JP2023024332A - 被覆用組成物及び被覆物品 - Google Patents
被覆用組成物及び被覆物品 Download PDFInfo
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- JP2023024332A JP2023024332A JP2022121054A JP2022121054A JP2023024332A JP 2023024332 A JP2023024332 A JP 2023024332A JP 2022121054 A JP2022121054 A JP 2022121054A JP 2022121054 A JP2022121054 A JP 2022121054A JP 2023024332 A JP2023024332 A JP 2023024332A
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Abstract
Description
特許文献2には、フッ素樹脂、耐熱性バインダー及び熱安定剤を含有する被覆用組成物が開示されている。
(A)~(C)の樹脂粒子の平均粒子径が0.1~10μmであり、かつメチルセルロースを実質的に含まないことを特徴とする被覆用組成物である。
上記耐熱性樹脂(A)は、ポリアミドイミド及び/又はポリイミド(A-1)並びにポリエーテルスルホン(A-2)であることが好ましい。
上記耐熱性樹脂(A)は、ポリアミドイミド及び/又はポリイミド(A-1)と、ポリエーテルスルホン(A-2)との質量比((A-1):(A-2))が85:15~65:35で、
ポリエーテルスルホンとポリアミドイミド及び/又はポリイミド(A)との合計量の非溶融加工性の含フッ素重合体(B)と溶融加工性の含フッ素重合体(C)の合計量に対する質量比((A):(B)+(C))が15:85~35:65であることが好ましい。
上記溶融加工性の含フッ素樹脂重合体(C)は、テトラフルオロエチレン-ヘキサフロオロプロピレン共重合体(FEP)及び/又はテトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体(PFA)であることが好ましい。
上記被覆用組成物は、金属又は非金属無機材料からなる基材上に直接塗布されるか、又は、耐熱性樹脂からなる層の上に塗布されることが好ましい。
上記被覆物品は、上記プライマー層と上記上塗り層の間に、さらに中塗り層を有するものであってよい。
本開示は、耐熱性樹脂(A)、非溶融加工性の含フッ素重合体(B)及び溶融加工性の含フッ素重合体(C)が水媒体に分散し、
(A)~(C)の樹脂粒子の平均粒子径が0.1~10μmであり、
かつメチルセルロースを実質的に含まない被覆用組成物である。
上記(A)~(C)の成分を含有する被覆用組成物は、塗装性を確保するために、増粘剤としてメチルセルロースを添加するのが一般的であった。しかし、このようなメチルセルロースを含有する被覆用組成物は、スプレー塗装工程において、発泡を生じてしまい、これが塗膜性能に悪影響を及ぼすことがあった。
HLB=20×[(界面活性剤中に含まれる親水基の分子量)/(界面活性剤の分子量)]
非アルキルフェノール型ノニオン界面活性剤(b)は、下記一般式(I):
R-O-A-H (I)
(式中、Rは直鎖状又は分岐鎖状の炭素数8~19の飽和又は不飽和の非環式脂肪族炭化水素基、あるいは、炭素数8~19の飽和環式脂肪族炭化水素基を表す。Aはオキシエチレンユニットを3~25個及びオキシプロピレンユニットを0~5個有するポリオキシアルキレン鎖を表す。)で表されるノニオン界面活性剤であることが好ましい。
上記一般式(I)で表されるノニオン界面活性剤としては、下記一般式(II):
C xH 2x+1CH(C yH 2y+1)C zH 2zO(C 2H 4O) nH (II)
(式中、xは1以上の整数、yは1以上の整数、zは0又は1、但しx+y+zは8~18の整数、nは4~20の整数を表す。)で表されるポリオキシエチレンアルキルエーテル系界面活性剤、又は、
下記一般式(III):
C xH 2x+1-O-A-H (III)
(式中、xは8~18の整数、Aはオキシエチレンユニットを5~20個及びオキシプロピレンユニットを1又は2個有するポリオキシアルキレン鎖を表す。)で表されるポリオキシエチレンアルキルエーテル系界面活性剤が好ましい。
耐熱性樹脂(A)は、150℃以上の条件で連続使用することができる樹脂を意味する。このような樹脂であって、含フッ素樹脂以外のものを挙げることができる。なお,(B)(C)に該当する含フッ素樹脂は、耐熱性樹脂(A)には該当しない。
