TW201842036A - 組成物及塗膜 - Google Patents
組成物及塗膜 Download PDFInfo
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- TW201842036A TW201842036A TW107107382A TW107107382A TW201842036A TW 201842036 A TW201842036 A TW 201842036A TW 107107382 A TW107107382 A TW 107107382A TW 107107382 A TW107107382 A TW 107107382A TW 201842036 A TW201842036 A TW 201842036A
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- Prior art keywords
- coating film
- composition
- fluororesin
- heat
- resistant resin
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 238000002411 thermogravimetry Methods 0.000 description 1
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- 229910052853 topaz Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
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Abstract
提供賦予與基材之密合性優良,且非黏著性優良的塗膜之組成物。一種組成物,其特徵為包含氟樹脂、耐熱性樹脂、水,及沸點為205℃以上之溶劑。
Description
本發明係關於組成物及塗膜。
煎鍋、加熱板、鍋、電鍋之內鍋等的調理器具中,為了防止加熱調理時調理材料之燒焦或乾黏,一般係進行於鋁或不鏽鋼等之金屬基材上,設置由耐熱性、非黏著性、耐污染性等優良的氟樹脂所形成之被覆層。
專利文獻1中,提出一種氟樹脂被覆用組成物,其特徵為將聚伸芳硫醚樹脂、聚醯胺醯亞胺樹脂及/或聚醯亞胺樹脂,以及氟樹脂之至少3成分分散於液體介質中。
專利文獻2中,提出一種氟橡膠硫化用水性組成物,其含有選自由氟橡膠、氟樹脂、硫化劑,以及於300℃加熱30分鐘後之分解殘渣為0.3重量%以下的界面活性劑及具有300℃以下之沸點與於常溫下30dyne/cm以上之表面張力的極性溶劑所成群組的至少1種添加成分。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開昭53-74532號公報 [專利文獻2]國際公開第00/53675號
[發明所欲解決之課題]
然而,以往的技術中,塗膜與基材之密合性,及塗膜之非黏著性的兼備並不充分。
本發明鑑於上述現狀,其目的為提供賦予與基材之密合性優良,非黏著性優良的塗膜之組成物,及該塗膜。 [解決課題之手段]
本發明者等人發現藉由使用沸點為特定範圍之溶劑,會完全解決上述課題,而完成本發明。
即,本發明為一種組成物,其特徵為包含氟樹脂、耐熱性樹脂、水,及沸點為205℃以上之溶劑。
上述氟樹脂與上述耐熱性樹脂之質量比較佳為1/99~40/60。
上述氟樹脂及上述耐熱性樹脂之合計量,相對於上述氟樹脂、上述耐熱性樹脂、上述水及上述溶劑之合計量而言,較佳為20~50質量%。
上述溶劑之含量,相對於上述氟樹脂、上述耐熱性樹脂、上述水及上述溶劑之合計量而言,較佳為5~50質量%。
上述氟樹脂較佳為熔融加工性氟樹脂。
上述耐熱性樹脂較佳為聚伸芳硫醚或聚醚碸。
上述耐熱性樹脂,較佳為聚伸芳硫醚或聚醚碸,與聚醯胺醯亞胺。
上述溶劑較佳為選自由二乙二醇、三乙二醇、四乙二醇、甘油、二乙二醇單丁基醚、三丙二醇單甲基醚、三乙二醇單甲基醚、三乙二醇單丁基醚、聚乙二醇單甲基醚、三乙二醇二甲基醚、四乙二醇二甲基醚、聚乙二醇二甲基醚,及1,4-丁二醇所成群組的至少1種。
上述組成物較佳為塗料。
上述組成物較佳為單塗層用塗料。
本發明亦為由上述組成物所形成之塗膜。
