JP7206511B2 - 粉体状プライマー組成物 - Google Patents
粉体状プライマー組成物 Download PDFInfo
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- JP7206511B2 JP7206511B2 JP2021037540A JP2021037540A JP7206511B2 JP 7206511 B2 JP7206511 B2 JP 7206511B2 JP 2021037540 A JP2021037540 A JP 2021037540A JP 2021037540 A JP2021037540 A JP 2021037540A JP 7206511 B2 JP7206511 B2 JP 7206511B2
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GQWNEBHACPGBIG-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-[2-(1,3-benzothiazol-2-ylsulfanylamino)ethoxy]ethanamine Chemical compound C1=CC=C2SC(SNCCOCCNSC=3SC4=CC=CC=C4N=3)=NC2=C1 GQWNEBHACPGBIG-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011031 topaz Substances 0.000 description 1
- 229910052853 topaz Inorganic materials 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
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- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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Description
溶融性フッ素樹脂は、パーフルオロポリマーであることが好ましい。
本開示は、上記プライマー皮膜の上に、溶融性パーフルオロポリマーを含む皮膜が設けられた積層体でもある。
本開示は、金属基材が配管、パイプ又はダクトであり、その内面に上記積層体が設けられた塗装物品でもある。
本開示の粉体状プライマー組成物は、平均粒径が5~100μmである溶融性フッ素樹脂粉末及びポリエーテルサルフォン粉末を含み、前記溶融性フッ素樹脂粉末と前記ポリエーテルサルフォン(PES)粉末との重量比は50:50~95:5であることを特徴とする。
そこで、本開示は、バインダー樹脂として、PES粉末を用いると、ブリスターの発生を抑制できることを見出したものである。ブリスターは、積層塗膜の密着性が十分でない場合等に、積層塗膜内に、水蒸気等の水分が侵入することによって発生する塗膜の膨れであるが、PESは溶融流動性に優れるために金属基材と高い密着力を確保しやすく、よって、水分の透過性が小さくなるため、ブリスターの発生を抑制できる。
上記メルトフローレートの範囲内であれば、得られるプライマー皮膜と溶融性パーフルオロポリマー皮膜との密着性が、溶融性フッ素樹脂の流動特性に起因して一層向上する。
上記メルトフローレートの範囲内であれば、層間密着性と耐食性を両立することが可能となる。
上記アミン系酸化防止剤としては、例えば、フェニル基、ナフチル基等の芳香族性炭化水素基を分子中に有する芳香族アミンが挙げられ、例えば、N,N′-ジフェニル-p-フェニレンジアミン、N,N′-ジ-2-ナフチル-p-フェニレンジアミン、ジフェニルアミンとジイソブチレンとの反応生成物等のフェニレンジアミン系化合物;ジナフチルアミン、フェニル-α-ナフチルアミン、フェニル-β-ナフチルアミン、4,4′-ビス(α,α′-ジメチルベンジル)ジフェニルアミン、フェニルシクロヘキシル-p-フェニレンジアミン、スチレン化ジフェニルアミン等のその他の芳香族第2級アミン化合物等が挙げられる。
上記有機硫黄含有化合物としては、また、例えば、窒素原子に結合する水素原子の少なくとも1個が炭素数1~6の飽和又は不飽和の炭化水素基に置換されていてもよいチオ尿素が好ましく、チオ尿素、N,N′-ジエチルチオ尿素、N,N′-ジブチルチオ尿素、ジラウリルチオ尿素、N,N′-ジフェニルチオ尿素等のチオ尿素誘導体等であってもよい。
上記熱安定剤としては、1種又は2種以上を組み合わせて用いることができる。組み合わせて用いる場合、上述した熱安定剤の質量は、組み合わせた全ての熱安定剤の合計質量である。
また、本開示の粉体状プライマー組成物は、被塗装物に直接塗布されることが好ましい。
本開示の粉体状プライマー組成物は、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(以下、耐熱層ともいう)の上に塗布されることが好ましく、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ことがより好ましい。
本開示のプライマー皮膜は、被塗装物及び溶融性パーフルオロポリマー皮膜との密着性に優れる。
本開示は、プライマー皮膜の上に、溶融性パーフルオロポリマーを含む皮膜が設けられた積層体でもある。
また、粉体状プライマー組成物中の溶融性フッ素樹脂と同種のものを使用しても、異なるものを使用するようにしてもよい。
ただし、フッ素樹脂粒子の液体分散液を噴霧乾燥する工程を経て粉体塗料を製造する方法では、液体分散液を安定化させるための界面活性剤が粉体塗料、さらには、塗布された皮膜に残存することがある。このような場合には、パーフルオロポリマー皮膜の耐熱性や耐薬品性が損なわれるために好ましくない。
本開示の塗装物品は、上記プライマー皮膜と上記被塗装物及び上記溶融性パーフルオロポリマー皮膜との密着性に優れる。また、上記積層塗膜のブリスターの発生が抑制されている。
特に、本開示は、金属基材上に上記積層体が設けられた塗装物品でもある。金属基材である、配管、パイプ、ダクト等の内面に上記積層体が設けられた塗装物品とすることが好ましい。