より具体的には、ポリエーテルエーテルケトン樹脂、ポリフェニレンサルファイド樹脂、ポリアリールエーテルケトン(PAEK)、ポリエーテルケトンケトン(PEKK)、ポリエーテルケトン(PEK)及びポリエーテルエーテルケトンケトン(PEEKK)等の芳香族ポリエーテルケトン樹脂、ポリエーテルサルフォン(PES)、液晶ポリマー(LCP)、ポリサルフォン(PSF)、非晶性ポリアリレート(PAR)、ポリエーテルニトリル(PEN)、熱可塑ポリイミド(TPI)、ポリイミド(PI)、ポリエーテルイミド(PEI)、ポリアミドイミド(PAI)等を挙げることができる。
なかでも、ポリアミドイミド及び/又はポリイミド(A-1)であることが金属との接着性に優れるという点で特に好ましい。
上記芳香族ポリエーテルケトン樹脂としては、PEK、PEEK、PEEKK及びポリエーテルケトンエステル樹脂からなる群より選択される少なくとも1種が好ましく、PEEKがより好ましい
CF2=CF-ORf1 (1)
(式中、Rf1は、パーフルオロ有機基を表す。)で表されるパーフルオロ不飽和化合物等が挙げられる。本明細書において、上記「パーフルオロ有機基」とは、炭素原子に結合する水素原子が全てフッ素原子に置換されてなる有機基を意味する。上記パーフルオロ有機基は、エーテル酸素を有していてもよい。
上記溶融加工性含フッ素重合体(C)は、耐食性に一層優れる塗膜が得られる点で、FEP及びPFAからなる群より選択される少なくとも1種であることが好ましく、FEPであることがより好ましい。
上記平均粒子径は、レーザー光散乱法により測定することができる。
上記沸点は、1気圧(atm)において測定する値である。
上記第1の被覆物品は、上記プライマー層と上記上塗り層の間に、さらに中塗り層を有するものであってもよい。上記中塗り層としては特に限定されず、公知の中塗り塗料により形成することができる。
上記非金属無機材料としては、ホーロー、ガラス、セラミック等が挙げられる。
上記基材は、金属又は非金属無機材料とともに、他の材料を含んでもよい。
含フッ素層は、プライマー層と直接接していてもよく、他の層を介して接していてもよいが、直接接していることが好ましい。
第1及び第2の被覆物品は、調理器具、厨房用品又はその構成部材であることも好ましく、調理器具又はその構成部材であることがより好ましく、炊飯釜又はその構成部材であることが更に好ましい。
以下の実施例においては特に言及しない場合は、「部」「%」はそれぞれ「質量部」「質量%」を表す。
平均粒子径は、レーザー回折による粒度分布測定装置(マイクロトラック・ベル社製マイクロトラックMT-3000EXII型)により測定したものである。膜厚は、高周波式膜厚計(商品名:LZ-300C、ケット科学研究所製)を用いて測定した。
固形分29%のポリアミドイミド樹脂〔PAI〕ワニス(N-メチル-2-ピロリドン(以下、NMPという)を71%含む)を水中に投入してPAIを析出させた。これをボールミル中で48時間粉砕してPAI水性分散体(平均粒子径2μm)を得た。得られたPAI水性分散体の固形分は、20%であった。
数平均分子量約24000のポリエーテルスルホン樹脂〔PES〕60部及び脱イオン水60部を、セラミックボールミル中でPESからなる粒子が完全に粉砕されるまで約10分間攪拌した。次いで、NMP180部を添加し、更に、48時間粉砕し、分散体を得た。得られた分散体を更にサンドミルで1時間粉砕し、PES濃度が約20%のPES水性分散体(平均粒子径2μm)を得た。
製造例1で得られたPAI水性分散体に、テトラフルオロエチレンホモポリマー〔TFEホモポリマー、以下PTFEという〕水性分散体(平均粒子径0.28μm、固形分60%、分散剤として非アルキルフェノール型ポリエーテル系非イオン性界面活性剤をPTFEに対して6%含有している)とテトラフルオロエチレン-ヘキサフロオロプロピレン共重合体(以下、FEPという)水性分散体(平均粒子径0.20μm、固形分60%、分散剤として非アルキルフェノール型ポリエーテル系非イオン性界面活性剤をFEPに対して5%含有している)を、固形分の質量比でFEPがPTFEの8.4%となるように添加し、かつPAIが、PAI、PTFE及びFEPの固形分合計量の25%となるように加え、増粘剤として非アルキルフェノール型ポリエーテル系非イオン性界面活性剤(HLB値9.5)をポリマーの固形分に対して11%添加して、ポリマーの固形分37%の水性分散液(下塗り用被覆組成物(1))を得た。
製造例2で得られたPES水性分散体、及び、製造例1で得られたPAI水性分散体を、PESが、PESとPAIとの固形分合計量の75%となるように混合し、これにテトラフルオロエチレンホモポリマー〔TFEホモポリマー、以下PTFEという〕水性分散体(平均粒子径0.28μm、固形分60%、分散剤として非アルキルフェノール型ポリエーテル系非イオン性界面活性剤をPTFEに対して6%含有している)とテトラフルオロエチレン-ヘキサフロオロプロピレン共重合体(以下、FEPという)水性分散体(平均粒子径0.20μm、固形分60%、分散剤としてポリエーテル系非イオン性界面活性剤をFEPに対して5%含有している)を、固形分の質量比でFEPがPTFEの50%となり、かつPES及びPAIが、PES、PAI、PTFE及びFEPの固形分合計量の25%となるように加え、増粘剤として非アルキルフェノール型ポリエーテル系非イオン性界面活性剤(HLB値9.5)をポリマーの固形分に対して11%添加して、ポリマーの固形分37%の水性分散液(下塗り用被覆組成物(2))を得た。