本發明亦為具備上述塗膜之調理器具。
本發明亦為具備具有上述塗膜之內鍋的電鍋。
本發明亦為一種塗膜,其特徵為由含有水之組成物所形成,包含氟樹脂及耐熱性樹脂,藉由年糕接著性試驗之對年糕的接著性為20.0g/cm2
以下。
上述塗膜其棋盤格試驗之結果較佳為100/100。
本發明亦為具備基材與形成於上述基材上之上述塗膜的層合體。 [發明效果]
本發明之組成物,由於具有上述構成,可直接塗佈於基材,所得到之塗膜,與基材之密合性優良,而且非黏著性優良。因此,本發明之塗料組成物,有用於作為單塗層用塗料。
本發明之塗膜,由於具有上述構成,當形成於基材上時,與基材堅固地密合,而且非黏著性優良。即使僅以上述塗膜及上述基材之2層來構成層合體時,亦可成為該2層堅固地密合,又,非黏著性優良的層合體。
以下具體說明本發明。
本發明之組成物,其特徵為含有沸點為205℃以上之溶劑,藉由該特徵,可形成與基材之密合性優良,而且非黏著性優良的塗膜。
上述溶劑,必須為沸點205℃以上。溶劑之沸點過低時,有無法形成非黏著性優良的塗膜之虞。上述沸點較佳為220℃以上,更佳為235℃以上,又更佳為265℃以上。又,上述沸點,可為300℃以下。 上述沸點係於1氣壓(atm)所測定之值。 合併使用2種以上之溶劑時,只要其中至少1種溶劑之沸點為205℃以上即可。
上述溶劑之表面張力較佳為25dyn/cm以上。溶劑之表面張力為上述範圍內時,可形成非黏著性更優良的塗膜。上述表面張力更佳為35dyn/cm以上,又更佳為44dyn/cm以上。又,上述表面張力,較佳為72dyn/cm以下。 上述表面張力,可藉由平板法、環法、懸滴法等來測定。再者,上述表面張力係溶劑之溫度為20℃時的數值。
上述溶劑較佳為選自由二乙二醇、三乙二醇、四乙二醇、甘油、二乙二醇單丁基醚、三丙二醇單甲基醚、三乙二醇單甲基醚、三乙二醇單丁基醚、聚乙二醇單甲基醚、三乙二醇二甲基醚、四乙二醇二甲基醚、聚乙二醇二甲基醚,及1,4-丁二醇所成群組的至少1種,更佳為選自由二乙二醇、三乙二醇、四乙二醇、甘油、三丙二醇單甲基醚、三乙二醇單甲基醚、三乙二醇單丁基醚、聚乙二醇單甲基醚、三乙二醇二甲基醚、四乙二醇二甲基醚,及聚乙二醇二甲基醚所成群組的至少1種。又,又更佳為選自由三乙二醇、四乙二醇、甘油、三乙二醇單丁基醚、聚乙二醇單甲基醚、三乙二醇二甲基醚、四乙二醇二甲基醚,及聚乙二醇二甲基醚所成群組的至少1種,特佳為選自由三乙二醇、四乙二醇及甘油所成群組的至少1種。
上述組成物中,上述溶劑之含量,相對於構成上述組成物之氟樹脂、耐熱性樹脂、水及上述溶劑之合計量而言,較佳為5~50質量%,更佳為10質量%以上,又更佳為15質量%以上;更佳為40質量%以下,又更佳為30質量%以下。上述溶劑之含量於上述範圍內時,可形成與基材之密合性更優良、非黏著性更優良的塗膜。
本發明之組成物,其特徵亦為進一步包含氟樹脂。上述氟樹脂,為具有直接鍵結於構成主鏈或側鏈之碳原子的氟原子之聚合物。
上述氟樹脂較佳為具有熔融加工性。上述氟樹脂為具有熔融加工性者時,可形成非黏著性更優良的塗膜。上述「熔融加工性」,意指可使用擠出機及射出成形機等以往的加工機器,將聚合物熔融來進行加工。因此,上述氟樹脂,通常熔體流動速率(MFR)為0.01~100g/10分。
本說明書中,上述MFR係遵照ASTM D 1238,使用MELT INDEXER((股)安田精機製作所製),於依氟聚合物種類所規定之測定溫度(例如,後述PFA或FEP的情況係372℃、ETFE的情況係297℃)、荷重(例如,PFA、FEP及ETFE的情況係5kg)下,以由內徑2mm、長度8mm之噴嘴每10分鐘所流出之聚合物的質量(g/10分)的形式所得到之值。
上述氟樹脂,熔點較佳為100~333℃,更佳為140℃以上,又更佳為160℃以上,特佳為180℃以上,更佳為332℃以下。
本說明書中,上述含氟聚合物之熔點,係使用示差掃描熱量計[DSC]以10℃/分之速度升溫時之熔解熱曲線的極大值所對應的溫度。
上述氟樹脂可列舉低分子量聚四氟乙烯(PTFE)、四氟乙烯(TFE)/全氟(烷基乙烯基醚)(PAVE)共聚物(PFA)、TFE/六氟丙烯(HFP)共聚物(FEP)、乙烯(Et)/TFE共聚物(ETFE)、Et/TFE/HFP共聚物、聚氯三氟乙烯(PCTFE)、氯三氟乙烯(CTFE)/TFE共聚物、Et/CTFE共聚物及聚氟化亞乙烯(PVDF)等,較佳為選自由PFA及FEP所成群組之至少1種,更佳為FEP。
