TWI461571B - The use of organic and inorganic composite film - Google Patents

The use of organic and inorganic composite film Download PDF

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Publication number
TWI461571B
TWI461571B TW100135247A TW100135247A TWI461571B TW I461571 B TWI461571 B TW I461571B TW 100135247 A TW100135247 A TW 100135247A TW 100135247 A TW100135247 A TW 100135247A TW I461571 B TWI461571 B TW I461571B
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Taiwan
Prior art keywords
organic
steel sheet
cold
inorganic composite
rolled steel
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Application number
TW100135247A
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English (en)
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TW201219600A (en
Inventor
Katsuya Hoshino
Shinji Ootsuka
Takayoshi Yano
Tatsuya Miyoshi
Original Assignee
Jfe Steel Corp
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Publication of TW201219600A publication Critical patent/TW201219600A/zh
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Publication of TWI461571B publication Critical patent/TWI461571B/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B15/06—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 natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B15/082—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 comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • B32B15/09—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 comprising polyesters
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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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
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    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Description

有機無機複合皮膜之用途
本發明係關於具有優異壓製成形性的冷軋鋼板。
冷軋鋼板係廣泛被利用於以汽車車體用途為中心的廣大領域中。在此種用途中係經施行壓製成形後才供使用。特別係就從近年的CO2 排放量規範強化觀點，於車體輕量化目的下，高強度鋼板的使用比率有增加傾向。但是，冷軋鋼板中，特別係母材的強度超過440MPa者，因為隨母材強度上升，在壓製成形時會導致面壓上升，且因為冷軋鋼板的硬度接近模具的硬度，因而會有冷軋鋼板容易因模具而導致刮傷，出現通稱「模具刮傷」的傷痕之問題。即在連續壓製成形時，會有諸如模具的磨耗嚴重、成形品的外觀受損等，對汽車生產性造成深刻的不良影響。
就抑制冷軋鋼板的模具刮傷發生之方法，廣泛採取對模具施行表面處理。但是，該方法係在施行表面處理後，並沒有施行模具的調整。且，該方法會有成本高的問題。所以，強烈需求將冷軋鋼板自身形成不易發生模具刮傷(提升耐模具刮傷性)。
在冷軋鋼板表面上形成潤滑皮膜的技術亦有多數報告。專利文獻1有記載：在鋼板上形成潤滑皮膜的技術；該潤滑皮膜係含有：鹼金屬硼酸鹽、以及當作潤滑劑用的硬脂酸鋅與蠟之混成物。
專利文獻2有記載：在鋼板上所形成的物質，係以矽酸鋰為皮膜成分，且在其中經添加當作潤滑劑用之蠟與金屬皂的技術。
專利文獻3有記載：使具有矽醇基或羥基的聚胺甲酸乙酯樹脂形成1~15μm厚度，利用高面壓加工施行連續性形成優異的潤滑處理鋼板。
[先行技術文獻] [專利文獻]
專利文獻1：日本專利特開2007-275706號公報
專利文獻2：日本專利特開2002-307613號公報
專利文獻3：日本專利特開2001-234119號公報
然而，專利文獻1~3雖藉由所含有的潤滑劑等而顯現出潤滑性，但特別係如高強度冷軋鋼板，就面壓較高的部位便無法滿足要求特性。
本發明目的在於提供：就壓製成形時會有面壓上升的高強度鋼板等難成形材料，具有不易發生模具刮傷、可精巧施行壓製成形之優異壓製成形性的冷軋鋼板。
潤滑皮膜的潤滑性係依存於皮膜中潤滑劑之潤滑性能的部分頗大，認為需要新穎潤滑劑的開發。所以，本發明者等經深入鑽研，就潤滑的機構有考量利用因結晶性層狀物的層間滑動而造成變形的技術。若層間的滑動依較低應力產生的話，即便高押抵壓(面壓)，但引發滑動時的阻力仍較低，可期待顯現出優異的潤滑性。在發現具體的結晶性層狀物時，擷取層間利用諸如分子間作用力、氫鍵、靜電能等較弱鍵結力進行鍵結的物質。然後，藉由將該等所擷取的結晶性層狀物在冷軋鋼板表面上施行既定量塗佈，發現可大幅提升滑動性(滑動阻力變小)。且，就結晶性層狀物塗佈時的附著性觀點而言，發現將結晶性層狀物混合有機樹脂而形成有機無機複合皮膜係屬有效。此外，發現結晶性層狀物頗適用由2價與3價的金屬氫氧化物，利用靜電能與陰離子相鍵結的層狀複氫氧化物。
本發明係根據以上發現而完成，主旨如下。
[1]一種冷軋鋼板，係表面設有含有機樹脂與結晶性層狀物之有機無機複合皮膜，且該有機無機複合皮膜係平均膜厚0.10~2.0μm，相對於有機樹脂固形分100重量份，依固形分計含有0.5重量份以上的結晶性層狀物。
