TW202000453A - 層壓鋼板、其製造方法及使用於其的片材 - Google Patents
層壓鋼板、其製造方法及使用於其的片材 Download PDFInfo
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- TW202000453A TW202000453A TW108121335A TW108121335A TW202000453A TW 202000453 A TW202000453 A TW 202000453A TW 108121335 A TW108121335 A TW 108121335A TW 108121335 A TW108121335 A TW 108121335A TW 202000453 A TW202000453 A TW 202000453A
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- layer
- resin layer
- sheet
- fluorinated polymer
- laminated steel
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Abstract
本發明的實例係關於片材、包括上述片材的層壓鋼板及其製造方法,上述片材包括丙烯酸樹脂層以及直接形成於上述丙烯酸樹脂層的一面的氟化高分子樹脂層。
Description
本發明實例係關於層壓鋼板、其製造方法及使用於其的片材。更具體而言,多個實例係關於一種既具有耐候性、耐化學性及耐污染性又可以承受高溫層壓程序的層壓鋼板、其製造方法及使用於其的片材。
所謂層壓鋼板是指在以電鍍鋅鋼板、熱浸鍍鋅鋼板、冷軋鋼板、不銹鋼鋼板、熱鍍鋁鋅鋼板以及鋁線圈等為材料製成的鋼板表面上形成各種功能性膜層的產品。
上述層壓鋼板主要應用於冰箱、洗衣機、空調等家用電器外形殼,與普通塗裝鋼板相比,具有美麗的外觀特性和卓越的加工性的優點。
並且,層壓鋼板也用作建築物的內部及外部裝飾材料,在此情況下,在製造鋼板後,對鋼板進行單獨的加工步驟並且必須將膜黏結在其上,因此應滿足良好的加工性、黏結性、耐候性、耐腐蝕性等條件。
通常,使用聚對苯二甲酸乙二醇酯(PET)膜、聚氯乙烯(PVC)膜等作為層壓鋼板的保護膜,但聚對苯二甲酸乙二醇酯膜的耐紫外線(UV)性、加工性及耐裂紋性稍稍欠缺,而聚氯乙烯膜的耐候性、耐化學性及耐污染性不高,因此,這種層壓鋼板在用作建築內部及外部裝飾材料方面略顯不足。
為了改善此問題,最近嘗試使用耐候性良好的氟化高分子樹脂層來作為保護膜,然而,氟化高分子樹脂層在其特性上與其他功能性膜的接合力低,在透過塗敷原料樹脂來形成層壓膜以解決此問題的情況下,產品的適用性則不是很好。
並且,在將如保護膜等功能性膜層壓於鋼板的情況下,為了確保與鋼板的接合力而需要高溫條件,但氟化高分子樹脂層的耐熱性一般不高,因此存在無法承受高溫條件而導致膜變形的問題。
本發明實例提供一種既具有耐候性、耐化學性及耐污染性又可以承受高溫層壓程序的層壓鋼板、其的製造方法及使用於其的片材。
一實例的層壓鋼板包括:鋼板以及設置於上述鋼板上的第一片材,上述第一片材包括丙烯酸樹脂層以及直接形成於上述丙烯酸樹脂層的一面的氟化高分子樹脂層。
再一實例的層壓鋼板的製造方法包括:透過共擠壓(co-extrusion)丙烯酸樹脂與氟化高分子樹脂來製造第一片材的步驟;透過層壓上述第一片材與包括基材層的第二片材來製造複合片材的步驟,其中,上述基材層選自由聚酯樹脂層、聚烯烴樹脂層、聚氯乙烯樹脂層、鋁箔層以及其所組合之群;以及層壓上述複合片材和鋼板的步驟。
另一實例的片材包括透過共擠壓丙烯酸樹脂與氟化高分子樹脂來形成的丙烯酸樹脂層以及氟化高分子樹脂層。
上述實例的層壓鋼板在週邊具備有氟化高分子樹脂層,因此具有非常良好的耐候性(尤其,耐紫外線性)、耐化學性以及耐污染性。並且,在氟化高分子樹脂層的一面形成丙烯酸樹脂層,因此可以彌補氟化高分子樹脂層的低黏結力。
