any resin that is generally recognized as having heat resistance, and is preferably a resin having a continuous usable temperature of 150 ° C. or higher. However, the above-mentioned fluoropolymer (a) is excluded as the heat-resistant resin.
  The heat resistant resin is not particularly limited, and examples thereof include polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherimide resin, polyetheretherketone resin, aromatic polyester resin, and polyarylene sulfide resin. . As said heat resistant resin, 1 type (s) or 2 or more types can be used.
  The polyamide-imide resin [PAI] is a resin composed of a polymer having an amide bond and an imide bond in the molecular structure. The PAI is not particularly limited. For example, a reaction between an aromatic diamine having an amide bond in the molecule and an aromatic tetravalent carboxylic acid such as pyromellitic acid; an aromatic trivalent carboxylic acid such as trimellitic anhydride; It consists of a high molecular weight polymer obtained by a reaction with a diamine such as 4,4-diaminophenyl ether or a diisocyanate such as diphenylmethane diisocyanate; a reaction between a dibasic acid having an aromatic imide ring in the molecule and a diamine. Examples thereof include resins. As said PAI, what consists of a polymer which has an aromatic ring in a principal chain from the point which is excellent in heat resistance is preferable.
  The polyimide resin [PI] is a resin made of a polymer having an imide bond in the molecular structure. The PI is not particularly limited, and examples thereof include a resin made of a high molecular weight polymer obtained by a reaction of an aromatic tetravalent carboxylic anhydride such as pyromellitic anhydride. As said PI, what consists of a polymer which has an aromatic ring in a principal chain from the point which is excellent in heat resistance is preferable.
  The polyethersulfone resin [PES] has the following general formula:

It is resin which consists of a polymer which has a repeating unit represented by these. The PES is not particularly limited, and examples thereof include a resin made of a polymer obtained by polycondensation of dichlorodiphenyl sulfone and bisphenol.
  The above heat-resistant resin has excellent adhesion to the base material and has sufficient heat resistance even at the firing temperature when forming the fluorine-containing laminate, and the resulting fluorine-containing laminate has corrosion resistance and water vapor resistance. From the viewpoint of excellent properties, PAI, PI and / or PES are preferable. The above "PAI, PI and / or PES" means PAI alone, PI alone, PES alone, a mixture of PAI and PI, a mixture of PES and PAI, a mixture of PES and PI, PES and PAI and PI. It means a mixture.
  Each of PAI, PI, and PES may be composed of one type or two or more types.
  As said heat resistant resin, PAI and / or PI are more preferable from the point which is excellent in adhesiveness with a base material, and heat resistance. The above “PAI and / or PI” means PAI alone, PI alone, or a mixture of PAI and PI.
  As said heat resistant resin, PES and PAI and / or PI are still more preferable from the point which is excellent in corrosion resistance and water vapor resistance. The above-mentioned “PES and PAI and / or PI” means a mixture of PES and PAI, a mixture of PES and PI, or a mixture of PES, PAI and PI. The heat-resistant resin is particularly preferably a mixture of the PES and PAI.
  In the primer layer (A), the PES is preferably 65 to 85% by mass of the total amount of PES and PAI and / or PI.
  The primer layer (A) is composed of the fluoropolymer (a) and the heat-resistant resin. The heat-resistant resin is a solid content of the heat-resistant resin and the fluoropolymer (a). It is preferable that it is 15-50 mass% of a total amount.
  The primer layer (A) is mainly composed of a polymer component and additives described later. The primer layer (A) is preferably one in which the polymer component is a fluoropolymer (a) and a heat resistant resin. In the present specification, the “primer layer (A) is a polymer component comprising a fluoropolymer (a) and a heat-resistant resin” means that the polymer in the primer layer (A) is a fluoropolymer (a ) And heat resistant resin only. The primer layer (A) has excellent adhesion to both the base material and the fluorine-containing layer (B) described later, because the polymer component is a fluoropolymer (a) and a heat-resistant resin. It has it efficiently.
  The primer layer (A) is a polymer component comprising a fluorine-containing polymer (a) and a heat-resistant resin from the viewpoint of efficiently having excellent adhesion to both the substrate and the fluorine-containing layer (B) described later. In view of the fact that the corrosion resistance and water vapor resistance of the fluorine-containing laminate can be further improved, the fluorine-containing laminate (a) and the heat-resistant resin are further composed of other resins. May be.
  The other resin is not particularly limited, and examples thereof include phenol resin, urea resin, epoxy resin, urethane resin, melamine resin, polyester resin, polyether resin, acrylic resin, acrylic silicone resin, silicone resin, and silicone polyester resin. Can be mentioned. As said other resin, since it is obtained by baking the fluorine-containing laminated body of this invention, it is preferable that it is heat resistant.
  The fluorine-containing laminate of the present invention has a fluorine-containing layer (B) comprising a melt-processable fluorine-containing polymer (b) and a filler.
  In the fluorine-containing laminate of the present invention, the fluorine-containing layer (B) is formed on the primer layer (A). The fluorine-containing layer (B) has a fluorine-containing layer (C) described later laminated thereon.
  The melt processable fluorine-containing polymer (b) is a polymer having a melt processability among polymers having fluorine atoms directly bonded to carbon atoms constituting the main chain or side chain.
  As said melt-processable fluoropolymer (b), what has melt processability among the above-mentioned fluoropolymers (a) can be used. The melt-processable fluorine-containing polymer (b) is a fluorine-containing laminate in which the fluorine-containing layer (B) is excellent in adhesion between the primer layer (A) described above and the fluorine-containing layer (C) described later. Has a melting point of 150 to 350 ° C., and a melt viscosity at a temperature 50 ° C. higher than the melting point is 10 from the viewpoint of excellent corrosion resistance and water vapor resistance.⁶(Pascal / second) or less is preferable, and the above-mentioned TFE copolymer is preferable. The melt-processable fluoropolymer (b) may be one type or two or more types. The melt-processable fluoropolymer (b) is more preferably PFA and / or FEP. The above-mentioned “PFA and / or FEP” means that each of PFA and FEP may be used alone or a mixture thereof. The melt-processable fluoropolymer (b) is more preferably PFA from the viewpoint of excellent heat resistance.
  The fluorine-containing layer (B) is composed of a filler together with the melt-processable fluorine-containing polymer (b).