[2]上述[1]之冷軋鋼板，其中，上述結晶性層狀物係依[M2+ 1-x M3+ x (OH)2 ][An- ]x/n ‧zH2 O所示層狀複氫氧化物；上述M2+ 係Mg2+ 、Ca2+ 、Fe2+ 、Ni2+ 、Zn2+ 、Pb2+ 、Sn2+ 之1種或2種以上；上述M3+ 係Al3+ 、Fe3+ 、Cr3+ 、3/4Zr4+ 、Mo3+ 之1種或2種以上；上述An- 係OH- 、F- 、CO3 2- 、Cl- 、Br- 、(C2 O4 )2- 、I- 、(NO3 )- 、(SO4 )2- 、(BrO3 )- 、(IO3 )- 、(V10 O28 )6- 、(Si2 O5 )2- 、(ClO4 )- 、(CH3 COO)- 、[C6 H4 (CO2 )2 ]2- 、(C6 H5 COO)- 、[C8 H16 (CO2 )2 ]2- 、n(C8 H17 SO4 )- 、n(C12 H25 SO4 )- 、n(C18 H37 SO4 )- 、SiO4 4- 之1種或2種以上。
[3]上述[1]之冷軋鋼板，其中，上述結晶性層狀物係依[M2+ 1-x M3+ x (OH)2 ][An- ]x/n ‧zH2 O所示層狀複氫氧化物；上述M2+ 係Mg2+ 、Ca2+ 、Fe2+ 、Ni2+ 、Zn2+ 之1種或2種以上；上述M3+ 係Al3+ 、Fe3+ 、Cr3+ 之1種或2種以上；上述An- 係OH- 、CO3 2- 、Cl- 、(SO4 )2- 之1種或2種以上。
[4]上述[1]~[3]中之任一項之冷軋鋼板，其中，上述有機樹脂係從環氧樹脂、多羥基聚醚樹脂、聚酯樹脂、胺甲酸乙酯樹脂、矽樹脂、丙烯酸樹脂中選擇1種或2種以上。
根據本發明，可獲得即便壓製成形時有面壓上升的情況，容易發生模具刮傷之部位的滑動阻力仍小，具有優異壓製成形性的冷軋鋼板。
本發明的冷軋鋼板係冷軋鋼板的表面設有含有機樹脂與結晶性層狀物之有機無機複合皮膜；而，有機無機複合皮膜係平均膜厚0.10~2.0μm，相對於有機樹脂的固形分100重量份，依固形分計含有0.5重量份以上的結晶性層狀物。此係本發明冷軋鋼板最重要的要件。
藉由將結晶性層狀物既定量塗佈於冷軋鋼板的表面上，便可大幅提升滑動性。相關有機無機複合皮膜所含有結晶性層狀物的潤滑機制，可認為如下。當模具與冷軋鋼板進行滑動時，會因模具與冷軋鋼板的表面凝聚力，導致冷軋鋼板的表面產生剪切應力。藉由結晶性層狀物存在於冷軋鋼板與模具之間，結晶性層狀物便因層間的滑動而變形，並吸收表面所生成的剪切變形應力。所以，在冷軋鋼板遭磨耗，結晶性層狀物被從冷軋鋼板表面上削取後，因為結晶性層狀物會附著於模具上，而顯現出使模具與冷軋鋼板間之摩擦阻力減少的效果，因而即便假設高強度鋼板的高面壓條件，仍可獲得充分的效果。又，有機無機複合皮膜中含有有機樹脂之事，就塗佈時的附著性觀點而言亦屬有效，可將冷軋鋼板的表面由結晶性層狀物依均勻厚度被覆。
上述含有有機樹脂與結晶性層狀物的有機無機複合皮膜(以下簡稱「有機無機複合皮膜」)的厚度，係依SEM觀察截面時的厚度，將平均膜厚設為0.10μm以上且2.0μm以下。若平均膜厚未滿0.10μm，則較難在冷軋鋼板的表面上均勻成膜。反之，若平均膜厚超過2.0μm，則會有汽車製造時重要的點銲性降低之顧慮。另外，有機無機複合皮膜的厚度係可從利用5kV以下加速電壓的SEM，觀察經FIB(聚焦離子束，focused ion beam)施行加工之截面的結果進行測定。又，結晶性層狀物是否為結晶性之結晶構造的鑑定，係可利用薄膜X射線繞射進行
再者，結晶性層狀物係相對於有機樹脂固形分100重量份，依固形分計含有0.5重量份以上。若結晶性層狀物的固形分未滿0.5重量份，則模具與冷軋鋼板進行滑動時，因為與模具進行接觸的結晶層狀物較少，因而無法顯現出充分的效果。
另外，本發明中，所謂「結晶性層狀物」係單位晶格中，板狀共價鍵結晶利用諸如分子間作用力、氫鍵、靜電能等較弱鍵結進行積層的結晶。其中，構造可依[M2+ 1-x M3+ x (OH)2 ][An- ]x/n ‧zH2 O表示的層狀複氫氧化物，因為對帶正電的板狀2價與3價金屬氫氧化物，帶負電的陰離子為能保持電平衡，便利用靜電能鍵結且積層呈層狀，因而具有層狀的結晶構造，頗適用為本發明的結晶性層狀物。[M2+ 1-x M3+ x (OH)2 ][An- ]x/n ‧zH2 O所示層狀複氫氧化物之事，可利用X射線繞射進行鑑定，可獲知能依上式表示的物質係呈層狀結晶。