上述低分子量PTFE,係數平均分子量為60萬以下之PTFE。數平均分子量超過60萬之「高分子量PTFE」,為非熔融加工性,表現PTFE特有之纖維化特性(例如參照日本特開平10-147617號公報)。
上述低分子量PTFE,可為改質聚四氟乙烯(以下亦稱為「改質PTFE」)、亦可為均聚四氟乙烯(以下亦稱為「均PTFE」)。
上述改質PTFE,為由四氟乙烯(TFE)與TFE以外之單體(以下亦稱為「改質單體」)所構成的改質PTFE。
上述改質單體,只要係可與TFE共聚合者則無特殊限定,例如可列舉六氟丙烯(HFP)等之全氟烯烴;氯三氟乙烯(CTFE)等之氯氟烯烴;三氟乙烯、氟化亞乙烯(VDF)等之含氫之氟烯烴;全氟乙烯基醚;全氟烷基乙烯、乙烯等。又,所用之改質單體可為1種、亦可為複數種。
上述全氟乙烯基醚並無特殊限定,例如,可列舉下述通式(1) CF2
=CF-ORf(1) (式中,Rf表示全氟有機基)所示之全氟不飽和化合物等。本說明書中,上述「全氟有機基」,意指鍵結於碳原子之氫原子全部被氟原子取代而成的有機基。上述全氟有機基,亦可具有醚氧。
上述全氟乙烯基醚,例如可列舉上述通式(1)中,Rf為碳數1~10之全氟烷基的全氟(烷基乙烯基醚) (PAVE)。上述全氟烷基之碳數較佳為1~5。
上述PAVE中之全氟烷基,例如可列舉全氟甲基、全氟乙基、全氟丙基、全氟丁基、全氟戊基、全氟己基等,全氟烷基較佳為全氟丙基。即,上述PAVE較佳為全氟丙基乙烯基醚(PPVE)。
上述全氟乙烯基醚,進一步可列舉上述通式(1)中,Rf為碳數4~9之全氟(烷氧基烷基)基者、Rf為下述式:
(式中,m表示0或1~4之整數)所示之基者、Rf為下述式:
(式中,n表示1~4之整數)所示之基者等。
全氟烷基乙烯(PFAE)並無特殊限定,例如可列舉全氟丁基乙烯(PFBE)、全氟己基乙烯等。
上述改質PTFE中之改質單體,較佳為選自由HFP、CTFE、VDF、PAVE、PFAE及乙烯所成群組之至少1種。更佳為PAVE、又更佳為PPVE。
上述均PTFE,為實質上僅由TFE單位所構成者,例如,較佳為不使用改質單體所得到者。
上述改質PTFE,改質單體單位較佳為0.001~2莫耳%,更佳為0.001~1莫耳%。
本說明書中,構成PTFE之各單體的含量,可藉由依單體種類適當組合NMR、FT-IR、元素分析、螢光X射線分析來算出。
上述PFA並無特殊限定,較佳為TFE單位與PAVE單位之莫耳比(TFE單位/PAVE單位)為70/30以上且未達99/1之共聚物。更佳之莫耳比,為70/30以上且98.9/1.1以下,又更佳之莫耳比,為80/20以上且98.9/1.1以下。TFE單位過少時有機械物性降低的傾向,過多時有熔點變得過高,成形性降低的傾向。上述PFA,亦佳為來自可與TFE及PAVE共聚合之單體的單體單位為0.1~10莫耳%,且TFE單位及PAVE單位合計為90~99.9莫耳%之共聚物。可與TFE及PAVE共聚合之單體,可列舉HFP、CZ3
Z4
=CZ5
(CF2
)n
Z6
(式中,Z3
、Z4
及Z5
係相同或相異地表示氫原子或氟原子,Z6
表示氫原子、氟原子或氯原子,n表示2~10之整數)所示之乙烯基單體,及CF2
=CF-OCH2
-Rf7
(式中,Rf7
表示碳數1~5之全氟烷基)所示之烷基全氟乙烯基醚衍生物等。
上述PFA,熔點較佳為180~未達322℃,更佳為230~320℃,又更佳為280~320℃。
上述PFA,熔體流動速率(MFR)較佳為1~100g/10分。
上述PFA,熱分解開始溫度較佳為380℃以上。上述熱分解開始溫度更佳為400℃以上,又更佳為410℃以上。
本說明書中,熱分解開始溫度,係使用示差熱/熱重量測定裝置[TG-DTA](商品名:TG/DTA6200、Seiko電子公司製),將試樣10mg以升溫速度10℃/分由室溫升溫,試樣減少1質量%之溫度。
上述FEP並無特殊限定,較佳為TFE單位與HFP單位之莫耳比(TFE單位/HFP單位)為70/30以上且未達99/1的共聚物。更佳之莫耳比為70/30以上且98.9/1.1以下,又更佳之莫耳比為80/20以上且98.9/1.1以下。TFE單位過少時有機械物性降低的傾向,過多時有熔點變得過高,成形性降低的傾向。上述FEP,亦佳為來自可與TFE及HFP共聚合之單體的單體單位為0.1~10莫耳%,且TFE單位及HFP單位合計為90~99.9莫耳%之共聚物。可與TFE及HFP共聚合之單體,可列舉PAVE、烷基全氟乙烯基醚衍生物等。