  In the present specification, the above-mentioned “filler” is used for the purpose of imparting characteristics, improving physical properties, increasing the amount, etc. to the obtained fluorine-containing laminate, and does not dissolve in the liquid medium in the filler-containing composition described later. Means things. Examples of the above properties and physical properties include strength, durability, weather resistance, and flame retardancy.
  The filler is not particularly limited. For example, wood powder, quartz sand, carbon black, clay, talc, extender pigment, glittering flat pigment, scaly pigment, glass, various reinforcing materials, various fillers, conductive filler. Etc. As the filler, a glitter filler is preferred when the fluorine-containing laminate of the present invention is required to have glitter. The “brilliant filler” is a filler capable of imparting glitter to the resulting fluorine-containing laminate.
  Examples of the glitter filler include those classified into glitter flat pigments and scale pigments, glass, and the like, and these can be used alone or in combination of two or more. It does not specifically limit as what is classified into the said luster flat pigment or a scale-like pigment, For example, a mica, a metal powder, etc. are mentioned. The glass is not particularly limited, and examples thereof include glass beads, glass bubbles, glass flakes, and glass fibers. One or two or more types can be used as the glass classified into the glittering flat pigment and the scaly pigment and the glass.
  As the filler, a glittering filler made of mica, metal powder and / or glass beads is more preferable. Such glittering fillers only need to contain mica, metal powder and / or glass beads, may be mica, metal powder and / or glass beads only, mica, metal powder and / or It may be glass beads and other fillers that can give a glittering feeling to the fluorine-containing laminate. The above “mica, metal powder and / or glass beads” means mica alone, metal powder alone, glass beads alone, a mixture of mica and metal powder, a mixture of mica and glass beads, or the like, or metal powder and glass beads Means a mixture.
  As mica, metal powder and glass, generally, there may be a thing which cannot give a glittering feeling to the obtained fluorine-containing laminate, but the above-mentioned “shining filler comprising mica, metal powder and / or glass beads” The mica, the metal powder and / or the glass beads in can give a glittering feeling.
  The metal powder is not particularly limited, and examples thereof include powders of simple metals such as aluminum, iron, tin, zinc, and copper; powders of alloys such as aluminum alloy and stainless steel. The shape of the metal powder is not particularly limited, and examples thereof include a particulate shape and a flake shape. The flake shape is preferable from the viewpoint of excellent glitter.
  The filler is more preferably a glitter filler made of mica and / or aluminum powder from the viewpoint of excellent luster and economy. Examples of such glittering fillers include mica alone, aluminum powder alone, or a mixture of mica and aluminum powder. The shape of the aluminum powder is preferably a flake shape. The filler is particularly preferably a glittering filler made of mica from the viewpoint that the resulting fluorine-containing laminate is excellent in corrosion resistance.
  In the said fluorine-containing layer (B), it is preferable that the said filler is 0.001-10 mass% with respect to solid content of a melt-processable fluorine-containing polymer (b). When the content of the fluorine-containing layer (B) is less than 0.001% by mass, the resulting fluorine-containing laminate is not sufficient in the case where the fluorine-containing layer (B) is made of a filler capable of imparting a sense of brightness, and 10% by mass. If it exceeds 1, the corrosion resistance and water vapor resistance may be reduced. A preferable lower limit is 0.01% by mass, and a preferable upper limit is 5% by mass.
  The fluorine-containing layer (B) is mainly composed of a polymer component, a filler, and additives described later. The fluorine-containing layer (B) preferably has a polymer component that is a melt-processable fluorine-containing polymer (b). In the present specification, “the fluorine-containing layer (B) has a polymer component that is a melt-processable fluorine-containing polymer (b)” means that the polymer in the fluorine-containing layer (B) is a melt-processable fluorine-containing polymer. It means that it is only a polymer (b). The fluorine-containing layer (B) is superior to both the primer layer (A) and the fluorine-containing layer (C) described later because the polymer component is a melt-processable fluorine-containing polymer (b). It has good adhesion.
  The fluorine-containing laminate of the present invention has a fluorine-containing layer (C) composed of a melt-processable fluorine-containing polymer (c).
  In the fluorine-containing laminate of the present invention, the fluorine-containing layer (C) is formed on the above-mentioned fluorine-containing layer (B). The fluorine-containing layer (C) may be a coating film formed on the fluorine-containing layer (B), or may be a molded product such as a film or a sheet. Is fired at a temperature equal to or higher than the melting point of the melt-processable fluoropolymer (c). It is preferable that the said fluorine-containing layer (C) is a coating film formed on the fluorine-containing layer (B) from the point which is excellent in adhesiveness with a fluorine-containing layer (B).
  The melt processable fluorine-containing polymer (c) has melt processability among polymers having fluorine atoms directly bonded to carbon atoms constituting the main chain or side chain.
  As said melt-processable fluoropolymer (c), what has melt processability among the above-mentioned fluoropolymers (a) can be used. The melt processable fluoropolymer (c) is common to the melt processable fluoropolymer (b) in that it has melt processability among the fluoropolymers (a) described above. However, it is different from the above-mentioned melt-processable fluorine-containing polymer (b) in the fluorine-containing layer (B) in that it is in the fluorine-containing layer (C).
  The melt-processable fluoropolymer (c) has excellent film-forming properties, the fluorine-containing layer (C) has excellent adhesion to the above-mentioned fluorine-containing layer (B), and the resulting fluorine-containing polymer. From the point that the laminate is excellent in corrosion resistance and water vapor resistance, the same ones as the above-mentioned melt processable fluoropolymer (b) can be mentioned, among others, having a melting point of 150 to 350 ° C., and a temperature higher by 50 ° C. than the melting point. Has a melt viscosity of 10⁶(Pascal · second) or less is preferable, and examples thereof include a TFE copolymer. As the melt-processable fluoropolymer (c), PFA and / or FEP are preferable from the viewpoint of excellent heat resistance, non-adhesiveness and film-forming property. The “PFA and / or FEP” means PFA alone, FEP alone, or a mixture of PFA and FEP. As the melt-processable fluoropolymer (c), PFA is more preferable from the viewpoint of excellent heat resistance.