M2+ 較佳係Mg2+ 、Ca2+ 、Fe2+ 、Ni2+ 、Zn2+ 、Pb2+ 、Sn2+ 之1種或2種以上。其中，Mg2+ 、Ca2+ 、Fe2+ 、Ni2+ 、Zn2+ 確認係天然或人工生成的層狀複氫氧化物種，可依層狀複氫氧化物形式安定的存在，因而屬更佳。
M3+ 較佳係Al3+ 、Fe3+ 、Cr3+ 、3/4Zn4+ 、Mo3+ 之1種或2種以上。其中，Al3+ 、Fe3+ 、Cr3+ 確認係天然或人工生成的層狀複氫氧化物種，可依層狀複氫氧化物形式安定的存在，因而屬更佳。
An- 較佳係OH- 、F- 、CO3 2- 、Cl- 、Br- 、(C2 O4 )2- 、I- 、(NO3 )- 、(SO4 )2- 、(BrO3 )- 、(IO3 )- 、(V10 O28 )6- 、(Si2 O5 )2- 、(ClO4 )- 、(CH3 COO)- 、[C6 H4 (CO2 )2 ]2- 、(C6 H5 COO)- 、[C8 H16 (CO2 )2 ]2- 、n(C8 H17 SO4 )- 、n(C12 H25 SO4 )- 、n(C18 H37 SO4 )- 、SiO4 4- 之1種或2種以上。該等確認係依作為層狀複氫氧化物種的層間陰離子而導入，可依層狀複氫氧化物形式存在。其中，OH- 、CO3 2- 、Cl- 、(SO4 )2- 係在冷軋鋼板表面進行成膜時，相較於層狀複氫氧化物種的其他陰離子，較容易依層間陰離子形式導入，並可短時間成膜，因而頗適用為陰離子。
其次，針對使有機無機複合皮膜生成於冷軋鋼板表面上的方法進行說明。首先，針對結晶性層狀物的生成方法進行說明。此處就一例係例示使屬於結晶性層狀物之一種的層狀複氫氧化物生成粉狀的方法。例如在含有陽離子的水溶液中滴下含有陰離子之溶液的手法。在含有2價陽離子(M2+ )中之任1種以上、與3價陽離子(M3+ )中之任1種以上的水溶液中，滴下含有無機陰離子或有機陰離子(An- )中之任1種以上陰離子的水溶液。此時，依反應懸浮液的pH成為10±0.1之方式，滴下2.0莫耳-NaOH溶液，而調整溶液。反應懸浮液中所存在的2價陽離子與3價陽離子，係依氫氧化物形式呈膠體狀存在。此處，若在液中滴下OH- 、F- 、CO3 2- 、Cl- 、Br- 、(C2 O4 )2- 、I- 、(NO3 )- 、(SO4 )2- 、(BrO3 )- 、(IO3 )- 、(V10 O28 )6- 、(Si2 O5 )2- 、(ClO4 )- 、(CH3 COO)- 、[C6 H4 (CO2 )2 ]2- 、(C6 H5 COO)- 、[C8 H16 (CO2 )2 ]2- 、n(C8 H17 SO4 )- 、n(C12 H25 SO4 )- 、n(C18 H37 SO4 )- 、SiO4 4- 中之任1種以上的特定陰離子，氫氧化物便會依層狀複氫氧化物形式沉澱。其次，將所獲得沉澱物利用離心分離機進行分離，經乾燥便可獲得粉狀的層狀複氫氧化物。另外，所獲得粉狀的物質是否為層狀化合物之事，可利用X射線繞射進行確認。
其次，適當調配依上述所獲得粉狀層狀複氫氧化物、與有機樹脂，經攪拌而調製得塗料組成物。攪拌時可使用例如塗料用分散機(砂磨機)。又，攪拌時間係可適當調整。為使粉狀層狀複氫氧化物能充分分散於有機溶劑中，攪拌時間較佳係達30分鐘以上。有機樹脂較佳係從環氧樹脂、多羥基聚醚樹脂、聚酯樹脂、胺甲酸乙酯樹脂、矽樹脂、丙烯酸樹脂中選擇1種或2種以上。特別係就從耐蝕性的觀點，最好為以環氧系樹脂為基質，並在提升加工性之目的下將分子量施行適當最佳化者，或者對樹脂其中一部分利用諸如胺甲酸乙酯、聚酯、胺等施行改質者。