上述FEP,熔點較佳為150~未達322℃,更佳為200~320℃,又更佳為240~320℃。
上述FEP,MFR較佳為1~100g/10分。
上述FEP,熱分解開始溫度較佳為360℃以上。上述熱分解開始溫度更佳為380℃以上,又更佳為390℃以上。
上述氟樹脂之各單體單位的含量,可藉由依單體種類適當組合NMR、FT-IR、元素分析、螢光X射線分析來算出。
本發明之組成物,其特徵亦為進一步包含耐熱性樹脂(惟上述氟樹脂除外)。
上述耐熱性樹脂,可連續使用之溫度較佳為150℃以上。
上述耐熱性樹脂,可列舉聚伸芳硫醚、聚醚碸、聚醯胺醯亞胺、聚醯亞胺、聚醚醯亞胺、聚醚醚酮、芳香族聚酯等。
上述聚伸芳硫醚[PAS],為由具有下述通式
(式中,Ar表示伸芳基)所示之重複單位的聚合物所構成之樹脂。上述PAS並無特殊限定,例如可列舉聚苯硫醚[PPS]等。
上述聚醚碸[PES],為由具有下述通式
所示之重複單位的聚合物所構成之樹脂。上述PES並無特殊限定,例如可列舉由藉由二氯二苯基碸與雙酚之聚縮合所得的聚合物所構成之樹脂等。
上述聚醯胺醯亞胺[PAI],為由分子構造中具有醯胺鍵及醯亞胺鍵之聚合物所構成之樹脂。上述PAI並無特殊限定,例如可列舉由藉由分子內具有醯胺鍵之芳香族二胺與均苯四甲酸等之芳香族四元羧酸之反應;偏苯三甲酸酐等之芳香族三元羧酸與4,4-二胺基苯基醚等之二胺或二苯基甲烷二異氰酸酯等之二異氰酸酯之反應;分子內具有芳香族醯亞胺環之二元酸與二胺之反應等的各反應所得到之高分子量聚合物所構成之樹脂等。上述PAI,由耐熱性優良的觀點,較佳為由主鏈中具有芳香環之聚合物所構成者。
上述聚醯亞胺[PI],為由分子構造中具有醯亞胺鍵之聚合物所構成之樹脂。上述PI並無特殊限定,例如可列舉由藉由均苯四甲酸酐等之芳香族四元羧酸酐之反應等所得到的高分子量聚合物所構成之樹脂等。上述PI,就耐熱性優良的觀點而言,較佳為由主鏈中具有芳香環之聚合物所構成者。
上述耐熱性樹脂,就可形成與基材之密合性優良,而且非黏著性優良的塗膜而言,較佳為PAS或PES,更佳為PAS。 PAS及PES可各為由1種或2種以上所構成者。
上述耐熱性樹脂,亦佳為PAS或PES,與PAI。即,上述耐熱性樹脂,可為PAS與PAI之混合物,或PES與PAI之混合物。作為上述耐熱性樹脂,若除了PAS或PES以外也含有PAI時,可得到二次密合性(重複進行塗膜之加熱與冷卻後與基材之密合性)優良的塗膜。上述耐熱性樹脂更佳為PAS與PAI,即PAS與PAI之混合物。 PAS、PES及PAI,可各為由1種或2種以上所構成者。
上述耐熱性樹脂為PAS或PES,與PAI時,上述PAS或PES,較佳為該PAS或PES與PAI之合計量的80~99質量%。更佳為90~95質量%。
上述組成物中,上述氟樹脂與上述耐熱性樹脂之質量比(氟樹脂/耐熱性樹脂),較佳為1/99~40/60,更佳為5/95~30/70,又更佳為10/90~25/75。上述氟樹脂與上述耐熱性樹脂之質量比為上述範圍內時,可形成非黏著性更優良的塗膜。其理由推測係因由含有較多量之上述聚伸芳硫醚、聚醚碸等之上述耐熱性樹脂的組成物形成塗膜時,由調理材料等所產生的水不易侵入上述塗膜,於上述塗膜之表面形成水的薄膜,藉由該水的薄膜,上述調理材料等不易附著於上述塗膜。
上述組成物中,上述氟樹脂及上述耐熱性樹脂之合計量,相對於構成上述組成物之氟樹脂、耐熱性樹脂、水及上述溶劑之合計量而言,較佳為20~50質量%,更佳為25質量%以上,又更佳為30質量%以上,更佳為45質量%以下,又更佳為40質量%以下。上述氟樹脂及上述耐熱性樹脂之合計量為上述範圍內時,可形成與基材之密合性更優良、非黏著性更優良的塗膜。
本發明之組成物,其特徵亦為進一步包含水。藉由於組成物中存在水,可使組成物之黏度及黏性為高。藉此,塗裝性或膜厚之控制得到改善,可提高塗膜物性(例如耐蝕性)。
由可形成操作更容易、物性更優良的塗膜而言,上述組成物,固體成分濃度較佳為5~70質量%,更佳為10質量%以上,更佳為60質量%以下。
本發明之組成物,較佳為進一步包含填充材。藉由包含填充材,可形成與基材之密合性更優良,且非黏著性、於高溫下之硬度,及耐摩耗性更優良的塗膜。