  The fluorine-containing layer (C) is preferably a transparent layer when the resulting fluorine-containing laminate is required to have design properties such as glitter. When the fluorine-containing layer (C) is a transparent layer, the filler in the fluorine-containing layer (B) can be visually recognized through the fluorine-containing layer (C). When used, the fluorine-containing laminate of the present invention has a good glitter.
  Further, when the fluorine-containing layer (C) is a transparent layer, the fluorine-containing layer (C) does not have a color pigment that is usually considered to cause deterioration in corrosion resistance. The laminate has better corrosion resistance and water vapor resistance.
  The fluorine-containing layer (C) is mainly composed of a polymer component and additives described later. The fluorine-containing layer (C) is preferably one in which the polymer component is a melt-processable fluorine-containing polymer (c). In the present specification, “the fluorine-containing layer (C) has a polymer component that is a melt-processable fluorine-containing polymer (c)” means that the polymer in the fluorine-containing layer (C) is a melt-processable fluorine-containing polymer. It means that it is only a polymer (c). The fluorine-containing layer (C) has excellent adhesion to the fluorine-containing layer (B) because the polymer component is a melt-processable fluorine-containing polymer (c).
  In the fluorine-containing laminate of the present invention, the primer layer (A) preferably has a thickness of 5 to 30 μm. If it is less than 5 μm, pinholes are likely to occur, and the corrosion resistance of the fluorine-containing laminate may be reduced. If it exceeds 30 μm, cracks are likely to occur, and the water vapor resistance of the fluorine-containing laminate may be lowered. The upper limit with a preferable film thickness of the said primer layer (A) is 20 micrometers.
  In the fluorine-containing laminate of the present invention, the fluorine-containing layer (B) preferably has a thickness of 5 to 30 μm. When the thickness is less than 5 μm, when a filler having a glittering feeling is used to impart a glittering feeling to the fluorine-containing laminate, the glittering feeling of the resulting fluorine-containing laminate may not be sufficient. If it exceeds 30 μm, cracks are likely to occur in the fluorine-containing layer (B), and the water vapor resistance of the fluorine-containing laminate may be lowered. The minimum with preferable film thickness of the said fluorine-containing layer (B) is 10 micrometers, and a preferable upper limit is 20 micrometers.
  In the fluorine-containing laminate of the present invention, the fluorine-containing layer (C) preferably has a thickness of 10 to 90 μm. If it is less than 10 μm, pinholes are likely to occur, and the corrosion resistance and wear resistance of the fluorine-containing laminate may be reduced. When it exceeds 90 μm, when the fluorine-containing laminate is in the presence of water vapor, water vapor tends to remain in the fluorine-containing laminate, and the water vapor resistance may be poor. The minimum with preferable film thickness of the said fluorine-containing layer (C) is 30 micrometers, and a preferable upper limit is 70 micrometers.
  In the fluorine-containing laminate of the present invention, the primer layer (A), the fluorine-containing layer (B), and the fluorine-containing layer (C) are laminated in this order. If the said primer layer (A), the said fluorine-containing layer (B), and the said fluorine-containing layer (C) are laminated | stacked in this order in the fluorine-containing laminated body of this invention, the said primer layer (A) The upper surface of the above and / or the upper surface of the fluorine-containing layer (B) may be printed with characters, drawings, and the like.
  As described above, the fluorine-containing laminate of the present invention only needs to have the primer layer (A), the fluorine-containing layer (B), and the fluorine-containing layer (C). (C) A layer may be further provided thereon.
  In the fluorine-containing laminate of the present invention, as described above, the fluorine-containing layer (B) formed on the primer layer (A) is composed of a melt-processable fluorine-containing polymer (b) and a filler. Yes, the fluorine-containing layer (C) formed on the fluorine-containing layer (B) is made of a melt-processable fluorine-containing polymer (c).
  In the fluorine-containing laminate of the present invention, the melt-processable fluorine-containing polymer (b) and the melt-processable fluorine-containing polymer (c) are both melt-processable. Adhesion with the fluorine layer (C) is excellent, and corrosion resistance and water vapor resistance are excellent. The conventional laminate in which the primer layer, the intermediate layer made of TFE homopolymer, and the topcoat layer made of PFA are laminated in this order has a problem that it is inferior in water vapor resistance. This is considered to be due to easy separation from the intermediate layer. This peeling is caused by differences in thermal expansion coefficient and thermal contraction ratio between TFE homopolymer and PFA, resulting in residual internal stress (strain) in the intermediate layer and topcoat layer, and pinholes. This is considered to occur easily between the primer layer and the intermediate layer.
  The fluorine-containing laminate of the present invention has excellent adhesion between the fluorine-containing layer (B) and the fluorine-containing layer (C) as described above, and is excellent in corrosion resistance and water vapor resistance, and wear resistance. It will be excellent.
  In the fluorine-containing laminate of the present invention, since the filler can be uniformly dispersed in the fluorine-containing layer (B), when the filler having a glitter feeling is used, the glitter feeling is excellent. Is. The fluorine-containing laminate of the present invention is excellent in corrosion resistance even when the above metal powder is used as the filler because the filler is not in contact with the substrate.
  The fluorine-containing laminate forming method of the present invention is for forming the above-mentioned fluorine-containing laminate,
  A step (i) of forming a primer coating film (Ap) by coating a primer coating composition comprising a fluoropolymer (a) and a heat-resistant resin on a substrate;
  A step (ii) of forming a fluorine-containing coating film (Bp) by applying a filler-containing composition comprising a melt-processable fluorine-containing polymer (b) and a filler on the primer coating film (Ap), And
  A fluorine-containing laminate is formed by forming a fluorine-containing film (Cp) on the fluorine-containing coating film (Bp) using a melt-processable fluorine-containing composition comprising a melt-processable fluorine-containing polymer (c). Step (iii)
Is included.
  In the step (i), the primer coating composition comprises a fluoropolymer (a) and a heat resistant resin. The primer coating composition may be liquid or powder. When the primer coating composition is in a liquid state, it comprises a liquid medium together with the fluoropolymer (a) and a heat resistant resin. The liquid medium is usually composed of water and / or an organic liquid. In the present specification, the “organic liquid” means an organic compound that is liquid at a room temperature of about 20 ° C.