再者，視需要，亦可添加當作添加劑用之諸如：有機著色顏料(例如：縮合多環系有機顏料、酞菁系有機顏料等)、著色染料(例如：水溶性偶氮系金屬染料等)、無機顏料(例如：氧化鈦等)、導電性顏料(例如：鋅、鋁、鎳等金屬粉末、磷化鐵、銻摻雜型氧化錫等)、偶合劑(例如鈦偶合劑等)、三聚氰胺-三聚氰酸加成物等之1種或2種以上。
其次，將所獲得塗料組成物塗佈於冷軋鋼板的表面上，並施行烘烤。另外，在將所獲得塗料組成物塗佈於冷軋鋼板的表面時，就手段並無特別的限定。最好使用輥塗機。加熱乾燥(烘烤)處理係可使用例如：乾燥機、熱風爐、高頻感應加熱爐、紅外線爐等，就從耐蝕性的觀點，較佳為高頻感應加熱爐。加熱處理最好依到達板溫為50~350℃、較佳為80℃~250℃的範圍實施。若加熱溫度未滿50℃，則皮膜中的溶劑會大量殘留，導致耐蝕性不足。又，若加熱溫度超過350℃，不僅不符經濟效益，且皮膜會出現缺陷而有導致耐蝕性降低的可能性。由上述，可獲得表面具有含有機樹脂與結晶性層狀物之有機無機複合皮膜的冷軋鋼板。
另外，藉由成膜處理等所使用的處理液中含有雜質，即便諸如N、Pb、Na、Mn、Ba、Sr、Si等被導入於有機無機複合皮膜中，仍不會損及本發明的效果。
[實施例]
其次，針對本發明利用實施例進行更詳細說明。層狀複氫氧化物係在表1所示含有2價陽離子(M2+ )中之任1種以上、與3價陽離子(M3+ )中之任1種以上的水溶液(表1中，水溶液1組成)中，滴下含有無機陰離子或有機陰離子(An- )中之任1種以上陰離子的水溶液(表1中，水溶液2組成)並進行精製。此時，依反應懸浮液的pH成為10±0.1的方式滴下2.0莫耳-NaOH溶液，而調整溶液。接著，過濾所獲得沉澱物，經乾燥便獲得粉狀的層狀複氫氧化物。另外，經X射線繞射確認係屬於層狀複氫氧化物。
將成為表面上所形成有機無機複合皮膜的塗料組成物，就樹脂組成物係使用表2所示有機樹脂，在其中將依上述手法所生成的層狀複氫氧化物，依如表3所示方式進行適當調配，並使用塗料用分散機(砂磨機)攪拌45分鐘而調製。
塗膜的底層用鋼板係使用經施行調質軋延且板厚0.7mm的冷軋鋼板。施行依上述所獲得冷軋鋼板表面的鹼脫脂處理，經水洗乾燥後，將上述塗料組成物利用輥塗機施行塗佈，依如表3所示，將烘烤溫度設為140℃施行烘烤(加熱乾燥)。另外，有機無機複合皮膜的膜厚係利用塗料組成物的固形分(加熱殘分)、或塗佈條件(輥的軋縮力、旋轉速度等)進行調整。
測定依如上述所獲得冷軋鋼板表面的有機無機複合皮膜之平均膜厚，且鑑定層狀複氫氧化物。又，表示精巧壓製成形容易度的壓製成形性之評價手法，係實施動摩擦係數測定與耐模具刮傷性評價。另外，各測定方法、鑑定方法係如下。
(1)有機無機複合皮膜之平均膜厚的測定方法
使用FIB對皮膜截面施行45°濺鍍，並依極低加速SEM觀察截面，擷取10處進行測定，將其平均值視為皮膜的平均膜厚。
(2)層狀複氫氧化物之鑑定方法
利用X射線繞射法確認結晶性層狀複氫氧化物的存在。將使用Cu-Kα線且利用X射線繞射法所獲得尖峰、與ICDD卡片進行比對，而鑑定層狀複氫氧化物。合致的卡片係如下。
(a)碳酸氫氧鎂鋁水合物
ICDD卡片參考碼：01-089-0460
[Mg0.667 Al0.333 (OH)2 ][CO3 2- ]0.167 ‧0.5H2 O
(b)碳酸氫氧鋅鋁水合物
ICDD卡片參考碼：00-048-1021
[Zn0.71 Al0.29 (OH)2 ][CO3 2- ]0.145 ‧H2 O
(c)碳酸氫氧化鐵水合物
ICDD卡片參考碼：00-050-1380
[Fe0.67 Fe0.33 (OH)2 ][CO3 2- ]0.145 ‧0.33H2 O
(d)硫酸氫氧鐵鎳水合物
ICDD卡片參考碼：00-042-0573
[Ni0.75 Fe0.25 (OH)2 ][SO4 2- ]0.125 ‧0.5H2 O
