TW202246422A - 粉體狀底漆組成物 - Google Patents
粉體狀底漆組成物 Download PDFInfo
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- TW202246422A TW202246422A TW111108539A TW111108539A TW202246422A TW 202246422 A TW202246422 A TW 202246422A TW 111108539 A TW111108539 A TW 111108539A TW 111108539 A TW111108539 A TW 111108539A TW 202246422 A TW202246422 A TW 202246422A
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Abstract
本發明提供一種粉體狀底漆組成物，其可抑制於積層塗膜中發生起泡。
本發明之粉體狀底漆組成物之特徵在於：包含平均粒徑為5～100 μm之熔融性氟樹脂粉末及聚醚碸粉末，且上述熔融性氟樹脂粉末與上述聚醚碸粉末之重量比為50：50～95：5。
Description
本發明係關於一種粉體狀底漆組成物。
一般而言，利用氟樹脂所具有之優異之耐熱性、耐化學品性、阻燃性等，廣泛使用氟樹脂、其中廣泛使用全氟聚合物作為化學工場或半導體工場中之耐蝕襯裡用塗佈材料。然而，全氟聚合物與金屬之密合性較差，因此於大多數情形，會將對金屬基材之密合性優異之底漆層作為由全氟聚合物所構成之面塗層（topcoat）之下塗層，設置於金屬基材之表面。
先前，已知有各種底漆，其等使各種金屬基材、與以四氟乙烯/全氟烷基乙烯基醚共聚物（PFA）粒子或四氟乙烯/六氟丙烯共聚物（FEP）粒子等熔融性全氟聚合物為主成分之膜厚50 μm以上之面塗層接著。例如，有以有機溶劑為分散介質之底漆、或含有醯胺系樹脂作為黏合劑樹脂之主成分之粉體狀底漆等。
專利文獻1中揭示有一種液狀塗料組成物，其由含醯胺基性高分子化合物（A）、抗氧化性物質（B）、及氟樹脂（C）所構成。具體而言，揭示有一種使用聚醯胺醯亞胺之有機溶劑系底漆組成物。
專利文獻2中揭示有一種底漆組成物，其係將作為醯胺醯亞胺樹脂、醯亞胺樹脂、醚醯亞胺樹脂或聚醚碸樹脂之高分子材料、與平均粒徑為5～30 μm之熔融性氟樹脂以特定比率進行摻合而獲得者。
專利文獻3中揭示有一種粉體狀底漆組成物，其含有：具有醯胺基及/或醯亞胺基之高分子化合物（A）、抗氧化性物質（B）、及氟樹脂（C）。
先前技術文獻
專利文獻
專利文獻1：國際公開第2004/048489號
專利文獻2：日本特開2008-45140號公報
專利文獻3：國際公開第2009/119493號
[發明所欲解決之課題]
本發明之目的在於提供一種粉體狀底漆組成物，其可抑制包含全氟聚合物層之積層皮膜中發生起泡。
[解決課題之技術手段]
本發明係一種粉體狀底漆組成物，其特徵在於：包含平均粒徑為5～100 μm之熔融性氟樹脂粉末及聚醚碸粉末，且上述熔融性氟樹脂粉末與上述聚醚碸粉末之重量比為50：50～95：5。
熔融性氟樹脂之熔體流動速率較佳為0.1～50 g/10分鐘。
熔融性氟樹脂較佳為全氟聚合物。
本發明亦係一種底漆皮膜，其由上述粉體狀底漆組成物所形成。
本發明亦係一種積層體，其係於上述底漆皮膜之上設有包含熔融性全氟聚合物之皮膜者。
本發明亦係一種塗裝物品，其係於金屬基材上設有上述積層體者。
本發明亦係一種塗裝物品，其係於金屬基材之內表面設有上述積層體者，上述金屬基材為配管、管道管（pipe）或導管（duct）。
[發明之效果]
根據本發明，可提供一種粉體狀底漆組成物，其可抑制於積層塗膜中發生起泡。因此，可實現熔融性全氟聚合物皮膜之長壽命化。
以下，對本發明進行詳細說明。
本發明之粉體狀底漆組成物之特徵在於：包含平均粒徑為5～100 μm之熔融性氟樹脂粉末及聚醚碸粉末，且上述熔融性氟樹脂粉末與上述聚醚碸（PES）粉末之重量比為50：50～95：5。
於將底漆組成物製成液狀底漆之情形時，期待製成水系底漆，但於以水為分散介質之底漆組成物中，熔融性氟樹脂粒子之分散穩定性存在問題。又，於含有醯胺系樹脂或醯亞胺系樹脂之粉末作為黏合劑樹脂之主成分的粉體狀底漆組成物中，存在以下問題，即，在與面塗層之積層塗膜中容易發生起泡。