  When the liquid medium of the primer coating composition is mainly composed of an organic liquid, the heat-resistant resin and the fluoropolymer (a) are dispersed as particles in the liquid medium and / or It is dissolved in a liquid medium. The organic liquid is not particularly limited, and examples thereof include nitrogen-containing organic liquids such as N-methyl-2-pyrrolidone, 2-pyrrolidone and N, N-dimethylacetamide; toluene, xylene, trimethylbenzene, methylethylbenzene, propylbenzene, Aromatic hydrocarbon solvents such as butylbenzene; saturated hydrocarbon solvents having 6 to 12 carbon atoms; lactones such as γ-butyrolactone; acyclic esters such as butyl acetate; ketones such as methyl isobutyl ketone and methyl ethyl ketone Glycols such as ethylene glycol, triethylene glycol and propylene glycol; glycol ethers such as butyl cellosolve; monoalcohols such as 1-butanol and diacetone alcohol;
  As the aromatic hydrocarbon solvent, commercially available products such as Solvesso 100, Solvesso 150, Solvesso 200 (all trade names, manufactured by Exxon Chemical) may be used. As the saturated hydrocarbon solvent, a commercially available mineral spirit (Japanese Industrial Standard, Industrial Gasoline No. 4) or the like may be used.
  The said organic liquid may be used independently and may use 2 or more types together.
  When the liquid medium of the primer coating composition is mainly composed of water, the heat-resistant resin is dispersed as particles in the liquid medium or dissolved in the liquid medium, and contains fluorine. The polymer (a) is dispersed as particles in the liquid medium.
  When the liquid medium is mainly composed of water, the primer coating composition is usually added with a surfactant for the purpose of dispersing and stabilizing the particles composed of the fluoropolymer (a). It will be. The surfactant is not particularly limited, and examples thereof include nonionic surfactants such as fluorine-containing nonionic surfactants; anionic surfactants such as fluorine-containing anionic surfactants; And cationic surfactants such as cationic surfactants. The primer coating composition can be used in combination with the surfactant together with the surfactant for the purpose of dispersing and stabilizing the particles comprising the fluoropolymer (a).
  The primer coating composition is also a method described in JP-B-49-17017, that is, particles having a dispersoid consisting of the fluoropolymer (a) and a heat-resistant resin, To an aqueous dispersion in which the dispersion medium is mainly composed of water, an organic solvent that is a layer transition liquid and a layer transition agent are added, and particles composed of the fluoropolymer (a) and particles composed of a heat resistant resin are added. It may be an organosol obtained by a method of transferring the layer to the organic solvent.
  The primer coating composition is preferably a liquid from the viewpoint of excellent adhesion to a substrate, and more preferably a liquid medium mainly composed of water from the viewpoint of environmental problems.
  When the primer coating composition is in a liquid form, the primer coating composition preferably has a viscosity of 0.1 to 50000 mPa · s. When it is less than 0.1 mPa · s, sagging or the like is likely to occur at the time of application on the substrate, and it may be difficult to obtain a target film thickness. In some cases, the thickness of the primer coating film (Ap) obtained may not be uniform, resulting in poor surface smoothness or the like. A more preferred lower limit is 1 mPa · s, and a more preferred upper limit is 30000 mPa · s.
  In the primer coating composition, the fluoropolymer (a) preferably has an average particle size of 0.01 to 5 μm. When the heat resistant resin is dispersed as particles in the primer coating composition, those having an average particle diameter of 0.5 to 8 μm are preferable.
  In the primer coating composition, the heat resistant resin is preferably PES, PAI and / or PI, more preferably PAI and / or PI, as described above for the primer layer (A) of the fluorine-containing laminate. PES and PAI and / or PI are more preferable.
  In the primer coating composition, the PES is preferably 65 to 85% by mass of the total amount of PES and PAI and / or PI. If the amount is less than 65% by mass, the water vapor resistance of the resulting fluorine-containing laminate may be reduced, and if it exceeds 85% by mass, the corrosion resistance may be reduced.
  The ratio of the PES is substantially the same in the primer layer (A) of the fluorine-containing laminate because the above-mentioned heat-resistant resin is not decomposed even in firing performed at the time of forming the fluorine-containing laminate described later. It is.
  In the primer coating composition, the heat resistant resin is preferably 15 to 50% by mass of the total solid content of the heat resistant resin and the fluoropolymer (a).
  In the present specification, the “solid content” means a solid at 20 ° C.
  In the present specification, the above-mentioned “total amount of solid content of the heat-resistant resin and the fluoropolymer (a)” is applied at a temperature of 80 to 100 ° C. or less after the primer coating composition is applied on the substrate. And the total mass of the heat-resistant resin and the fluoropolymer (a) in the residue after baking at 380 to 400 ° C. for 45 minutes.
  When the heat-resistant resin is less than 15% by mass of the total solid content of the heat-resistant resin and the fluoropolymer (a), the primer layer (A) in the resulting fluoropolymer laminate and the substrate are adhered to each other. The power may not be enough. If it exceeds 50% by mass, the adhesion between the primer layer (A) and the fluorine-containing layer (B) in the resulting fluorine-containing laminate may not be sufficient. A more preferable lower limit is 20% by mass, and a more preferable upper limit is 40% by mass.
  For the purpose of further improving the coating workability and the corrosion resistance and water vapor resistance of the resulting fluorine-containing laminate together with the fluorine-containing polymer (a) and the heat-resistant resin, the primer coating composition is further described above. It may consist of additives other than the filler in the fluorine-containing layer (B).
  The additives are not particularly limited, for example, a leveling agent, a solid lubricant, an anti-settling agent, a moisture absorbent, a surface conditioner, a thixotropic agent, a viscosity modifier, an antigelling agent, an ultraviolet absorber, Examples include light stabilizers, plasticizers, anti-coloring agents, anti-skinning agents, anti-scratch agents, anti-fungal agents, antibacterial agents, antioxidants, anti-static agents, and silane coupling agents.
  In the step (i), a primer coating film (Ap) is formed by applying a primer coating composition on a substrate.
  The base material may be subjected to a surface treatment such as a degreasing treatment or a surface roughening treatment, if necessary. The surface roughening treatment method is not particularly limited, and examples thereof include chemical etching with acid or alkali, anodization (alumite treatment), and sandblasting. The surface treatment is preferably performed from the viewpoint that the primer coating composition can be uniformly applied without causing repellency and the adhesion between the substrate and the primer coating film (Ap) is improved. .