上述填充材,新莫氏硬度較佳為7以上。藉由包含具有特定硬度之填充材,可形成與基材之密合性更優良,且非黏著性、於高溫下之硬度,及耐摩耗性更優良的塗膜。
上述填充材,較佳為選自由鑽石、氟化鑽石、剛玉、矽石、氮化硼、碳化硼、碳化矽、二氧化矽、雲母、金綠寶石、黃玉、綠寶石、石榴石、石英、玻璃細片、熔融氧化鋯、碳化鉭、碳化鈦、氧化鋁,及碳化鎢所成群組的至少1種;更佳為選自由鑽石、碳化硼、碳化矽、氧化鋁及熔融氧化鋯所成群組的至少1種;又更佳為鑽石及碳化矽。
氟化鑽石可藉由將鑽石氟化而得到。鑽石之氟化,例如可由於第26次氟化學討論會要旨集、平成14 (2002)年11月14日發行、p24~25中揭示之公知方法進行。即,於由鎳或含有鎳之合金等之對氟具有耐蝕性的材料所構成之反應器中,封入鑽石,並導入氟氣進行氟化即可。
上述組成物中,上述填充材之含量,相對於上述氟樹脂及上述耐熱性樹脂之合計量而言,較佳為0.1~10質量%,更佳為0.3質量%以上,更佳為5.0質量%以下。上述填充材之含量為上述範圍內時,可形成與基材之密合性更優良,且非黏著性、於高溫下之硬度,及耐摩耗性更優良的塗膜。
上述組成物亦佳為含有界面活性劑。上述界面活性劑,可使用以往公知者。
上述組成物亦可進一步包含添加劑。上述添加劑並無特殊限定,例如可列舉流平劑、固體潤滑劑、沈降防止劑、水分吸收劑、表面調整劑、搖變性賦予劑、黏度調節劑、凝膠化防止劑、紫外線吸收劑、光安定劑、塑化劑、浮色防止劑、結皮(skinning)防止劑、擦傷防止劑、防黴劑、抗菌劑、抗氧化劑、防靜電劑、矽烷耦合劑、碳黑、黏土、體質顏料、鱗片狀顏料、硫酸鋇、玻璃、各種強化材、各種增量材、導電性填料、金、銀、銅、鉑、不鏽鋼等之金屬粉末等。
上述添加劑之含量,相對於上述氟樹脂及上述耐熱性樹脂之合計量而言,較佳為0.1~30質量%,更佳為1質量%以上,更佳為25質量%以下。
上述組成物,可藉由將上述氟樹脂、上述耐熱性樹脂、上述水及上述溶劑,依需要之上述填充材、上述界面活性劑及上述添加劑以於混合機、輥磨機中混合的通常之混合方法混合來調製。
上述組成物較佳為塗料。上述組成物可為水性塗料。
藉由將上述組成物塗佈於基材,可形成塗膜。所形成之塗膜,與基材之密合性優良,而且非黏著性優良。
上述組成物雖亦可重複塗佈,但能夠以1次塗裝即形成具有所期望特性之塗膜。上述組成物可適合地利用作為單塗層用塗料。進一步地,上述組成物亦能夠以1次塗裝即形成厚的塗膜。
上述組成物之塗佈方法並無特殊限定,例如可列舉噴霧塗裝、輥塗裝、刮刀之塗裝、浸液(浸漬)塗裝、含浸塗裝、旋流(spin flow)塗裝、淋幕(curtain flow)塗裝等,其中尤以噴霧塗裝為佳。
塗佈上述組成物後,可將塗膜乾燥、亦可燒成。上述乾燥較佳於70~300℃之溫度進行5~60分鐘。上述燒成較佳於260~410℃之溫度進行10~30分鐘。
本發明亦為由上述組成物所形成之塗膜(以下亦稱為第1塗膜)。本發明之第1塗膜,係由上述組成物所形成者,因此與基材之密合性優良,而且非黏著性優良。
本發明亦為一種塗膜(以下亦稱為第2塗膜),其特徵為由含有水之組成物形成,包含氟樹脂及耐熱性樹脂,藉由年糕接著性試驗之對年糕的接著性為20.0g/cm2
以下。本發明之第2塗膜,藉由上述特徵,與基材之密合性優良,而且非黏著性優良。
上述第2塗膜,其特徵為藉由年糕接著性試驗之對年糕的接著性為20.0g/cm2
以下。上述接著性為上述範圍內時,調理材料等中所含有的直鏈澱粉或支鏈澱粉等之黏著性高的物質不易附著。上述接著性較佳為18.0g/cm2
以下,更佳為15.0g/cm2
以下,又更佳為14.0g/cm2
以下。又,上述接著性可為0.1g/cm2
以上。 上述接著性,係藉由以下之年糕接著性試驗所測定之值。 於厚度2.0mm之純鋁板上以厚度20μm形成測定接著性之塗膜,製作塗裝板(3cm×3cm)。於上述塗裝板之與塗膜相反側的面上,將2枚銅板(各為3cm×3cm×2.0mm)以具有100℃以上之耐熱性的膠帶固定,進一步地於上述銅板之上以金屬絲製作握柄,得到樣本。於加熱至90℃之加熱板上,依序重疊放置經噴砂粗面化之鋁板(3cm×5cm)、年糕切塊(佐藤食品工業公司製佐藤的切片年糕切片),及上述樣本。此時,上述樣本係為塗膜與年糕切塊以直接接觸的方式重疊者。於90℃加熱2分30秒後,以彈簧秤勾住上述握柄將上述樣本於垂直方向拉伸,記錄於塗膜由年糕切塊分離之時間點的重量(g)。由所得之重量減去樣本重量(包含銅板、膠帶、金屬絲)並除以塗裝板之面積(9cm2