因此，本發明發現：若使用PES粉末作為黏合劑樹脂，則可抑制起泡發生。起泡係於積層塗膜之密合性不充分之情形等時，因水蒸氣等水分滲入至積層塗膜內而發生之塗膜之鼓出，但PES由於熔融流動性優異，故而容易確保與金屬基材之較高之密合力，由此，水分之透過性變小，因此可抑制起泡發生。
如上所述，本發明之粉體狀底漆組成物使用聚醚碸（PES）粉末作為耐熱性樹脂粉末。
PES係由具有下述通式：
所表示之重複單元之聚合物所構成之樹脂。
作為PES，並無特別限定，例如較佳地使用藉由使二鹵代二苯基化合物與二元酚（dihydric phenol）化合物進行縮聚、或者使二元酚之鹼金屬二鹽與二鹵代二苯基化合物進行縮聚而獲得者。
作為上述二鹵代二苯基化合物，可例舉具有碸基之二鹵代二苯基化合物，例如4,4'-二氯二苯基碸、4,4'-二氟二苯基碸等二鹵代二苯基碸類、1,4-雙(4-氯苯基磺醯基)苯、1,4-雙(4-氟苯基磺醯基)苯等雙(鹵代苯基磺醯基)苯類、4,4'-雙(4-氯苯基磺醯基)聯苯、4,4'-雙(4-氟苯基磺醯基)聯苯等雙(鹵代苯基磺醯基)聯苯類等。其中，就容易獲取之方面而言，較佳為二鹵代二苯基碸類，更佳為4,4'-二氯二苯基碸或4,4'-二氟二苯基碸，特佳為4,4'-二氯二苯基碸。該等二鹵代二苯基化合物亦可混合兩種以上而使用。
作為上述二元酚化合物，除了對苯二酚、鄰苯二酚、間苯二酚、4,4'-聯苯二酚以外，亦可例舉：2,2-雙(4-羥基苯基)丙烷、2,2-雙(4-羥基苯基)甲烷、2,2-雙(4-羥基苯基)乙烷等雙(4-羥基苯基)烷烴類、4,4'-二羥基二苯基碸等二羥基二苯基碸類、4,4'-二羥基二苯醚等二羥基二苯醚類、或者其等之苯環之氫原子之至少一個被取代成甲基、乙基、丙基等低級烷基、甲氧基、乙氧基、丙氧基等低級烷氧基、或氯原子、溴原子、氟原子等鹵素原子所獲得者。尤其就價格及獲取之容易性方面而言，較佳為對苯二酚、4,4'-聯苯二酚、2,2-雙(4-羥基苯基丙烷)、4,4'-二羥基二苯醚、或4,4'-二羥基二苯基碸，特佳為4,4'-二羥基二苯基碸。上述二元酚化合物亦可混合兩種以上而使用。
本發明中所使用之PES較佳為實質上等莫耳量地使用二元酚化合物與二鹵代二苯基碸化合物並使其等進行縮聚而成者。
PES粉末之平均粒徑較佳為0.1～50 μm，更佳為1～30 μm。若PES粒子之平均粒徑處於該範圍內，則可兼顧與金屬基材之密合性及塗裝性。
上述平均粒徑係藉由雷射繞射法所測定之值。具體而言，係利用Microtrac公司製造之MT-3300II所測得之體積基準之中值粒徑。
作為本發明中所使用之上述熔融性氟樹脂，可例舉藉由使用下述單體中之一種或兩種以上作為單體成分進行聚合而獲得者等，上述單體例如為：氯三氟乙烯等氯氟乙烯單體；三氟乙烯等氟乙烯單體；四氟乙烯、六氟丙烯、全氟(烷基乙烯基醚)等全氟單體等。作為上述單體成分，亦可為進而包含乙烯、丙烯等乙烯單體之一種或兩種以上者。上述全氟單體係主鏈由碳原子及氟原子以及視情況之氧原子所構成，且不具有CH或CH
2者，上述全氟單體包含全氟乙烯單體及全氟(烷基乙烯基醚)單體。上述氧原子通常為醚氧。
關於上述熔融性氟樹脂，又，亦可使用具有羥基、羰基等官能基之單體作為少量地與上述單體成分一起進行共聚之共聚單體，亦可使用具有環狀結構之單體作為少量地與上述單體成分一起進行共聚之共聚單體。作為上述環狀結構，例如可例舉具有環狀縮醛結構等環狀醚結構者等，較佳為構成上述環狀醚結構之至少2個碳原子為上述熔融性氟樹脂之主鏈之一部分者。
作為上述熔融性氟樹脂，例如可例舉：乙烯/四氟乙烯共聚物[ETFE]、乙烯/氯三氟乙烯共聚物、丙烯/四氟乙烯共聚物等烯烴/氟烯烴共聚物；四氟乙烯/六氟丙烯共聚物[FEP]、四氟乙烯/全氟(烷基乙烯基醚)共聚物[PFA]等全氟聚合物。上述全氟聚合物係以上述全氟單體為單體成分者。
作為上述熔融性氟樹脂，根據用途而有所不同，但較佳為上述全氟聚合物。作為上述全氟聚合物，更佳為使用四氟乙烯作為共聚單體進行共聚而成者，關於作為其他共聚單體之上述全氟單體，並無特別限定。特別是FEP或PFA在與作為基材之金屬的密合中、及與作為面塗層之全氟聚合物皮膜或經層壓之全氟聚合物膜之層間密合中均可獲得較佳之結果，就該方面而言較為適宜。