  The application method is not particularly limited, and when the primer coating composition is liquid, for example, spray coating, roll coating, doctor blade coating, dip (immersion) coating, impregnation coating, spin flow coating, curtain Examples include flow coating, and spray coating is preferable. In the case where the primer coating composition is a powder, electrostatic coating, fluid dipping method, rolining method and the like can be mentioned, among which electrostatic coating is preferable.
  The step (i) may be any method as long as it forms the primer coating film (Ap) by applying the primer coating composition on a substrate. After the application, the step (ii) is performed. It may be fired before performing, or may not be fired, and when the primer coating composition is liquid, it is further dried after the application. Or it may not dry.
  The drying is preferably performed at a temperature of 70 to 300 ° C. for 5 to 60 minutes. The firing is preferably performed at a temperature of 260 to 410 ° C. for 10 to 30 minutes.
  When the primer coating composition is in a liquid state, it is usually preferably dried after being coated on the substrate, and since the coating film laminate is baked in the step (iii) described below, More preferably, no firing is performed.
  When the above-mentioned primer coating composition is a powder, it is preferable that it is usually fired after being coated on a substrate.
  The primer coating film (Ap) is formed by coating the primer coating composition on a substrate. The primer coating film (Ap) may be formed only by the coating in the step (i), or may be formed by drying after the coating. After the above application, it may be formed by baking as necessary after drying. The primer coating film (Ap) becomes the primer layer (A) in the resulting fluorine-containing laminate.
  Hereinafter, the step (i) may be referred to as “step (1)”.
  In the step (ii), a fluorine-containing coating film (Bp) is formed by coating a filler-containing composition on the primer coating film (Ap).
  The filler-containing composition comprises a melt-processable fluoropolymer (b) and a filler. The filler-containing composition is preferably a liquid filler-containing liquid composition, and is preferably composed of a melt processable fluoropolymer (b), a filler, and a liquid medium. The liquid medium is usually composed of water and / or an organic liquid.
  When the liquid medium of the filler-containing liquid composition is mainly composed of an organic liquid, the melt-processable fluoropolymer (b) is dispersed as particles in the liquid medium and / or The filler is dissolved in a liquid medium, and the filler is dispersed in the liquid medium as particles. The organic liquid is not particularly limited, and examples thereof include the same organic liquid that can be used as the liquid medium of the primer coating composition.
  When the liquid medium of the filler-containing liquid composition is mainly composed of water, the melt-processable fluoropolymer (b) and the filler are dispersed as particles in the liquid medium. As the filler-containing liquid composition, the liquid medium may be an organic liquid, but from the viewpoint of environmental problems, the liquid medium is a filler-containing aqueous dispersion mainly composed of water. Is preferred. In the above filler-containing aqueous dispersion, the liquid medium may contain a water-soluble organic liquid such as a low molecular weight alcohol as long as it is mainly made of water, but is preferably made only of water. .
  When the liquid medium is mainly composed of water, the filler-containing composition usually has a surface active property for the purpose of stabilizing the dispersion of the particles comprising the melt-processable fluoropolymer (b). An agent is added. The surfactant is not particularly limited, and examples thereof include the same surfactants that can be used in the primer coating composition.
  The viscosity of the filler-containing composition is preferably 0.1 to 50000 mPa · s, as in the case where the primer coating composition is liquid. A more preferred lower limit is 1 mPa · s, and a more preferred upper limit is 30000 mPa · s.
  The said filler containing composition WHEREIN: As for the particle | grains which consist of the said melt-processable fluoropolymer (b), what has an average particle diameter of 0.01-5 micrometers is preferable. The filler preferably has an average particle size of 1 to 100 μm.
  The filler-containing composition, together with the melt-processable fluorine-containing polymer (b) and the filler, further improves the coating workability and the corrosion resistance and water vapor resistance of the resulting fluorine-containing laminate, and contains the filler. For the purpose of uniformly dispersing in the fluorine layer (B), it may further comprise the same additives as those usable in the above-described primer coating composition. The filler-containing composition is preferably formed by adding a pigment dispersant for the purpose of dispersing and stabilizing the filler such as a luster flat pigment.
  In the step (ii), a fluorine-containing coating film (Bp) is formed by coating a filler-containing composition on the primer coating film (Ap).
The application method is not particularly limited, and examples thereof include the same method as the application method when the primer coating composition is in liquid form, and spray coating is particularly preferable.
  The step (ii) only needs to form the fluorine-containing coating film (Bp) by coating the filler-containing composition on the primer coating film (Ap). It may be dried before performing step (iii), may not be dried, may be fired, or may not be fired.
  It is preferable to perform the drying in the said process (ii) at the temperature of 70-300 degreeC for 5 to 60 minutes similarly to the drying in the said process (i).
  The firing in the step (ii) is preferably performed at a temperature of 260 to 410 ° C. for 10 to 30 minutes, similarly to the firing in the step (i).
  The filler-containing composition is preferably one that is usually dried after being applied onto the primer coating film (Ap), and since the coating film laminate is baked in the step (iii) described later, More preferably, no firing is performed.
  The fluorine-containing coating film (Bp) is formed by coating the filler-containing composition on the primer coating film (Ap). In the step (ii), the fluorine-containing coating film (Bp) may be formed only by the coating, or may be formed by drying after the coating. And after the said application | coating, after drying as needed, you may form by baking. The fluorine-containing coating film (Bp) becomes a fluorine-containing layer (B) in the resulting fluorine-containing laminate.
  In the step (ii), the filler-containing composition is preferably a liquid-containing filler-containing liquid composition, and the step (ii) includes the filler-containing composition on the primer coating film (Ap). The step of forming the fluorine-containing coating film (Bp) by applying a liquid composition (hereinafter sometimes referred to as “step (2)”) is preferable.
  The step (iii) is to form a fluorine-containing laminate by forming a fluorine-containing film (Cp) on the fluorine-containing coating film (Bp) using the melt-processable melt-processable fluorine-containing composition. is there.
  The melt processable fluorine-containing composition comprises a melt processable fluorine-containing polymer (c).
  The melt-processable fluorine-containing composition may be a molded product such as a film or sheet, may be a liquid, or may be a powder. When the melt-processable fluorine-containing composition is liquid, it is composed of a liquid medium together with the melt-processable fluorine-containing polymer (c). The liquid medium is usually composed of water and / or an organic liquid.