根據較佳實例,在上述氟化高分子樹脂層與鋼板之間***耐熱性良好的基材層,從而可防止耐熱性不足的氟化高分子樹脂層在高溫層壓程序中變形。
並且,根據較佳實例,透過共擠壓來層壓上述丙烯酸樹脂層與氟化高分子樹脂層,因此在它們之間無需單獨的黏結劑,而且,經共擠壓的膜的表面幾乎沒有粗糙度的差異,因此可以更確實地抑制高溫層壓過程中的變形。
以下,對本發明進行更詳細的說明。
在以下的實例說明中,在記載各個層、孔、窗或區域等形成於各個層、孔、窗或區域等的“上(on)”或“下(under)”的情況下,“上”和“下”包括所有“直接(directly)”或“介於(indirectly)其他結構要素”來形成的情況。
並且,對於各個結構要素的上與下的基準以所附圖式為基準進行說明。出於說明的目的,所附圖式中的各個結構要素的尺寸可被誇大,且並不意味著實際應用的尺寸。
並且,應理解的是,除非另有說明,本發明書所記載的用於表示結構組分的物性數值、尺寸等的所有數值範圍在所有情況下均由術語“約”修飾。
一實例的層壓鋼板包括:鋼板以及設置於上述鋼板上的第一片材,上述第一片材包括丙烯酸樹脂層以及直接形成於上述丙烯酸樹脂層的一面的氟化高分子樹脂層。
〈層壓鋼板〉
圖1示出一實例的層壓鋼板的層結構。
參照圖1,一實例的層壓鋼板10包括:鋼板340;以及配置於上述鋼板340上的第一片材100,上述第一片材100包括:丙烯酸樹脂層120;以及直接形成於上述丙烯酸樹脂層120的一面的氟化高分子樹脂層110。
根據一實例,上述層壓鋼板10在上述鋼板340與上述第一片材100之間還可包括第二片材200,上述第二片材200包括選自由聚酯樹脂層、聚烯烴樹脂層、聚氯乙烯樹脂層、鋁箔層以及其所組合之群中的基材層230。
第一片材
上述第一片材100包括:丙烯酸樹脂層120;以及直接形成於上述丙烯酸樹脂層120的一面的氟化高分子樹脂層110。
像這樣,可以透過在氟化高分子樹脂層的一面形成丙烯酸樹脂層,來彌補氟化高分子樹脂層的低黏結力。
根據一實例,上述第一片材可透過共擠壓來形成。
具體地,上述第一片材100透過共擠壓來形成。即,上述第一片材100包括透過共擠壓丙烯酸樹脂與氟化高分子樹脂來形成的丙烯酸樹脂層以及氟化高分子樹脂層。
由此,在上述丙烯酸樹脂層與上述氟化高分子樹脂層之間不存在黏結劑,因此可以防止因黏結劑導致的物性下降。並且上述丙烯酸樹脂層與上述氟化高分子樹脂層之間即使沒有黏結劑也可以具有非常良好的接合力。
〈氟化高分子樹脂層〉
上述氟化高分子樹脂層110包含50重量%以上、70重量%以上或90重量%以上的氟化高分子樹脂。
例如,上述氟化高分子樹脂可以為聚偏氟乙烯(PVdF)樹脂。由此,上述氟化高分子樹脂層可以為聚偏氟乙烯樹脂層,即,聚偏氟乙烯膜。
上述聚偏氟乙烯樹脂可以為偏氟乙烯(VF2)的均聚物或共聚物。在此情況下,上述共聚物可包含至少50重量%的偏氟乙烯以及可與偏氟乙烯共聚合的剩餘量的其他單體。
作為可與上述偏氟乙烯共聚合的共聚單體,較佳為氟化單體,具體地,可以為氟乙烯;三氟乙烯(VF3);三氟氯乙烯(CTFE);1,2-二氟乙烯;四氟乙烯(TFE);六氟丙烯(HFP);全氟(烷基乙烯基)醚,如全氟(甲基乙烯基)醚(PMVE)、全氟(乙基乙烯基)醚(PEVE)及全氟(丙基乙烯基)醚(PPVE);全氟(1,3-二氧雜環戊烯);全氟(2,2-二甲基-1,3-二氧雜環戊烯)(PDD)以及它們的混合物。較佳地,上述共聚單體可以為三氟氯乙烯、六氟丙烯、三氟乙烯或四氟乙烯。
較佳地,使用流變儀以100s-1
的剪切速率在230℃的溫度下測定時,上述聚偏氟乙烯樹脂可具有4000泊(Poise)至12000泊範圍的黏度。具有上述黏度範圍的聚偏氟乙烯樹脂可更適合擠出及注塑成型。
根據一實例,上述氟化高分子樹脂層可配置於上述層壓鋼板的最週邊層。由此,上述層壓鋼板可具有非常良好的耐候性(尤其,耐紫外線性)、耐化學性及耐污染性。
〈丙烯酸樹脂層〉