(e)氫氧鋁鎂水合物
ICDD卡片參考碼：00-038-0478
[Mg0.75 Al0.25 (OH)2 ][OH- ]0.25 ‧0.5H2 O
(f)氯氧化氫氧鐵鎂水合物
ICDD卡片參考碼：00-020-0500
[Mg0.75 Fe0.25 (OH)2 ][Cl- ]0.25 ‧0.5H2 O
(g)氯化氫氧鈣鋁水合物
ICDD卡片參考碼：00-035-0105
[Ga0.67 Al0.33 (OH)2 ][Cl- ]0.33 ‧0.67H2 O
(h)碳酸氫氧鎂鉻水合物
ICDD卡片參考碼：00-045-1475
[Mg0.67 Cr0.33 (OH)2 ][CO3 2- ]0.157 ‧0.5H2 O
(i)碳酸氧化氫氧鋁鐵水合物
ICDD卡片參考碼：00-051-1527
[Fe0.67 Al0.33 (OH)2 ][CO3 2- ]0.157 ‧0.5H2 O
(j)碳酸氧化氫氧鋁鎳水合物
ICDD卡片參考碼：00-015-0087
[Ni0.67 Al0.33 (OH)2 ][CO3 2- ,OH- ]0.157 ‧0.5H2 O
(3)動摩擦係數之測定方法
為評價壓製成形性(特別係拉抽‧流入部的壓製成形性)，依如下述測定各試體材料的動摩擦係數。圖1所示係摩擦係數測定裝置的概略正視圖。如同圖所示，將從試體材料所採取的摩擦係數測定用試料1固定於試料台2上，試料台2係固定於可水平移動的滑動機台3上面。在滑動機台3的下面設有具接觸到其之輥4且可上下移動的滑動機台支撐台5，並在滑動機台支撐台5上安裝第1荷重元7。該第1荷重元7係藉由將其上推而測定由壓珠6對摩擦係數測定用試料1的押抵荷重N。供測定在使上述押抵力產生作用的狀態下，使滑動機台3朝水平方向移動的滑動阻力F用之第2荷重元8，係安裝於滑動機台3其中一端部。另外，將當作潤滑油用的杉村化學公司製加壓用洗淨油Preton R352L，塗佈於摩擦係數測定用試料1的表面上並施行試驗。
圖2所示係所使用壓珠6的第1形狀、尺寸概略立體示意圖(以下稱「壓珠形狀1」)。在壓珠6的下面押抵於摩擦係數測定用試料1的表面之狀態下進行滑動。圖2所示壓珠6的形狀係寬10mm、試料滑動方向長度12mm，且滑動方向二端的下部係由曲率4.5mmR的曲面構成，被試料押抵的壓珠下面係具有寬10mm、滑動方向長度3mm的平面。
圖3所示係所使用壓珠6的第2形狀、尺寸概略立體示意圖(以下稱「壓珠形狀2」)。在壓珠6的下面押抵於摩擦係數測定用試料1的表面之狀態下進行滑動。圖3所示壓珠6的形狀係寬10mm、試料滑動方向長度69mm，且滑動方向二端的下部係由曲率4.5mmR的曲面構成，被試料押抵的壓珠下面係具有寬10mm、滑動方向長度60mm的平面。
針對動摩擦係數的測定，為使成為假設高強度鋼板壓製成形的面壓，便在室溫(25℃)中，依押抵荷重N為400、1200、1600kgf等3條件實施。另外，試料的抽拉速度(滑動機台3的水平移動速度)係100cm/min、或20cm/min。利用該等條件測定押抵荷重N與滑動阻力F，且試體材料與壓珠6間的動摩擦係數μ係依式：μ=F/N計算出。
壓珠形狀、押抵荷重及抽拉速度的組合係如下。
條件1：壓珠形狀1、押抵荷重400kgf、抽拉速度100cm/min
條件2：壓珠形狀1、押抵荷重1200kgf、抽拉速度100cm/min
條件3：壓珠形狀1、押抵荷重1600kgf、抽拉速度100cm/min
條件4：壓珠形狀2、押抵荷重400kgf、抽拉速度20cm/min
(4)耐模具刮傷性之評價方法