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。
PFA粉末(A)(MFR:27g/10min、平均粒径:38μm)700g、ポリエーテルサルフォン粉末(平均粒径:10μm)300gを混合して、PFA粉体状プライマー組成物を得た。
脱脂されたSUS304基材(200mm×200mm×1.5mm)に80メッシュのアルミナとしてトサエメリー(宇治電化学工業社製)を0.5MPaの圧力でブラストを行い、エアーでブラスト粉を除去した後に、上記により得たPFA粉体状プライマー組成物を静電粉体塗装法にて膜厚が30~50μmとなるように塗装し、350℃で30分間焼成した。
次いで、PFA粉体塗料(MFR:27g/10min、平均粒径:38μm)を静電塗装し、350℃で30分間焼成を行う工程を繰り返して、約300μmの厚みの塗装膜を持つ塗装物品を得た。
この塗装物品を、山崎式ライニングテスターによる浸透試験(試験液:純水、内部温度:100℃、外部温度:20℃、試験時間:24時間)により、塗装膜にブリスターが発生する面積の割合を評価した。
PFA粉(A)に代えて、FEP粉末(MFR:19g/10min、平均粒径:45μm)を用いたこと以外は、実施例1と同様の手順を実施してFEP粉体状プライマー組成物を得た。
そして、PFA粉体塗料に代えて、FEP粉体塗料(MFR:19g/10min、平均粒径:45μm)を用いたこと以外は、実施例1と同様の手順で塗装物品を作製して、塗装膜にブリスターが発生する面積の割合を評価した。
実施例1で得たPFA粉体プライマー組成物に、さらに炭酸カルシウム粉末(平均粒径:1μm)50gを添加して混合したこと以外は、実施例1と同様の手順を実施してPFA粉体状プライマー組成物を得た。そして、実施例1と同様の手順で塗装物品を作製して、塗装膜にブリスターが発生する面積の割合を評価した。
PFA粉末(A)に代えて、FEP粉末(MFR:19g/10min、平均粒径:45μm)を用い,さらに硫酸バリウム粉末(平均粒径:1μm)50gを添加して混合したこと以外は、実施例1と同様の手順を実施してFEP粉体状プライマー組成物を得た。
そして、PFA粉体塗料に代えて、FEP粉体塗料(MFR:19g/10min、平均粒径:45μm)を用いたこと以外は、実施例1と同様の手順で塗装物品を作製して、塗装膜にブリスターが発生する面積の割合を評価した。
PFA粉末(A)(MFR:27g/10min、平均粒径:38μm)に代えて、PFA粉末(B)(MFR:24g/10min、平均粒径:17μm)を用いたこと以外は、実施例1と同様の手順を実施してPFA粉体状プライマー組成物を得た。
そして、実施例1と同様の手順で塗装物品を作製して、塗装膜にブリスターが発生する面積の割合を評価した。
PFA粉末(A)(MFR:27g/10min、平均粒径:38μm)に代えて、PFA粉末(C)(MFR:6g/10min、平均粒径:32μm)を用いたこと以外は、実施例1と同様の手順を実施してPFA粉体状プライマー組成物を得た。
そして、実施例1と同様の手順で塗装物品を作製して、塗装膜にブリスターが発生する面積の割合を評価した。
PFA粉末(A)(MFR:27g/10min、平均粒径:38μm)に代えて、PFA粉末(D)(MFR:46g/10min、平均粒径:33μm)を用いたこと以外は、実施例1と同様の手順を実施してPFA粉体状プライマー組成物を得た。
そして、実施例1と同様の手順で塗装物品を作製して、塗装膜にブリスターが発生する面積の割合を評価した。
ポリエーテルサルフォン粉末に代えて、ポリアミドイミド粉末(酸価:80mgKOH/g、平均粒径:20μm)を用いたこと以外は、実施例1と同様の手順を実施してPFA粉体状プライマー組成物を得た。
そして、実施例1と同様の手順で塗装物品を作製して、塗装膜にブリスターが発生する面積の割合を評価した。
ポリエーテルサルフォン粉末に代えて、ポリアミドイミド粉末(酸価:80mgKOH/g、平均粒径:20μm)とポリフェニレンサルファイド粉末(ASTM D1238によるMFR:5000g/10min、平均粒径:35μm)を用いたこと以外は、実施例1と同様の手順を実施してPFA粉体状プライマー組成物を得た。
そして、実施例1と同様の手順で塗装物品を作製して、塗装膜にブリスターが発生する面積の割合を評価した。
PFA粉末(A)(MFR:27g/10min、平均粒径:38μm)400g、ポリエーテルサルフォン粉末(平均粒径:10μm)600gを混合して、PFA粉体状プライマー組成物を得た。
その後は、実施例1と同様の手順で塗装物品を作製して、塗装膜にブリスターが発生する面積の割合を評価した。
PFA粉末(A)(MFR:27g/10min、平均粒径:38μm)970g、ポリエーテルサルフォン粉末(平均粒径:10μm)30gを混合して、PFA粉体状プライマー組成物を得た。
その後は、実施例1と同様の手順で塗装物品を作製して、塗装膜にブリスターが発生する面積の割合を評価した。
Claims (7)
- 平均粒径が5~100μmである溶融性フッ素樹脂粉末及びポリエーテルサルフォン粉末を含み、
前記溶融性フッ素樹脂粉末と前記ポリエーテルサルフォン粉末との重量比は50:50~95:5であり、更に、平均粒径が0.1~50μmである硫酸バリウム及び炭酸カルシウムより選択される少なくとも1種を、溶融性フッ素樹脂粉末の固形分に対し、1~20質量%含有することを特徴とする、粉体状プライマー組成物。 - 溶融性フッ素樹脂のメルトフローレートが0.1~50g/10分である、請求項1に記載の粉体状プライマー組成物。
- 溶融性フッ素樹脂がパーフルオロポリマーである、請求項1または2に記載の粉体状プライマー組成物。
- 請求項1~3のいずれかに記載の粉体状プライマー組成物から形成されるプライマー皮膜。
- 請求項4に記載のプライマー皮膜の上に、溶融性フッ素樹脂を含む皮膜が設けられた積層体。
- 金属基材上に請求項5に記載の積層体が設けられた塗装物品。
- 金属基材が配管、パイプ又はダクトであり、その内面に請求項5に記載の積層体が設けられた塗装物品。
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