作為上述熔融性氟樹脂，必須為熔融性。若為熔融性，則可藉由下述焙燒進行熔融而成膜。
上述熔融性氟樹脂之熔融性一般以MFR表示作為流動性之指標。MFR係以依據ASTMD3159，於5 Kg之負載從直徑2 mm之噴嘴歷時10分鐘所擠出之重量表示者。於上述熔融性氟樹脂為PFA、FEP等全氟聚合物之情形時，在372℃測定MFR，於為ETFE之情形時，在297℃測定MFR。
上述熔融性氟樹脂之MFR較佳為0.1～50 g/10分鐘。
若處於上述熔體流動速率之範圍內，則所獲得之底漆皮膜與熔融性全氟聚合物皮膜之密合性因熔融性氟樹脂之流動特性而進一步提高。
尤其是，上述全氟聚合物之MFR較佳為1～40 g/10分鐘。更佳之下限為10 g/10分鐘，更佳之上限為30 g/10分鐘。
若處於上述熔體流動速率之範圍內，則可兼顧層間密合性與耐蝕性。
上述熔融性氟樹脂可藉由調整上述分子量，而成為具有上述範圍內之熔體流動速率者。
上述熔融性氟樹脂粉末之平均粒徑為5～100 μm。若平均粒徑脫離該範圍，則可能導致塗裝性或塗佈效率降低。又，可能難以抑制起泡發生。上述平均粒徑之較佳之下限為10 μm，更佳之下限為15 μm，進而較佳之下限為20 μm。較佳之上限為90 μm。
上述平均粒徑係藉由雷射繞射法所測定之值。具體而言，係利用Microtrac公司製造之MT-3300II所測得之體積基準之中值粒徑。
上述熔融性氟樹脂粉末之製造方法並無特別限定，例如可藉由乳化聚合等先前公知之聚合方法等進行共聚而獲得。對於藉由共聚所獲得之熔融性氟樹脂，視需要以成為具有上述範圍內之平均粒徑之熔融性氟樹脂粉末之方式進行粉碎。作為上述粉碎之方法，並無特別限定，例如可使用先前公知之方法。例如可例舉利用輥將藉由上述乳化聚合法所獲得之熔融性氟樹脂乾燥粉末壓縮成片狀，利用粉碎機進行粉碎並進行分級之方法等。
上述熔融性氟樹脂粉末與聚醚碸粉末之固形物成分質量比為50：50～95：5。若上述熔融性氟樹脂粉末過少，則所獲得之底漆皮膜與熔融性氟樹脂皮膜之密合性降低，引起層間剝離，若過多，則上述底漆皮膜與被塗裝物之密合力降低。上述固形物成分質量比之較佳之下限為70：30，更佳之下限為76：24，並且較佳之上限為85：15。
本發明之粉體狀底漆組成物較佳為進而含有選自硫酸鋇、碳酸鈣等金屬鹽粉末中之至少一種。若含有其等，則進一步抑制積層塗膜之起泡發生。
上述金屬鹽粉末之平均粒徑較佳為0.1～50 μm，更佳為0.1～10 μm。若耐熱性樹脂粒子之粒徑處於該範圍內，則可確保被塗裝物與包含全氟聚合物之面塗層之較高密合力。
上述平均粒徑係藉由雷射繞射法所測定之值。具體而言，係利用Microtrac公司製造之MT-3300II所測得之體積基準之中值粒徑。
於本發明之粉體狀底漆組成物中含有上述金屬鹽粉末之情形時，相對於上述熔融性氟樹脂粉末之固形物成分，上述金屬鹽粉末較佳為1～20質量%。更佳之下限為3質量%，更佳之上限為10質量%。
本發明之粉體狀底漆組成物亦可為含有熱穩定劑者。本發明之粉體狀底漆組成物藉由含有上述熱穩定劑，可防止熔融性氟樹脂塗膜形成中之加熱等所導致之上述熔融性氟樹脂粉末之氧化，減輕熱劣化，其結果為，可進一步提高密合穩定性。
作為上述熱穩定劑，就防止上述熔融性氟樹脂粉末之氧化之方面而言，較佳為胺系抗氧化劑及/或有機含硫化合物。
作為上述胺系抗氧化劑，例如可例舉於分子中具有苯基、萘基等芳香族性烴基之芳香族胺，例如可例舉：N,N'-二苯基-對苯二胺、N,N'-二-2-萘基-對苯二胺、二苯胺與二異丁烯之反應產物等苯二胺系化合物；二萘胺、苯基-α-萘胺、苯基-β-萘胺、4,4'-雙(α,α'-二甲基苄基)二苯胺、苯基環己基-對苯二胺、苯乙烯化二苯胺等其他芳香族二級胺化合物等。
作為上述胺系抗氧化劑，可例舉具有以苯并三唑為基本骨架之化學結構之苯并三唑系化合物，係可形成金屬鹽等鹽者。作為上述苯并三唑系化合物，並無特別限定，例如可例舉：苯并三唑、2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基-5-四辛基苯基)苯并三唑等。