製造例4にメチルセルロースをポリマーの固形分に対して0.068%添加した以外は製造例4と同様にしてポリマーの固形分36%の下塗り用被覆用組成物(3)を得た。
増粘剤を非アルキルフェノール型ポリエーテル系非イオン性界面活性剤(HLB値9.5)に替えてメチルセルロースをポリマーの固形分に対して0.61%添加した以外は製造例3と同様にして、ポリマーの固形分33%の下塗り用被覆用組成物(4)を得た。
増粘剤を非アルキルフェノール型ポリエーテル系非イオン性界面活性剤(HLB値9.5)に替えてメチルセルロースをポリマーの固形分に対して0.61%添加した以外は製造例4と同様にして、ポリマーの固形分33%の下塗り用被覆用組成物(5)を得た。
製造例4にメチルセルロースをポリマーの固形分に対して0.14%添加した以外は製造例4と同様にしてポリマーの固形分36%の下塗り用被覆用組成物(6)を得た。
縦5cm、横10cmに切断した厚みが1.5mmのアルミニウム板(A-1050P)の表面をアセトンで脱脂した後、JIS B 1982に準拠して測定した表面粗度Ra値が2.5~4.0μmとなるようにサンドブラストを行い、表面を粗面化した。エアーブローにより表面のダストを除去した後、製造例及び比較製造例で得られた下塗り用被覆用組成物を、乾燥膜厚が約10μmとなるように、RG-2型重力式スプレーガン(商品名、アネスト岩田社製、ノズル径1.0mm)を用い、吹き付け圧力0.2MPaでスプレー塗装した。得られたアルミニウム板上の塗布膜を80~100℃で15分間乾燥し、室温まで冷却した。
実施例5の中塗りとしては、ACX-34に炭化ケイ素を2.0質量%混合したもの、上塗りとしてはACX-34にガラスフレークを1.5質量%とダイヤモンド粉末を1.0質量%混合したものを塗装した。
PTFE水性塗料の場合、RG-2型重力式スプレーガン(商品名、アネスト岩田社製、ノズル径1.0mm)を用い、吹き付け圧力0.2MPaでスプレー塗装し、380℃で20分間焼成し、冷却して、上塗りに膜厚が約20μmのPTFE層を形成することにより、試験用塗装板を得た。得られた試験用塗装板は、アルミニウム板上に下塗り層、及びPTFEからなる上塗り層が形成されていた。
中塗りが充填材含有粉体塗料の場合、印加電圧40KV、圧力0.08MPaの条件で炭化ケイ素を含有するACX-34を静電塗装し、続いて上塗りのガラスフレークとダイヤモンド粉末を含有するACX-34を同様に静電塗装した。380℃で20分間焼成し、冷却して、中塗りに膜厚が約40μmの充填材含有PFA(PFA98%と炭化ケイ素2%を含む)層、上塗りに約5μmの充填材含有PFA(PFA97.5%、ガラスフレーク1.5%、ダイヤモンド粉末1.0%を含む)層を形成することにより、試験用塗装板を得た。得られた試験用塗装板は、アルミニウム板上に下塗り層、PFAと炭化ケイ素からなる中塗り層、及びPFA、ガラスフレーク、ダイヤモンド粉末からなる上塗り層形成されていた。上記で得られた塗装板で耐食試験を行った。
下記の評価を行った。
(下塗り用被覆組成物の塗装試験)
縦5cm、横10cmに切断した厚みが1.5mmのアルミニウム板(A-1050P)の表面をアセトンで脱脂した後、実施例及び比較例で得られた下塗り用被覆組成物を、乾燥膜厚が約10μmとなるように、W-101型重力式スプレーガン(商品名、アネスト岩田社製、ノズル径1.2mm)を用い、吹き付け圧力0.1MPaでスプレー塗装した。塗装直後の泡の数を調べた。
得られた試験用塗装板の塗膜表面にカッターナイフでクロスカットを入れ、基材に達する傷を入れた。この試験板を、おでんの素(ヱスビー食品株式会社製)20gを水1リットルに溶解した溶液中に浸漬し、70℃に保温して、カッターナイフでクロスカットを入れた試験板を1000時間浸漬し、クロスカット部の膨れの数を数えた。
下記の通り、点数を付与した。
5点 膨れなし
4点 膨れ(3mm以下)が3個以下
3点 膨れが4~6個、又は4mm以上の膨れ
2点 膨れが7~10個、又は10mm以上の膨れ、又は4mm以上の膨れ3個以上
1点 膨れが11個以上
B型粘度計(東機産業株式会社製TVB10型)を使用し、No.2ローター、60rpm、25℃の条件で粘度を測定した。
(A)~(C)の樹脂粒子の平均粒子径が0.1~10μmであり、
HLBが10以下である非イオン性界面活性剤を含有し、
かつ、塗料全量に対して、メチルセルロース量が、0.050質量%未満であることを特徴とする被覆用組成物である。
Claims (10)
- 耐熱性樹脂(A)、非溶融加工性の含フッ素重合体(B)及び溶融加工性の含フッ素重合体(C)が水媒体に分散し、
(A)~(C)の樹脂粒子の平均粒子径が0.1~10μmであり、