上述丙烯酸樹脂層120包含50重量%以上、70重量%以上或90重量%以上的丙烯酸樹脂。
例如,上述丙烯酸樹脂可以為聚甲基丙烯酸甲酯(PMMA)樹脂。由此,上述丙烯酸樹脂層可以為聚甲基丙烯酸甲酯樹脂層,即,聚甲基丙烯酸甲酯膜。
上述聚甲基丙烯酸甲酯樹脂可以為甲基丙烯酸甲酯(MMA)單體的均聚物或與其他共聚單體的共聚物。在上述聚甲基丙烯酸甲酯樹脂為共聚物的情況下,較佳地,甲基丙烯酸甲酯及共聚單體為以50:50至99:1的重量比來共聚合的聚合物。
作為可以與上述甲基丙烯酸甲酯共聚合的共聚單體的例,可以例舉烷基(甲基)丙烯酸酯、丙烯腈、丁二烯、苯乙烯、異戊二烯及它們的混合物等。作為較佳的共聚物,例如,可以選擇甲基丙烯腈及丙烯酸乙酯中的一種以上作為共聚單體來以1重量%至20重量%的含量共聚合而成。
上述聚甲基丙烯酸甲酯樹脂可以官能化,例如,可以包含酸、醯基氯、醇或酐官能團,這些官能團可以透過接枝(graft)或共聚合具有官能團的化合物的方式來導入。其中,較佳地為由丙烯酸共聚物提供的酸官能團。以包含官能團的聚甲基丙烯酸甲酯的重量為基準,具有官能團的化合物的含量可以為15重量%以下。
在3.8kg的負荷下以230℃的溫度測定時,上述聚甲基丙烯酸甲酯樹脂的熔融體積指數(MVI)可以為0.5g/10分鐘至10g/10分鐘。
上述丙烯酸樹脂層還可包括紫外線吸收劑。
可以使用苯並***類、苯並三嗪類等來作為上述紫外線吸收劑。
以上述丙烯酸樹脂層的重量為基準,上述紫外線吸收劑的含量可以為0.1重量%至10重量%或0.5重量%至5重量%。
如上所述的紫外線吸收劑可以彌補上述丙烯酸樹脂層的低耐紫外線性。
〈第一片材的物性〉
根據一實例,上述氟化高分子樹脂層的厚度可以為5µm至12µm或3µm至15µm。
根據一實例,上述丙烯酸樹脂層的厚度可以為10µm至50µm、10µm至30µm或20µm至30µm。
作為具體的一例,上述氟化高分子樹脂層的厚度可以為5µm至12µm,上述丙烯酸樹脂層的厚度可以為20µm至30µm。
根據一實例,上述丙烯酸樹脂層與上述氟化高分子樹脂層的表面粗糙度(Ra)可以分別為0.01µm至2.0µm。
上述氟化高分子樹脂層的表面粗糙度(Ra)可以為0.01µm至2.0µm、0.1µm至1.5µm或0.1µm至1.0µm。並且,上述丙烯酸樹脂層的表面粗糙度(Ra)可以為0.01µm至2.0µm、0.1µm至1.5µm或0.1µm至1.0µm。
上述第一片材透過共擠壓來一次性製造而成,因此上述丙烯酸樹脂層與上述氟化高分子樹脂層之間的表面粗糙度可以幾乎沒有差異。
根據一實例,上述丙烯酸樹脂層的表面粗糙度與上述氟化高分子樹脂層的表面粗糙度(Ra)之差可以為0.7µm以下。例如,上述氟化高分子樹脂層的表面粗糙度(Ra)與上述丙烯酸樹脂層的表面粗糙度(Ra)可以具有0.7µm以下、0.5µm以下、0.3µm以下、0.2µm以下或0.1µm以下之差異。在上述丙烯酸樹脂層與上述氟化高分子樹脂層之間的表面粗糙度之差異在上述較佳範圍內的情況下,在防止膜在與鋼板的高溫層壓過程中變形方面可具有更良好的效果。
上述第一片材的透光率可以為85%以上、90%以上或94%以上(以ASTM D1006為基準)。上述第一片材的霧度可以在50%至75%的範圍或65%至75%的範圍內(以ASTM D1006為基準)。
上述第一片材可具有良好的耐候性(耐紫外線性)。根據一實例,在以1500W/m2
及70℃溫度的條件下,於波長為300nm至400nm的光下暴露96小時時,上述第一片材可具有3.0以下的色差(△E)。
第二片材
上述第二片材200包括基材層230。
上述基材層230選自聚酯樹脂層、聚烯烴樹脂層、聚氯乙烯樹脂層、鋁箔層及其所組合之群。
上述聚酯樹脂層可包含聚對苯二甲酸乙二醇酯(PET)樹脂、聚萘二甲酸乙二醇酯(PEN)樹脂、共聚合聚對苯二甲酸乙二醇酯(Co-PET)等。作為具體的一例,上述聚酯樹脂層可以為聚對苯二甲酸乙二醇酯樹脂層,即,聚對苯二甲酸乙二醇酯膜。並且,還可以在聚對苯二甲酸乙二醇酯膜的至少一面做發紋圖案處理從而提升美觀性。