作為上述有機含硫化合物，例如可例舉2-巰基苯并咪唑、2-巰基甲基苯并咪唑等巰基苯并咪唑系化合物；2-巰基苯并噻唑、2-巰基苯并噻唑之環己基胺鹽、二硫化二苯并噻唑（dibenzothiazyl disulfide）、2-(N,N'-二乙基硫胺基甲醯基硫)苯并噻唑、2-(4'-
啉二硫)苯并噻唑、N-環己基-2-苯并噻唑次磺醯胺、N-氧聯二伸乙基-2-苯并噻唑次磺醯胺、N-第三丁基-2-苯并噻唑次磺醯胺、N,N'-二環己基-2-苯并噻唑次磺醯胺、N,N'-二異丙基苯并噻唑-2-次磺醯胺等巰基苯并噻唑系化合物；2-巰基咪唑啉等巰基咪唑啉系化合物；伸戊基二硫代胺基甲酸、哌可二硫代胺基甲酸（pipecolyl dithiocarbamic acid）、二甲基二硫代胺基甲酸、二乙基二硫代胺基甲酸、二丁基二硫代胺基甲酸、N-乙基-N-苯基二硫代胺基甲酸等二硫代胺基甲酸類等；其等亦可為例如Zn、Sn、Cd、Cu、Fe等之金屬鹽、哌啶鹽、哌可鹽等有機鹽等。
作為上述有機含硫化合物，例如可例舉秋蘭姆（thiuram）系化合物，例如可例舉：一硫化四甲基秋蘭姆等一硫化秋蘭姆；二硫化四甲基秋蘭姆、二硫化四乙基秋蘭姆、二硫化四丁基秋蘭姆等二硫化秋蘭姆；四硫化二伸戊基秋蘭姆等其他秋蘭姆系化合物等。
作為上述有機含硫化合物，又，例如較佳為與氮原子鍵結之氫原子之至少1個可被取代為碳數1～6之飽和或不飽和烴基之硫脲，亦可為硫脲、N,N'-二乙基硫脲、N,N'-二丁基硫脲、二月桂基硫脲、N,N'-二苯基硫脲等硫脲衍生物等。
作為上述熱穩定劑，其中，就要求在本發明之粉體狀底漆組成物或熔融性氟樹脂塗料中所含之熔融性氟樹脂之熔點附近之溫度以上、例如於約250℃以上之高溫的穩定性之方面而言，較佳為含芳香環之化合物，更佳為芳香族胺、巰基苯并噻唑系化合物及巰基苯并咪唑系化合物等。
上述熱穩定劑可藉由先前公知之方法進行製造，但通常可使用市售品。
作為上述熱穩定劑，可使用一種或組合兩種以上而使用。於組合使用之情形時，上述熱穩定劑之質量係所組合之所有熱穩定劑之合計質量。
於本發明之粉體狀底漆組成物中包含上述熱穩定劑之情形時，就熱穩定效果、及防止上述熱穩定劑之分解所致之起泡之觀點而言，相對於上述熔融性氟樹脂粉末之固形物成分，上述熱穩定劑較佳為0.001～5質量%。更佳之下限為0.003質量%，更佳之上限為2質量%。
本發明之熔融性氟樹脂塗料用底漆亦可視需要進而含有添加劑。作為上述添加劑，並無特別限定，例如可例舉一般塗料之底漆中所使用者等。作為上述添加劑，例如可例舉：顏料、填充材、調平劑、固體潤滑劑、水分吸收劑、表面調整劑、紫外線吸收劑、光穩定劑、塑化劑、抗分色劑、抗擦傷劑、防黴劑、抗菌劑、抗氧化劑、抗靜電劑、矽烷偶合劑等。
作為上述添加劑，具體而言，例如可例舉：碳、氧化鈦、紅丹、雲母等著色顏料、防銹顏料、焙燒顏料、體質顏料、光致發光扁平顏料、鱗片狀顏料、木粉、石英砂、碳黑、黏土、滑石、金剛石、氟化金剛石、鋼玉、矽石、氮化硼、碳化硼、碳化矽、熔鋁氧、電氣石、翡翠、鍺、氧化鋯、碳化鋯、金綠寶石、黃玉、綠寶石、石榴石、玻璃、玻璃粉、雲母粉、金屬粉（金、銀、銅、鉑、不鏽鋼、鋁等）、各種強化材、各種增量材、導電性填料等。
相對於上述粉體狀底漆組成物，上述添加劑之含量較佳為0～10.0質量%，更佳為0～5.0質量%。
本發明之粉體狀底漆組成物例如係藉由先前公知之方法等進行製備。例如，可藉由以下方式進行製備，即，利用混合機將上述熔融性氟樹脂粉末及聚醚碸粉末、以及視需要之熱穩定劑等進行混合。作為混合機，並無特別限定，可使用通常之V型攪拌器、亨舍爾混合機等。
本發明之粉體狀底漆組成物係用以形成設置於熔融性全氟聚合物皮膜之下層之底漆皮膜者，較佳為用以形成下述之底漆皮膜者，即，以與熔融性全氟聚合物皮膜之下層直接相接之方式設置之底漆皮膜。再者，熔融性全氟聚合物皮膜之下層意指該熔融性全氟聚合物皮膜與被塗裝物（基材）之間。關於上述熔融性全氟聚合物皮膜，將於下文敍述。
又，本發明之粉體狀底漆組成物較佳為直接塗佈於被塗裝物。
將本發明之粉體狀底漆組成物塗佈於被塗裝物上，適當地進行加熱，藉此可形成底漆皮膜。
作為上述被塗裝物，只要為可供熔融性全氟聚合物皮膜形成者，便無特別限定。
本發明之粉體狀底漆組成物較佳為直接塗佈於由金屬或非金屬無機材料所構成之基材上，或塗佈於由耐熱性樹脂所構成之層（以下亦稱為耐熱層）之上，更佳為直接塗佈於由金屬或非金屬無機材料所構成之基材上。