),藉以得到塗膜對年糕之接著性(g/cm2
)。 此外,上述膠帶及金屬絲,係使用相對於上述樣本可無視之程度的重量者。
圖1為示意性顯示上述年糕接著性試驗之方法的圖。如圖1所示,於加熱板8之上配置鋁板6,於鋁板6之上配置年糕切塊7,於年糕切塊7之上配置樣本5。樣本5係由具備塗膜1a及鋁板1b之塗裝板1、固定於塗裝板1之與塗膜1a相反側的面之2枚銅板2及3,及設置於銅板3之上的握柄4所構成。樣本5係配置為塗膜1a與年糕切塊7直接接觸。
上述第2塗膜,其特徵亦為包含氟樹脂及耐熱性樹脂。上述氟樹脂及上述耐熱性樹脂之適宜的態樣係如上所述。
上述第2塗膜中,上述氟樹脂及上述耐熱性樹脂之合計量,相對於該塗膜而言,較佳為80~99質量%,更佳為85~95質量%。
上述第2塗膜,其特徵亦為由含有水之組成物形成。藉由於組成物中存在水,可使組成物之黏度及黏性為高。藉此,塗裝性或膜厚之控制得到改善,可提高塗膜物性(例如耐蝕性)。即,上述第2塗膜,相較於由不含水之組成物形成的塗膜而言,具有優良的塗膜物性。
上述第2塗膜,棋盤格試驗之結果較佳為100/100。藉此,上述第2塗膜,與基材之密合性更優良。 上述棋盤格試驗,係藉由根據JIS K5400,重複10次之賽珞凡膠帶剝離來進行。
上述第2塗膜,例如可藉由將上述本發明之組成物以上述方法塗佈於基材,並視需要乾燥,隨後燒成來形成。
本發明亦為具備基材,於形成於上述基材上之上述第2塗膜的層合體。上述層合體,即使僅由上述基材及上述塗膜之2層所構成的情況時,該2層亦堅固地密合,又,非黏著性優良。因此,可適合地利用作為電鍋等之調理器具。
上述基材之材料並無特殊限定,例如可列舉鐵、鋁、銅等之金屬單質及此等之合金類等之金屬;琺瑯、玻璃、陶瓷等之非金屬無機材料等。上述合金類可列舉不鏽鋼等。上述基材之材料較佳為金屬,更佳為鋁或不鏽鋼,又更佳為鋁。
上述基材亦可為依需要進行過脫脂處理、粗面化處理等之表面處理者。上述粗面化處理之方法並無特殊限定,例如可列舉酸或鹼之化學蝕刻、陽極氧化(耐酸鋁處理)、噴砂等。
上述塗膜之膜厚較佳為1~50μm,更佳為5μm以上,更佳為40μm以下。膜厚過小時,有耐蝕性及耐摩耗性不良之虞,膜厚過大時,有容易產生龜裂之虞。
上述塗膜,可藉由將上述本發明之組成物以上述方法塗佈於上述基材,並視需要乾燥,隨後燒成來形成。
上述層合體,亦可為包含上述基材及上述塗膜以外之層者,但就可充分發揮上述基材與上述塗膜之高的接著性,與上述塗膜之優良特性而言,較佳僅具有上述基材及上述塗膜。
上述本發明之第1塗膜、本發明之第2塗膜,及本發明之層合體,可使用於利用氟樹脂所具有之非黏著性、耐熱性、滑動性等的用途,例如,作為利用非黏著性者,可列舉煎鍋、壓力鍋、鍋、烤鍋、電鍋、烤箱、加熱板、烤麵包模、菜刀、瓦斯爐等之調理器具;電壺、製冰盤、模具、排油煙機等之廚房用品;混合輥、壓延輥、輸送帶、漏斗等之食品工業用零件;辦公室自動化(OA)用滾筒、OA用帶、OA用分離爪、製紙輥、薄膜製造用壓延輥等之工業用品;發泡苯乙烯成形用等之模具、模板、合板/化妝板製造用脫模板等之成形模具脫模、工業用容器(特別是半導體工業用)等,作為利用滑動性者,可列舉鋸子、銼刀等之工具;熨斗、剪刀、菜刀等之家庭用品;金屬箔、電線、食品加工機、包裝機、紡織機械等之滑動軸承、照相機/時鐘之滑動零件、管路、汽門、培林等之汽車零件、雪鏟、鍬、滑槽等。 其中尤可適合地使用於調理器具或廚房用品,特別可適合地使用於電鍋之內鍋。
本發明亦為具備上述本發明之第1塗膜的調理器具。又,本發明亦為具備具有上述本發明之第1塗膜的內鍋之電鍋。又,具備上述本發明之第2塗膜的調理器具、具備具有上述本發明之第2塗膜的內鍋之電鍋、具備上述本發明之層合體的調理器具,及具備具有上述本發明之層合體的內鍋之電鍋,亦為本發明之適合的態樣。 [實施例]
接著列舉實施例以說明本發明,但本發明不僅限定於該實施例。
實施例之各數值係藉由以下方法測定。
塗裝板之製作 將厚度2.0mm之純鋁板(A-1050P)表面以丙酮脫脂後,進行噴砂,以根據JIS B 1982所測定之表面粗度Ra值成為2.0~3.0μm的方式粗面化。藉由送風(air blow)將表面之灰塵去除後,將實施例及比較例所得到之組成物,使用噴嘴徑1.0mm之重力式噴槍,以噴霧壓力0.2MPa進行噴霧塗裝。將上述鋁板上之塗膜於80~100℃乾燥15分鐘。之後,於380℃燒成20分鐘,製作具有膜厚約20μm之塗膜的塗裝板。