  When the liquid medium of the melt-processable fluorine-containing composition is mainly composed of an organic liquid, the melt-processable fluorine-containing polymer (c) is dispersed as particles in the liquid medium, and / or It is dissolved in the liquid medium. The organic liquid is not particularly limited, and examples thereof include the same organic liquid that can be used as the liquid medium of the primer coating composition.
  When the liquid medium of the melt processable fluorine-containing composition is mainly composed of water, the melt processable fluorine-containing polymer (c) is dispersed as particles in the liquid medium. When the liquid medium is an aqueous dispersion mainly composed of water, the melt-processable fluorine-containing composition is usually intended to stabilize the dispersion of particles composed of the melt-processable fluorine-containing polymer (c). As described above, a surfactant is added. It does not specifically limit as said surfactant, For example, the same thing etc. as surfactant which can be used for the above-mentioned primer coating composition are mentioned.
  When the melt processable fluorine-containing polymer (c) is dispersed as particles in the liquid medium, the melt processable fluorine-containing polymer preferably has an average particle diameter of 0.01 to 5 μm. In the case of a powder, one having an average particle diameter of 5 to 50 μm is preferable. When the melt processable fluorine-containing composition is a powder, a more preferable lower limit of the average particle diameter of the particles made of the melt processable fluorine-containing polymer (c) is 10 μm, and a more preferable upper limit is 30 μm. is there.
  The melt-processable fluorine-containing composition is preferably a fluorine-containing powder that is a powder because it is easy to obtain a thick coating film with a small number of coatings.
  The melt-processable fluorine-containing composition, together with the melt-processable fluorine-containing polymer (c), is further described above for the purpose of further improving the coating workability and the corrosion resistance and water vapor resistance of the resulting fluorine-containing laminate. It may be composed of the same additives as those that can be used in the primer coating composition.
  In the step (iii), the fluorine-containing laminate is formed by forming the fluorine-containing film (Cp) on the fluorine-containing coating film (Bp) using the melt-processable fluorine-containing composition.
  In the method for forming the fluorine-containing film (Cp), when the melt-processable fluorine-containing composition is a powder, the melt-processable fluorine-containing composition is applied onto the fluorine-containing coating film (Bp). It consists of. When the melt-processable fluorine-containing composition is a powder, the application method is not particularly limited. For example, the same method as the application method when the primer coating composition is a powder may be used. Among these, electrostatic coating is preferable.
  The method for forming the fluorine-containing film (Cp) includes applying the melt-processable fluorine-containing composition onto the fluorine-containing coating film (Bp) when the melt-processable fluorine-containing composition is in a liquid state. It will be. When the melt-processable fluorine-containing composition is in a liquid state, the application method is not particularly limited, and examples thereof include the same method as the application method when the primer coating composition is in a liquid state. Of these, spray coating is preferable.
  The method for forming the fluorine-containing film (Cp) is to apply the melt-processable fluorine-containing composition onto the fluorine-containing coating film (Bp) when the melt-processable fluorine-containing composition is liquid. What is necessary is just to have dried after the said application | coating, and the thing which is not dried may be sufficient.
It is preferable to perform the said drying for 5 to 60 minutes at the temperature of 70-300 degreeC similarly to the drying in the said process (i) and the said process (ii).
  The method for forming the fluorine-containing film (Cp) is, for example, when the melt-processable fluorine-containing composition is a film-like molded article, for example, a film-like molded article previously molded by a conventionally known method or the like. Conventionally known methods such as mounting on a fluorine-containing coating film (Bp) and thermocompression bonding may be mentioned.
  The fluorine-containing film (Cp) is formed by using the melt-processable fluorine-containing composition on the fluorine-containing coating film (Bp). Even if the said fluorine-containing film | membrane (Cp) is the said process (iii) and the said melt-processable fluorine-containing composition is a liquid, it may be formed by drying as needed after the said application | coating. Alternatively, when the melt-processable fluorine-containing composition is a molded product, it may be formed by thermocompression bonding. The fluorine-containing film (Cp) is a fluorine-containing layer (C) in the resulting fluorine-containing laminate.
  In the step (iii), a fluorine-containing film (Cp) is formed on the fluorine-containing coating film (Bp) to form a fluorine-containing laminate.
  In the method of forming the fluorine-containing laminate, when the melt-processable fluorine-containing composition is powder or liquid, the melt-processable fluorine-containing composition is applied onto the fluorine-containing coating film (Bp). Then, after forming the fluorine-containing film (Cp), a method of firing a coating film laminate including the primer coating film (Ap), the fluorine-containing coating film (Bp), and the fluorine-containing film (Cp), etc. Can be mentioned.
  The firing is preferably performed at a temperature of 260 to 410 ° C. for 10 to 30 minutes, similarly to the firing in the step (i) and the step (ii).
  When the melt-processable fluorine-containing composition is a molded product such as a film, the step (iii) can form the fluorine-containing film (Cp) and simultaneously obtain the fluorine-containing laminate.
  In the method of forming the fluorine-containing laminate, when the melt-processable fluorine-containing composition is a molded product, the primer coating film (Ap) and the fluorine-containing coating film (Bp) perform the following steps, respectively. It is preferable that it is formed by baking beforehand.
  In the step (iii), it is preferable to use a fluorine-containing powder composed of powder as the melt-processable fluorine-containing composition, and by applying the fluorine-containing powder on the fluorine-containing coating film (Bp). The step of forming the fluorine-containing film (Cp) (hereinafter sometimes referred to as “step (3)”), the primer coating film (Ap), the fluorine-containing coating film (Bp), and the fluorine-containing film. A step of forming a fluorine-containing laminate by firing a coating film laminate comprising (Cp) (hereinafter sometimes referred to as “step (4)”) is preferable.
  In the method for forming a fluorine-containing laminate of the present invention, after the step (i) for forming the primer coating film (Ap) or after the step (ii) for forming the fluorine-containing coating film (Bp), characters, It may have a step of printing a drawing or the like. The said character, drawing, etc. are the character, line, etc. which show the quantity of water, for example, when the below-mentioned coated article is a rice cooker.