作為上述金屬，可例舉鐵、鋁、銅等金屬單質及其等之合金類等。作為上述合金類，可例舉不鏽鋼（SUS）等。作為上述非金屬無機材料，可例舉琺瑯、玻璃、陶瓷等。上述基材亦可於包含金屬或非金屬無機材料之同時包含其他材料。
作為上述基材，較佳為由金屬所構成者，更佳為由鋁或不鏽鋼所構成者。
本發明之粉體狀底漆組成物特別適用於金屬基材。作為上述金屬基材，具體而言，可例舉配管、管道管、導管等工業零件相關用途等。於其等之內表面塗佈粉體狀底漆組成物。將本發明之粉體狀底漆組成物用於上述金屬基材可確保較高之接著力，就該方面而言較為有利。
針對上述被塗裝物，亦可視需要預先實施清洗、噴砂等表面處理。上述噴砂係吹送矽砂、氧化鋁粉等砂，由於使被塗裝物之表面粗糙化，故而會提高密合性，就該方面而言，較佳為進行上述噴砂。
作為對上述被塗裝物進行塗佈之方法，並無特別限定，可根據被塗裝物之形態等進行適當選擇，例如可例舉靜電塗裝等先前公知之方法等。上述塗佈可按照乾燥膜厚成為20～150 μm之方式進行。亦可於上述塗佈時進行加熱，例如亦可於60～120℃進行塗佈。
本發明亦係關於一種底漆皮膜，其由本發明之粉體狀底漆組成物所形成。
本發明之底漆皮膜與被塗裝物及熔融性全氟聚合物皮膜之密合性優異。
上述底漆被膜之膜厚適宜的是20～150 μm。更佳為50～100 μm。
於上述底漆皮膜之上塗佈熔融性全氟聚合物塗料，進行加熱焙燒，藉此可形成熔融性全氟聚合物皮膜。
本發明亦係一種積層體，其係於底漆皮膜之上設有包含熔融性全氟聚合物之皮膜者。
上述熔融性全氟聚合物塗料係以熔融性全氟聚合物為主成分者，可為視需要適當地含有添加劑等其他成分者，並無特別限定。
作為上述熔融性全氟聚合物塗料中所使用之熔融性全氟聚合物，更佳為使用四氟乙烯作為共聚單體進行共聚而成者，關於作為其他共聚單體之上述全氟單體，並無特別限定。
又，可使用與粉體狀底漆組成物中之熔融性氟樹脂種類相同者，亦可使用不同者。
上述熔融性全氟聚合物塗料較佳為粉體塗料。作為上述粉體塗料之製法，並無特別限定，例如可例舉先前公知之方法等，可使用下述等方法：視需要將熔融性全氟聚合物及其他成分進行熔融混練後進行粉碎之方法；藉由上述熔融性全氟聚合物粉末之粉碎方法中所說明之方法進行粉碎並進行分級之方法。
但是，於經由對氟樹脂粒子之液體分散液進行噴霧乾燥之步驟而製造粉體塗料的方法中，用以使液體分散液穩定化之界面活性劑有時會殘存於粉體塗料中，甚至殘存於所塗佈之皮膜中。於此種情形時，會損害全氟聚合物皮膜之耐熱性或耐化學品性，因此欠佳。
上述粉體塗料可用作以下塗料，例如：藉由靜電塗裝法來形成一般膜厚為20～100 μm之薄塗皮膜之塗料、藉由靜電塗裝法來形成一般膜厚為100～1500 μm之厚塗皮膜之塗料、藉由旋轉襯裡法來形成一般膜厚為1000～5000 μm之厚塗皮膜之塗料。於藉由靜電塗裝法來獲得厚塗皮膜時，在多數情況會將下述步驟反覆進行2次以上：將粉體塗料塗佈於被塗裝物後，進行加熱焙燒而使其成膜。
藉由靜電塗裝法來形成薄塗皮膜之粉體塗料中所含之熔融性全氟聚合物較佳為平均粒徑為5～50 μm。若平均粒徑未達5 μm，則於塗佈時容易發生靜電排斥，存在難以獲得平滑皮膜之傾向，即便平均粒徑超過50 μm，亦存在難以獲得平滑皮膜之傾向。更佳之平均粒徑之範圍為10～40 μm。
藉由靜電塗裝法來形成厚塗皮膜之粉體塗料中所含之熔融性全氟聚合物較佳為平均粒徑為20～100 μm。若平均粒徑未達20 μm，則存在難以獲得厚塗皮膜之傾向，若平均粒徑超過100 μm，則存在塗佈效率降低之傾向。更佳之平均粒徑之範圍為30～90 μm。
藉由旋轉襯裡法來形成厚塗皮膜之粉體塗料中所含之熔融性全氟聚合物較佳為平均粒徑為150～500 μm。若平均粒徑未達150 μm，或平均粒徑超過500 μm，則存在氣泡容易殘留於皮膜中之傾向，存在難以獲得平滑皮膜之傾向。更佳之平均粒徑之範圍為200～450 μm。
上述粉體塗料之平均粒徑係藉由雷射繞射法所測定之值。具體而言，係利用Microtrac公司製造之MT-3300II所測定之體積基準之中值粒徑。