年糕接著性試驗(非黏著性) 於厚度2.0mm之純鋁板上,以厚度20μm形成測定接著性之塗膜,製作塗裝板(3cm×3cm)。於上述塗裝板之與塗膜相反側的面上,將2枚銅板(各為3cm×3cm×2.0mm)以具有100℃以上之耐熱性的膠帶固定,進一步地於上述銅板之上以金屬絲製作握柄,得到樣本。於加熱至90℃之加熱板上,依序重疊放置經噴砂粗面化之鋁板(3cm×5cm)、年糕切塊(佐藤食品工業公司製佐藤的切片年糕切片),及上述樣本。此時,上述樣本係為塗膜與年糕切塊以直接接觸的方式重疊。於90℃加熱2分30秒後,以彈簧秤勾住上述握柄將上述樣本於垂直方向拉伸,記錄於塗膜由年糕切塊分離之時間點的重量(g)。由所得之重量減去樣本重量(包含銅板、膠帶、金屬絲)並除以塗裝板之面積(9cm2
),藉以得到塗膜對年糕之接著性(g/cm2
)。
棋盤格試驗(密合性) 根據JIS K5400(重複10次之賽珞凡膠帶剝離)。
實施例及比較例 實施例1 第1成分 FEP之60%水性分散液 第2成分 PPS之40%水性分散液(將PPS粉體40重量份、TEG 20重量份、離子交換水33重量份、聚氧乙烯烷基醚6重量份、乙炔二醇1重量份,於砂磨機中混合粉碎所得到之水性分散液) 將上述各成分以成為表1記載之摻合比的方式混合,於攪拌機中攪拌約30分鐘調製組成物。藉由上述方法製作塗裝板,評估塗膜之非黏著性及密合性。結果示於表1。
實施例2 除了使用PES粉體以取代PPS粉體以外,係重複與實施例1同樣之程序。結果示於表1。
實施例3 除了使用PFA水性分散液以取代FEP水性分散液以外,係重複與實施例1同樣之程序。結果示於表1。
實施例4 除了使用BDG以取代TEG以外,係重複與實施例1同樣之程序。結果示於表1。
實施例5 除了使用BTG以取代TEG以外,係重複與實施例1同樣之程序。結果示於表1。
實施例6 除了變更氟樹脂與黏結劑之摻合比以外,係重複與實施例1同樣之程序。結果示於表1。
實施例7 第1成分 FEP之60%水性分散液 第2成分 PPS之40%水性分散液(將PPS粉體40重量份、TEG 20重量份、離子交換水33重量份、聚氧乙烯烷基醚6重量份、乙炔二醇1重量份,於砂磨機中混合粉碎所得到之水性分散液) 第3成分 碳黑之20%水性分散液 第4成分 硫酸鋇之20%水性分散液 將上述各成分以成為表1記載之摻合比的方式混合,於攪拌機中攪拌約30分鐘,調製組成物。之後之加工方法係使用與實施例1同樣的方法。結果示於表1。
實施例8 除了使用TEG/PG=1/1(質量比)混合溶劑以取代TEG以外,係重複與實施例7同樣之程序。結果示於表1。
比較例1 除了使用離子交換水以取代TEG以外,係重複與實施例1同樣之程序。結果示於表1。
比較例2 除了使用MMB以取代TEG以外,係重複與實施例1同樣之程序。結果示於表1。
比較例3 除了使用NMP以取代TEG以外,係重複與實施例1同樣之程序。結果示於表1。
表中之比係表示質量比。 表中之溶劑量意指相對於氟樹脂、黏結劑(耐熱性樹脂)、水及溶劑之合計量而言的溶劑量(質量%)。 關於表中之添加劑的數值,意指相對於氟樹脂及黏結劑(耐熱性樹脂)之合計量而言,添加劑之量(質量%)。 又,實施例、比較例及表中之縮寫係如以下所示。 FEP:四氟乙烯/六氟丙烯共聚物 PFA:四氟乙烯/全氟(烷基乙烯基醚)共聚物 PPS:聚苯硫醚 PES:聚醚碸 TEG:三乙二醇 BDG:二乙二醇單丁基醚 BTG:三乙二醇單丁基醚 PG:丙二醇 MMB:3-甲基-3-甲氧基丁醇 NMP:N-甲基-2-吡咯啶酮
1‧‧‧塗裝板
1a‧‧‧塗膜
1b‧‧‧鋁板
2‧‧‧銅板
3‧‧‧銅板
4‧‧‧握柄
5‧‧‧樣本
6‧‧‧鋁板
7‧‧‧年糕切塊
8‧‧‧加熱板
[圖1]示意性顯示年糕接著性試驗之方法的圖。
Claims (16)
- 一種組成物,其特徵為包含氟樹脂、耐熱性樹脂、水,及沸點為205℃以上之溶劑。
- 如請求項1之組成物,其中前述氟樹脂與前述耐熱性樹脂之質量比為1/99~40/60。
- 如請求項1或2之組成物,其中,相對於前述氟樹脂、前述耐熱性樹脂、前述水及前述溶劑之合計量而言,前述氟樹脂及前述耐熱性樹脂之合計量為20~50質量%。