  The printing method is not particularly limited, and examples thereof include pad transfer printing. It does not specifically limit as printing ink used for the said printing, For example, the composition which consists of PES, a TFE homopolymer, and a titanium oxide is mentioned.
  The fluorine-containing laminate forming method of the present invention is for forming the above-mentioned fluorine-containing laminate,
A step (1) of forming a primer coating film (Ap) by applying a primer coating composition comprising a fluoropolymer (a) and a heat-resistant resin on a substrate;
Step (2) of forming a fluorine-containing coating film (Bp) by applying a filler-containing liquid composition comprising a melt-processable fluorine-containing polymer (b) and a filler on the primer coating film (Ap). ,
A step (3) of forming a fluorine-containing film (Cp) by applying a fluorine-containing powder comprising a melt-processable fluorine-containing polymer (c) on the fluorine-containing coating film (Bp), and
Step (4) of forming the fluorine-containing laminate by firing the coating film laminate comprising the primer coating film (Ap), the fluorine-containing coating film (Bp), and the fluorine-containing film (Cp).
It is preferable that it contains.
  In the method for forming a fluorine-containing laminate of the present invention, the fluorine-containing layer (C) in the fluorine-containing laminate can be obtained by applying a fluorine-containing powder comprising a melt-processable fluorine-containing polymer (c) with a small number of coatings. Can be a thick film as described above. As described above, the fluorine-containing laminate obtained by the method for forming a fluorine-containing laminate of the present invention has excellent adhesion between the fluorine-containing layer (B) and the fluorine-containing layer (C), and excellent corrosion resistance and water vapor resistance. At the same time, since the fluorine-containing layer (C) is a thick film as described above, it is particularly excellent in wear resistance.
  In the fluorine-containing laminate forming method of the present invention, since the filler is well dispersed in the filler-containing liquid composition, the filler is uniformly dispersed in the fluorine-containing layer (B) of the resulting fluorine-containing laminate, It is possible to stably exhibit characteristics such as glitter feeling of the filler.
  Since the fluorine-containing laminate forming method of the present invention has the above-described configuration, it is suitable as a method for forming a fluorine-containing laminate on a substrate.
  The coated article of the present invention comprises a base material and the above-mentioned fluorine-containing laminate. The substrate is not particularly limited, and examples thereof include simple metals such as iron, aluminum and copper and metals such as alloys thereof; nonmetallic inorganic materials such as enamel, glass and ceramics. Examples of the alloys include stainless steel. As said base material, a metal is preferable and aluminum and stainless steel are more preferable.
  The coated article of the present invention is not particularly limited, and can be used for applications utilizing non-adhesiveness, heat resistance, slipperiness, etc. possessed by the fluoropolymer, for example, using non-adhesiveness, Cooking utensils such as frying pans, pressure cookers, pans, grill pans, rice cookers, ovens, hot plates, baking molds, kitchen knives, gas tables, etc .; Examples of utilizing slipperiness include tools such as saws and files; household items such as irons; metal foils and the like. Especially, it is preferable that they are a rice cooker, a pressure cooker, and a grill pan in which corrosion resistance and water vapor resistance are requested | required, and it is more preferable that it is a rice cooker in which designability is requested | required.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited only to these examples. “%” And “part” represent mass% and mass part, respectively.
Production Example 1 Preparation of Polyethersulfone Resin Aqueous Dispersion 60 parts of a polyethersulfone resin [PES] having a number average molecular weight of about 24,000 and 60 parts of deionized water were completely pulverized in a ceramic ball mill. Stir for about 10 minutes. Subsequently, 180 parts of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added, and further pulverized for 48 hours to obtain a dispersion. The obtained dispersion was further pulverized with a sand mill for 1 hour to obtain a PES aqueous dispersion having a PES concentration of about 20%. The particle diameter of the particles composed of PES in the PES aqueous dispersion was 2 to 3 μm.
Production Example 2 Preparation of Polyamideimide Resin Aqueous Dispersion A polyamideimide resin [PAI] varnish (containing 71% NMP) having a solid content of 29% was poured into water to precipitate PAI. This was pulverized for 48 hours in a ball mill to obtain an aqueous PAI dispersion. The solid content of the obtained PAI aqueous dispersion was 20%, and the average particle size of PAI in the PAI aqueous dispersion was 2 μm.
Production Example 3 Preparation of Primer Coating Composition The PES aqueous dispersion obtained in Production Example 1 and the PAI aqueous dispersion obtained in Production Example 2 were prepared by adding PES to the total solid content of PES and PAI. The mixture was mixed to 85%, and an aqueous dispersion of tetrafluoroethylene homopolymer [TFE homopolymer] (average particle size 0.28 μm, solid content 60%, polyether nonionic surfactant as a dispersant). 6% of TFE homopolymer) is added so that PES and PAI are 20% of the total solid content of PES, PAI and TFE homopolymer, and methylcellulose is added as a thickener to TFE homopolymer. 0.7% based on the solid content of the polyester, and 6% polyether nonionic surfactant as a dispersion stabilizer based on the solid content of the TFE homopolymer. An aqueous dispersion of 34% solid content of TFE homopolymer was obtained.
Production Example 4 Preparation of Filler-Containing Aqueous Dispersion Tetrafluoroethylene / perfluoro (alkyl vinyl ether) [PFA] Aqueous Dispersion (average particle size 0.35 μm, solid content 48%, polyether nonionic interface as dispersant) Mica (mica coated with titanium dioxide having a specific gravity of about 3 and an average particle size of 30 μm) as a filler is added to the PFA solid content by 0.6%. As a result, an aqueous dispersion having a solid content of 48% was obtained.

After degreasing the surface of the aluminum plate (A-1050P) with acetone, the surface is roughened by sandblasting so that the surface roughness Ra value measured according to JISB 1982 is 2.5 to 4.0 μm. did. After removing dust on the surface by air blow, the coating composition for primer obtained in Production Example 3 was subjected to an RG-2 type gravity spray gun (trade name, Anest Iwata) so that the dry film thickness was about 10 μm. Using a nozzle diameter of 1.0 mm, spray coating was performed at a spraying pressure of 0.2 MPa. The obtained coating film on the aluminum plate was dried at 80 to 100 ° C. for 15 minutes and cooled to room temperature. The filler-containing aqueous dispersion obtained in Production Example 4 was spray-coated on the obtained primer coating film in the same manner as the primer coating composition so that the dry film thickness was about 15 μm. The obtained filler-containing coating film was dried at 80 to 100 ° C. for 15 minutes and cooled to room temperature. Electrostatic coating of PFA powder paint (trade name: ACX-31, manufactured by Daikin Industries, Ltd., PFA average particle diameter 25 μm) on the obtained filler-containing coating film under the conditions of an applied voltage of 50 KV and a pressure of 0.08 MPa. And it baked at 380 degreeC for 20 minute (s), the PFA layer whose film thickness is about 40 micrometers was formed, and the coating plate for a test was obtained. The obtained test coating plate had a primer layer, a filler-containing layer, and a PFA layer formed on an aluminum plate.