除動摩擦係數之外，冷軋鋼板在滑動距離較長部位處，會因冷軋鋼板與模具的凝聚導致滑動阻力增加，因而容易造成模具刮傷。所以，使用圖1所示摩擦係數測定裝置，重複實施滑動試驗計50次，將動摩擦係數增加0.01以上的重複次數，設為會產生模具刮傷的重複次數，而實施耐模具刮傷性的評價。此處，即便重複實施50次滑動試驗，仍未出現動摩擦係數上升的情況，便將重複次數設為50次以上。試驗條件係與上述(3)動摩擦係數的測定方法同樣，為使成為假設高強度鋼板之壓製成形的面壓，而依上述條件1~條件3實施。
依如上述所獲得試驗結果，合併條件記於表3中。
由表3所示試驗結果中得知下述事項。No.1係未含有結晶性層狀物的例子，屬於與本發明的比較例。該比較例係動摩擦係數較高、耐模具刮傷性差。No.2~27係含有有機樹脂與結晶性層狀物的例子，屬於本發明一例。該No.2~27的本發明例若與No.1的比較例進行比較，則動摩擦係數較低、耐模具刮傷性良好。
(產業上之可利用性)
本發明的冷軋鋼板因為壓製成形性優異，因而可適用於以難成形材料為必要之以汽車車體用途為中心的廣範圍領域。
1．．．摩擦係數測定用試料
2．．．試料台
3．．．滑動機台
4．．．輥
5．．．滑動機台支撐台
6．．．壓珠
7‧‧‧第1荷重元
8‧‧‧第2荷重元
9‧‧‧滑軌
N‧‧‧押抵荷重
F‧‧‧滑動阻力
圖1係摩擦係數測定裝置的概略正視圖。
圖2係圖1中的壓珠6之第1形狀、尺寸的概略立體示意圖(壓珠形狀1)。
圖3係圖1中的壓珠6之第2形狀、尺寸的概略立體示意圖(壓珠形狀2)。

Claims (3)

  1. 一種將有機無機複合皮膜用於強度超過440MPa之冷軋鋼板的表面之用途，該有機無機複合皮膜係平均膜厚為0.10~2.0μm，至少含有有機樹脂及結晶性層狀物，且相對於有機樹脂固形分100重量份，依固形分計含有0.5重量份以上的結晶性層狀物；上述結晶性層狀物係依[M2+ 1-x M3+ x (OH)2 ][An- ]x/n ‧zH2 O所示之層狀複氫氧化物；上述M2+ 係Mg2+ 、Ca2+ 、Fe2+ 、Ni2+ 、Zn2+ 、Pb2+ 、Sn2+ 之1種或2種以上；上述M3+ 係Al3+ 、Fe3+ 、Cr3+ 、3/4Zr4+ 、Mo3+ 之1種或2種以上；上述An- 係OH- 、F- 、CO3 2- 、Cl- 、Br- 、(C2 O4 )2- 、I- 、(NO3 )- 、(SO4 )2- 、(BrO3 )- 、(IO3 )- 、(V10 O28 )6- 、(Si2 O5 )2- 、(ClO4 )- 、(CH3 COO)- 、[C6 H4 (CO2 )2 ]2- 、(C6 H5 COO)- 、[C8 H16 (CO2 )2 ]2- 、n(C8 H17 SO4 )- 、n(C12 H25 SO4 )- 、n(C18 H37 SO4 )- 、SiO4 4- 之1種或2種以上；x、n及z係分別滿足0<x≦0.33、1≦n≦2、0.33≦z≦1之數。
  2. 一種將有機無機複合皮膜用於強度超過440MPa之冷軋鋼板的表面之用途，該有機無機複合皮膜係平均膜厚為0.10~2.0μm，至少含有有機樹脂及結晶性層狀物，且相對於 有機樹脂固形分100重量份，依固形分計含有0.5重量份以上的結晶性層狀物；上述結晶性層狀物係依[M2+ 1-x M3+ x (OH)2 ][An- ]x/n ‧zH2 O所示層狀複氫氧化物；上述M2+ 係Mg2+ 、Ca2+ 、Fe2+ 、Ni2+ 、Zn2+ 之1種或2種以上；上述M3+ 係Al3+ 、Fe3+ 、Cr3+ 之1種或2種以上；上述An- 係OH- 、CO3 2- 、Cl- 、(SO4 )2- 之1種或2種以上；x、n及z係分別滿足0<x≦0.33、1≦n≦2、0.33≦z≦1之數。
  3. 如申請專利範圍第1或2項之有機無機複合皮膜之用途，其中，上述有機樹脂係從環氧樹脂、多羥基聚醚樹脂、聚酯樹脂、胺甲酸乙酯樹脂、矽樹脂、丙烯酸樹脂中選擇1種或2種以上。
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