本發明中所使用之粉體塗料可在藉由塗佈於被塗裝物後進行加熱焙燒而使其成膜等方式進行施工後，作為耐蝕襯裡等而用於各種用途。對於本發明中所使用之粉體塗料，藉由在本發明之範圍內如上所述般調整平均粒徑、熔體流動速率等，可將其製成適宜上述塗佈方法或適宜獲得焙燒後之膜厚之粉體塗料。
本發明亦係關於一種塗裝物品，其係於被塗裝物上設有積層體者，該積層體具有形成於上述被塗裝物上之本發明之底漆皮膜、及形成於上述底漆皮膜上之熔融性全氟聚合物皮膜。
於本發明之塗裝物品中，上述底漆皮膜與上述被塗裝物及上述熔融性全氟聚合物皮膜之密合性優異。又，上述積層塗膜之起泡發生得到抑制。
尤其是，本發明亦係一種塗裝物品，其係於金屬基材上設有上述積層體者。較佳為製成下述塗裝物品，其於作為金屬基材之配管、管道管、導管等之內表面設置有上述積層體。
關於上述被塗裝物、上述底漆皮膜、上述熔融性全氟聚合物皮膜，如上所述。
於本發明之塗裝物品中，較佳為上述被塗裝物與上述底漆皮膜直接相接。又，較佳為上述底漆皮膜與上述全氟聚合物皮膜直接相接。又，亦可於上述熔融性全氟聚合物皮膜上進而設置有層，但較佳為上述熔融性全氟聚合物皮膜為最外層。
[實施例]
以下，基於實施例對本發明進行具體說明。
於以下實施例中，在未特別提及之情形時，「份」「%」分別表示「質量份」「質量%」。
（實施例1）
將PFA粉末（A）（MFR：27 g/10 min，平均粒徑：38 μm）700 g、聚醚碸粉末（平均粒徑：10 μm）300 g加以混合而獲得PFA粉體狀底漆組成物。
將成為80目氧化鋁之TOSA EMERY（宇治電化學工業公司製造）以0.5 MPa之壓力進行噴砂至經除脂之SUS304基材（200 mm×200 mm×1.5 mm），利用空氣去除噴砂粉後，將藉由上述方式所獲得之PFA粉體狀底漆組成物以膜厚成為30～50 μm之方式藉由靜電粉體塗裝法進行塗裝，於350℃焙燒30分鐘。
繼而，靜電塗裝PFA粉體塗料（MFR：27 g/10 min，平均粒徑：38 μm），並於350℃進行30分鐘焙燒，反覆進行該步驟，獲得具有厚度約300 μm之塗裝膜之塗裝物品。
對於該塗裝物品，藉由利用山崎式襯裡測試機進行之滲透試驗（試驗液：純水，內部溫度：100℃，外部溫度：20℃，試驗時間：24小時）來評估塗裝膜發生起泡之面積的比例。
（實施例2）
使用FEP粉末（MFR：19 g/10 min，平均粒徑：45 μm）來代替PFA粉（A），除此以外，實施與實施例1相同之順序而獲得FEP粉體狀底漆組成物。
繼而，使用FEP粉體塗料（MFR：19 g/10 min，平均粒徑：45 μm）來代替PFA粉體塗料，除此以外，以與實施例1相同之順序來製作塗裝物品，評估塗裝膜發生起泡之面積的比例。
（實施例3）
向實施例1中所獲得之PFA粉體底漆組成物中進而添加碳酸鈣粉末（平均粒徑：1 μm）50 g並加以混合，除此以外，實施與實施例1相同之順序而獲得PFA粉體狀底漆組成物。繼而，以與實施例1相同之順序來製作塗裝物品，評估塗裝膜發生起泡之面積的比例。
（實施例4）
使用FEP粉末（MFR：19 g/10 min，平均粒徑：45 μm）來代替PFA粉末（A），進而添加硫酸鋇粉末（平均粒徑：1 μm）50 g並加以混合，除此以外，實施與實施例1相同之順序而獲得FEP粉體狀底漆組成物。
繼而，使用FEP粉體塗料（MFR：19 g/10 min，平均粒徑：45 μm）來代替PFA粉體塗料，除此以外，以與實施例1相同之順序來製作塗裝物品，評估塗裝膜發生起泡之面積的比例。
（實施例5）
使用PFA粉末（B）（MFR：24 g/10 min，平均粒徑：17 μm）來代替PFA粉末（A）（MFR：27 g/10 min，平均粒徑：38 μm），除此以外，實施與實施例1相同之順序而獲得PFA粉體狀底漆組成物。
繼而，以與實施例1相同之順序來製作塗裝物品，評估塗裝膜發生起泡之面積的比例。
（實施例6）
除了使用PFA粉末（C）（MFR：6 g/10 min，平均粒徑：32 μm）來代替PFA粉末（A）（MFR：27 g/10 min，平均粒徑：38 μm），除此以外，實施與實施例1相同之順序而獲得PFA粉體狀底漆組成物。
繼而，以與實施例1相同之順序來製作塗裝物品，評估塗裝膜發生起泡之面積的比例。
（實施例7）