(Evaluation methods)
The following evaluation was performed about the coating film of the obtained coating plate for a test.
Film thickness Measured using a high-frequency film thickness meter (trade name: LZ-300C, manufactured by Kett Science Laboratory).
Oden's Elemental Corrosion Resistance Test The surface of the coating film of the obtained test coating plate was scratched to reach the aluminum plate by cross-cutting with a cutter knife. This test coating plate is immersed in a solution of 20 g of Oden element (manufactured by Sakai Subs Foods Co., Ltd.) in 1 liter of water and kept at 70 ° C. to check for blistering and other abnormalities every 100 hours. The test was conducted visually and the test was conducted up to 1000 hours. When there was no abnormality such as the occurrence of blisters, it was accepted, and when there was an abnormality such as the occurrence of blisters, it was rejected.
Water Vapor Resistance Test The obtained test coating plate was left in 0.6 MPa water vapor for 8 hours, returned to normal pressure, taken out, and then heated at 200 ° C. for 1 minute. This was repeated up to 10 cycles, and the presence or absence of blisters was examined. When no blister occurred, it was accepted, and when blister occurred, it was rejected.
The test coating plates obtained in the examples passed the Oden element corrosion resistance test for up to 1000 hours, and also passed the water vapor resistance test for up to 10 cycles.
Comparative Example For the filler-containing aqueous dispersion obtained in Production Example 4, a test coated plate was prepared and evaluated in the same manner as in Example except that TFE homopolymer was used instead of PFA.
The obtained test coated plate passed the Oden elemental corrosion resistance test up to 1000 hours, but in the water vapor resistance test, blisters occurred in one cycle and failed. Moreover, peeling between the primer layer and the filler-containing layer was visually observed in the blister-generating portion of the test coating plate after performing the water vapor resistance test.
In the example in which the filler-containing layer was formed using the filler-containing aqueous dispersion composed of PFA, the obtained test coating plate was excellent in both corrosion resistance and water vapor resistance. In the comparative example in which the filler-containing layer was formed using an aqueous dispersion made of a polymer, although the obtained test coating plate was excellent in corrosion resistance, blistering occurred when left in water vapor, and water resistance It was inferior to.

  Since the fluorine-containing laminate and the method for forming a fluorine-containing laminate of the present invention have the above-described configuration, they are excellent in corrosion resistance and water vapor resistance, and can stably exhibit the characteristics of a filler such as glitter even during mass production. Fluorine-containing laminates and coated articles can be obtained.

Claims (9)

A substrate, a primer layer (A) composed of a fluoropolymer (a) and a heat-resistant resin, a fluorine-containing layer (B) composed of a melt-processable fluoropolymer (b) and a filler, and a melt A coated article production method for producing a coated article comprising a fluorine-containing laminate having a fluorine-containing layer (C) comprising a workable fluorine-containing polymer (c),
The heat-resistant resin is a polyamideimide resin, a polyimide resin, a polyethersulfone resin, a polyetherimide resin, a polyetheretherketone resin, an aromatic polyester resin and / or a polyarylene sulfide resin.
The filler is 0.01% by mass or more and 5% by mass or less with respect to the solid content of the melt-processable fluoropolymer (b),
A step (1) of forming a primer coating film (Ap) by applying a primer coating composition comprising a fluoropolymer (a) and a heat-resistant resin on a substrate;
A step (2) of forming a fluorine-containing coating film (Bp) by applying a melt-processable fluorine-containing polymer (b), a filler-containing liquid composition containing a filler and water on the primer coating film (Ap). ),
A step (3) of forming a fluorine-containing film (Cp) by applying a fluorine-containing powder comprising a melt-processable fluorine-containing polymer (c) on the fluorine-containing coating film (Bp); and
The primer coating film (Ap), have a step (4) forming the fluorine-containing laminate by firing the fluorine-containing coating film (Bp) and said comprising a fluorinated layer (Cp) applied film laminate ,
The method for producing a coated article, wherein in the filler-containing liquid composition, the melt-processable fluoropolymer (b) has an average particle size of 0.01 to 5 m . The method for producing a coated article according to claim 1, wherein the polyethersulfone resin is 65 to 85 mass% of the total amount of the polyethersulfone resin and the polyamideimide resin and / or the polyimide resin. The method for producing a coated article according to claim 1 or 2, wherein the heat resistant resin is 15 to 50% by mass of the total solid content of the heat resistant resin and the fluoropolymer (a). The melt-processable fluoropolymer (c) is a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer and / or a tetrafluoroethylene / hexafluoropropylene copolymer. Coated article manufacturing method. The fluoropolymer (a) is a tetrafluoroethylene homopolymer, a modified polytetrafluoroethylene, a tetrafluoroethylene / hexafluoropropylene copolymer, and / or a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer. The coated article manufacturing method according to claim 1, 2, 3, or 4. The melt-processable fluorine-containing polymer (b) is a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer and / or a tetrafluoroethylene / hexafluoropropylene copolymer, 6. A method for producing a coated article according to 4 or 5. The coated article manufacturing method according to claim 1, 2, 3, 4, 5 or 6, wherein the filler is a glittering filler made of mica, metal powder and / or glass beads. The primer layer (A) has a thickness of 5 to 30 μm,
The fluorine-containing layer (B) has a thickness of 5 to 30 μm,
The coated article manufacturing method according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the fluorine-containing layer (C) has a thickness of 10 to 90 µm. A process (2) forms a fluorine-containing coating film (Bp) by spray-coating a filler containing liquid composition, Claim 1, 2, 3, 4, 5, 6, 7 or 8 Coated article manufacturing method.