- 2或3之組成物,其中,相對於前述氟樹脂、前述耐熱性樹脂、前述水及前述溶劑之合計量而言,前述溶劑之含量為5~50質量%。
- 2、3或4之組成物,其中前述氟樹脂為熔融加工性氟樹脂。
- 2、3、4或5之組成物,其中前述耐熱性樹脂為聚伸芳硫醚或聚醚碸。
- 2、3、4、5或6之組成物,其中前述耐熱性樹脂為聚伸芳硫醚或聚醚碸,及聚醯胺醯亞胺。
- 2、3、4、5、6或7之組成物,其中前述溶劑為選自由二乙二醇、三乙二醇、四乙二醇、甘油、二乙二醇單丁醚、三丙二醇單甲醚、三乙二醇單甲醚、三乙二醇單丁醚、聚乙二醇單甲醚、三乙二醇二甲醚、四乙二醇二甲醚、聚乙二醇二甲醚及1,4-丁二醇所成群組中之至少1種。
- 2、3、4、5、6、7或8之組成物,其係塗料。
- 2、3、4、5、6、7、8或9之組成物,其係單塗層用塗料。
- 一種塗膜,其係由如請求項1、2、3、4、5、6、7、8、9或10之組成物而形成者。
- 一種調理器具,其具備如請求項11之塗膜。
- 一種電鍋,其具備具有如請求項11之塗膜的內鍋。
- 一種塗膜,其特徵係由含水之組成物形成, 包含氟樹脂及耐熱性樹脂, 藉由年糕接著性試驗之對年糕的接著性為20.0g/cm2 以下。
- 如請求項14之塗膜,其棋盤格試驗之結果為100/100。
- 一種層合體,其具備基材及形成於前述基材上之如請求項14或15之塗膜。
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TWI537345B (zh) * | 2011-12-12 | 2016-06-11 | 廣科工業股份有限公司 | 陶瓷塗料與保護塗層 |
JP6186921B2 (ja) * | 2012-07-25 | 2017-08-30 | ダイキン工業株式会社 | 被覆物品 |
JP6213170B2 (ja) * | 2013-11-12 | 2017-10-18 | 旭硝子株式会社 | 含フッ素樹脂塗料組成物および塗膜を有する塗装物品 |
US11072144B2 (en) * | 2013-11-26 | 2021-07-27 | Daikin Industries, Ltd. | Laminate |
JP6381483B2 (ja) * | 2014-10-29 | 2018-08-29 | 三菱電機株式会社 | コーティング組成物、防汚性部材、空気調和機及び換気扇 |
JP6476764B2 (ja) * | 2014-11-04 | 2019-03-06 | 日立化成株式会社 | 水系耐熱性樹脂組成物及び基材 |
US10407588B2 (en) | 2015-03-13 | 2019-09-10 | Daikin Industries, Ltd. | Coating composition and coated article |
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2017
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CN110352218A (zh) | 2019-10-18 |
CN116948398A (zh) | 2023-10-27 |
KR102189469B1 (ko) | 2020-12-14 |
JP6811649B2 (ja) | 2021-01-13 |
EP3594285A1 (en) | 2020-01-15 |
JP2018145325A (ja) | 2018-09-20 |
TWI749181B (zh) | 2021-12-11 |
US20200056065A1 (en) | 2020-02-20 |
WO2018163863A1 (ja) | 2018-09-13 |
CN110352218B (zh) | 2023-09-29 |
KR20190103298A (ko) | 2019-09-04 |
US11518901B2 (en) | 2022-12-06 |
EP3594285A4 (en) | 2020-11-25 |
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