使用PFA粉末（D）（MFR：46 g/10 min，平均粒徑：33 μm）來代替PFA粉末（A）（MFR：27 g/10 min，平均粒徑：38 μm），除此以外，實施與實施例1相同之順序而獲得PFA粉體狀底漆組成物。
繼而，以與實施例1相同之順序來製作塗裝物品，評估塗裝膜發生起泡之面積的比例。
（比較例1）
使用聚醯胺醯亞胺粉末（酸值：80 mgKOH/g，平均粒徑：20 μm）來代替聚醚碸粉末，除此以外，實施與實施例1相同之順序而獲得PFA粉體狀底漆組成物。
繼而，以與實施例1相同之順序來製作塗裝物品，評估塗裝膜發生起泡之面積的比例。
（比較例2）
使用聚醯胺醯亞胺粉末（酸值：80 mgKOH/g，平均粒徑：20 μm）及聚苯硫醚粉末（依據ASTM D1238所得之MFR：5000 g/10 min，平均粒徑：35 μm）來代替聚醚碸粉末，除此以外，實施與實施例1相同之順序而獲得PFA粉體狀底漆組成物。
繼而，以與實施例1相同之順序來製作塗裝物品，評估塗裝膜發生起泡之面積的比例。
（比較例3）
將PFA粉末（A）（MFR：27 g/10 min，平均粒徑：38 μm）400 g、聚醚碸粉末（平均粒徑：10 μm）600 g加以混合而獲得PFA粉體狀底漆組成物。
其後，以與實施例1相同之順序來製作塗裝物品，評估塗裝膜發生起泡之面積的比例。
（比較例4）
將PFA粉末（A）（MFR：27 g/10 min，平均粒徑：38 μm）970 g、聚醚碸粉末（平均粒徑：10 μm）30 g加以混合而獲得PFA粉體狀底漆組成物。
其後，以與實施例1相同之順序來製作塗裝物品，評估塗裝膜發生起泡之面積的比例。
[表1]
[產業上之可利用性]
| 熔融性氟樹脂 | 黏合劑樹脂 | [氟/黏合劑]比 | 添加劑 | 面塗層之熔融性氟樹脂 | 襯裡測試機評估 | ||||||
| 樹脂 | MFR（g/10 min） | 平均粒徑（μm） | 樹脂 | 平均粒徑（μm） | 樹脂 | MFR（g/10 min） | 平均粒徑（μm） | 100℃×24 hr浸漬後之起泡面積（%） | |||
| 實施例1 | PFA | 27 | 38 | PES | 10 | 7/3 | - | PFA | 27 | 38 | 8.0% |
| 實施例2 | FEP | 19 | 45 | PES | 10 | 7/3 | - | FEP | 19 | 45 | 8.5% |
| 實施例3 | PFA | 27 | 38 | PES | 10 | 7/3 | 碳酸鈣 | PFA | 27 | 38 | 7.9% |
| 實施例4 | FEP | 19 | 45 | PES | 10 | 7/3 | 硫酸鋇 | FEP | 19 | 45 | 7.4% |
| 實施例5 | PFA | 24 | 17 | PES | 10 | 7/3 | PFA | 27 | 38 | 9.2% | |
| 實施例6 | PFA | 6 | 32 | PES | 10 | 7/3 | - | PFA | 27 | 38 | 9.8% |
| 實施例7 | PFA | 46 | 33 | PES | 10 | 7/3 | - | PFA | 27 | 38 | 11.3% |
| 比較例1 | PFA | 27 | 38 | PAI | 43 | 7/3 | - | PFA | 27 | 38 | 13.7% |
| 比較例2 | PFA | 27 | 38 | PAI＋PPS | PAI：20 PPS：35 | 7/3 | - | PFA | 27 | 38 | 12.9% |
| 比較例3 | PFA | 27 | 38 | PES | 10 | 4/6 | - | PFA | 27 | 38 | 12.5% |
| 比較例4 | PFA | 27 | 38 | PES | 10 | 97/3 | - | PFA | 27 | 38 | 14.0% |
本發明之粉體狀底漆組成物因具有上述構成，而抑制積層塗膜之起泡發生，尤其適宜作為面向金屬基材之粉體狀底漆組成物。
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Claims (7)
- 一種粉體狀底漆組成物，其特徵在於：包含平均粒徑為5～100 μm之熔融性氟樹脂粉末及聚醚碸粉末，且 上述熔融性氟樹脂粉末與上述聚醚碸粉末之重量比為50：50～95：5。