かつメチルセルロースを実質的に含まないことを特徴とする被覆用組成物。 - 耐熱性樹脂(A)は、ポリアミドイミド及び/又はポリイミド(A-1)である請求項1記載の被覆用組成物。
- 耐熱性樹脂(A)は、ポリアミドイミド及び/又はポリイミド(A-1)並びにポリエーテルスルホン(A-2)である請求項1記載の被覆用組成物。
- ポリアミドイミド及び/又はポリイミド(A-1)と、ポリエーテルスルホン(A-2)との質量比((A-1):(A-2))が85:15~65:35で、
ポリエーテルスルホンとポリアミドイミド及び/又はポリイミド(A)との合計量の非溶融加工性の含フッ素重合体(B)と溶融加工性の含フッ素重合体(C)の合計量に対する質量比((A):(B)+(C))が15:85~35:65である請求項3記載の被覆用組成物。 - 非溶融加工性の含フッ素重合体(B)は、ポリテトラフルオロエチレン及び/又は変性ポリテトラフルオロエチレンである請求項1~4のいずれかに記載の被覆用組成物。
- 溶融加工性の含フッ素樹脂重合体(C)は、テトラフルオロエチレン-ヘキサフロオロプロピレン共重合体(FEP)及び/又はテトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体(PFA)である請求項に1~4のいずれかに記載の被覆用組成物。
- さらに、HLBが10以下である非イオン性界面活性剤を含有する請求項1~4のいずれかに記載の被覆用組成物。
- 金属又は非金属無機材料からなる基材上に直接塗布されるか、又は、耐熱性樹脂からなる層の上に塗布される請求項1~4のいずれかに記載の被覆用組成物。
- 基材と、
請求項1~4のいずれかに記載の被覆用組成物を基材に直接塗布し、形成したプライマー層と、
含フッ素重合体を含む上塗り層を有することを特徴とする被覆物品。 - プライマー層と上塗り層の間に、さらに中塗り層を有する請求項9記載の被覆物品。
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JPH11349887A (ja) * | 1998-06-05 | 1999-12-21 | Daikin Ind Ltd | フッ素樹脂被覆用水性プライマー組成物 |
JP2004204073A (ja) * | 2002-12-25 | 2004-07-22 | Daikin Ind Ltd | 被覆用組成物、塗膜及び被覆物品 |
JP2009532247A (ja) * | 2006-04-04 | 2009-09-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 非付着性仕上げ塗り |
JP2020176216A (ja) * | 2019-04-19 | 2020-10-29 | ダイキン工業株式会社 | 被覆組成物及び被覆物品 |
CN112480757A (zh) * | 2020-12-15 | 2021-03-12 | 深圳市易珑科技有限公司 | 环境友好型水性高固体份不粘涂层底漆、其制备方法及其应用 |
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JP2003053261A (ja) | 2001-08-10 | 2003-02-25 | Daikin Ind Ltd | フッ素樹脂塗膜製造方法、フッ素樹脂塗膜及び加工物品 |
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JPH0539451A (ja) * | 1990-06-23 | 1993-02-19 | Sumitomo Electric Ind Ltd | 弗素樹脂被覆物 |
JPH11349887A (ja) * | 1998-06-05 | 1999-12-21 | Daikin Ind Ltd | フッ素樹脂被覆用水性プライマー組成物 |
JP2004204073A (ja) * | 2002-12-25 | 2004-07-22 | Daikin Ind Ltd | 被覆用組成物、塗膜及び被覆物品 |
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CN112480757A (zh) * | 2020-12-15 | 2021-03-12 | 深圳市易珑科技有限公司 | 环境友好型水性高固体份不粘涂层底漆、其制备方法及其应用 |
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JP2023054152A (ja) * | 2017-06-27 | 2023-04-13 | 株式会社三洋物産 | 遊技機 |
JP2023054151A (ja) * | 2017-06-27 | 2023-04-13 | 株式会社三洋物産 | 遊技機 |
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