- 如請求項1之粉體狀底漆組成物，其中，熔融性氟樹脂之熔體流動速率為0.1～50 g/10分鐘。
- 如請求項1或2之粉體狀底漆組成物，其中，熔融性氟樹脂為全氟聚合物。
- 一種底漆皮膜，其由請求項1至3中任一項之粉體狀底漆組成物所形成。
- 一種積層體，其係於請求項4之底漆皮膜之上設有包含熔融性氟樹脂之皮膜者。
- 一種塗裝物品，其係於金屬基材上設有請求項5之積層體者。
- 一種塗裝物品，其係於金屬基材之內表面設有請求項5之積層體者，上述金屬基材為配管、管道管（pipe）或導管（duct）。
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| US7597939B2 (en) * | 2007-02-01 | 2009-10-06 | E.I. Du Pont De Nemours And Company | Process for applying fluoropolymer powder coating as a primer layer and an overcoat |
| WO2009119493A1 (ja) | 2008-03-28 | 2009-10-01 | ダイキン工業株式会社 | 粉体塗料及び含フッ素積層体 |
| JP6149739B2 (ja) * | 2014-01-16 | 2017-06-21 | 旭硝子株式会社 | プライマー組成物及びそれを用いた積層体 |
| KR101900167B1 (ko) | 2014-01-23 | 2018-09-18 | 다이킨 고교 가부시키가이샤 | 피복 물품 및, 내식성 도막의 형성 방법 |
| JP7259834B2 (ja) | 2018-02-23 | 2023-04-18 | Ａｇｃ株式会社 | 積層体及びその製造方法、ならびに成形体及びその製造方法 |
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2021
- 2021-03-09 JP JP2021037540A patent/JP7206511B2/ja active Active
-
2022
- 2022-03-04 EP EP22767007.2A patent/EP4306602A1/en active Pending
- 2022-03-04 WO PCT/JP2022/009284 patent/WO2022191049A1/ja active Application Filing
- 2022-03-04 CN CN202280019337.XA patent/CN116997620A/zh active Pending
- 2022-03-04 KR KR1020237030358A patent/KR20230140573A/ko active Search and Examination
- 2022-03-09 TW TW111108539A patent/TW202246422A/zh unknown
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2023
- 2023-08-28 US US18/456,591 patent/US20230399528A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022191049A1 (ja) | 2022-09-15 |
| JP7206511B2 (ja) | 2023-01-18 |
| EP4306602A1 (en) | 2024-01-17 |
| JP2022137848A (ja) | 2022-09-22 |
| KR20230140573A (ko) | 2023-10-06 |
| CN116997620A (zh) | 2023-11-03 |
| US20230399528A1 (en) | 2023-12-14 |
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