上述聚烯烴樹脂層還可包括聚乙烯樹脂、聚丙烯樹脂等。作為具體的一例,上述聚烯烴樹脂層可以為聚丙烯(PP)樹脂層,即,聚丙烯膜。
例如,上述聚氯乙烯樹脂層可以使用專業鋼板用耐熱等級的聚氯乙烯樹脂層。
上述基材層的厚度可以為15µm至160µm、15µm至150µm或20µm至150µm。
具體地,上述聚酯樹脂層、上述聚烯烴樹脂層及上述聚氯乙烯樹脂層的厚度可以分別為15µm至160µm、15µm至150µm或20µm至150µm,上述鋁箔層的厚度可以為6µm至30µm、10µm至30µm或17µm至30µm。
並且,上述基材層可以為選自由聚酯樹脂層、聚烯烴樹脂層、聚氯乙烯樹脂層及鋁箔層所組成之群中的兩種以上。例如,上述基材層可以為聚酯樹脂層及鋁箔層、聚烯烴樹脂層及鋁箔層或聚氯乙烯樹脂層及鋁箔層的層壓片材,較佳聚酯樹脂層及上述鋁箔層的層壓片材,但並不限定於此。這種基材層的厚度可以為6µm至150µm、15µm至150µm或25µm至150µm。
根據一實例,上述第二片材200還可包括形成於上述基材層230的至少一面(上部面或下部面)的至少一個功能層220。例如,功能層可位於上述基材層的上部面或下部面,或者基材層可位於上述基材層的上部面及下部面。
根據一實例,上述功能層可選自由印刷層、著色層、圖案層以及鋁蒸鍍層所組成之群。這種功能層可以在層壓鋼板導入圖案、顏色、花紋等從而改善外觀。
並且,上述第二片材200還可包括用於提高與上述第一片材的黏結性的黏結劑層210。上述黏結劑層210可以包括光學上透明的黏結劑。
上述黏結劑可使用以賦予上述第一片材(尤其,丙烯酸樹脂層)與第二片材(功能層或基材層)之間的結合力的方式改性的或市場上銷售的黏結劑。
鋼板
上述鋼板340可包括電鍍鋅鋼板、熱浸鍍鋅鋼板、冷軋鋼板、不銹鋼鋼板、熱鍍鋁鋅鋼板、鋁線圈等。
在上述鋼板340的一面可形成預處理層330、底漆塗膜層320及黏結劑層310中至少一個層。
上述預處理層330產生對鋼板的表面進行改性的作用,透過去除上述鋼板表面的異物使得在鋼板形成底漆塗膜層的程序變得容易。
上述底漆塗膜層320可以提高鋼板耐久性及增加鋼板與其它層的表面結合力,從而順利執行程序。
上述黏結劑層310用於提高與上述第二片材200的黏結性,可包含光學上透明的黏結劑。
層壓構成例
根據一實例,以鋼板、預處理層、底漆塗膜層、黏結劑層、基材層、功能層、黏結劑層、丙烯酸樹脂層以及氟化高分子樹脂層的順序對上述層壓鋼板進行層壓,上述基材層選自由聚酯樹脂層、聚烯烴樹脂層、聚氯乙烯樹脂層及鋁箔層所組成之群,上述功能層可選自由印刷層、著色層、圖案層以及鋁蒸鍍層所組成之群。
並且,在上述層壓的構成中,上述基材層與上述功能層可以相互更換層壓順序(即,上下關係)。
〈層壓鋼板的製造方法〉
圖2及圖3分別示出一實例的層壓鋼板製造方法
參照圖2及圖3,一實例的層壓鋼板10的製造方法包括:透過共擠壓丙烯酸樹脂與氟化高分子樹脂來製造第一片材100的步驟;透過層壓上述第一片材100與包括基材層230的第二片材200來製造複合片材11的步驟,其中,上述基材層230選自由聚酯樹脂層、聚烯烴樹脂層、聚氯乙烯樹脂層、鋁箔層以及其所組合之群;以及層壓上述複合片材11和鋼板340的步驟。
製造第一片材的步驟
首先,共擠壓丙烯酸樹脂及氟化高分子樹脂來製造第一片材100。
透過上述共擠壓,氟化高分子樹脂層110與丙烯酸樹脂層120可形成為一體,而無需額外的黏結劑或高溫層壓程序。
不同的是,在使用黏結劑的情況下,黏合劑可能滲透到片材中,從而可引起諸如反射率等光學物性下降的問題,並且,在使用高溫層壓程序的情況下,可能發生片材物性下降的問題。並且,在使用黏合劑或高溫層壓程序的情況下,需要追加額外程序,因此,在費用方面不是較佳的。
圖4示出示出透過共擠壓來製造第一片材的程序例
參照圖4,可透過兩台擠壓機或一台具有兩個噴嘴的擠壓機20,來同時擠壓丙烯酸樹脂及氟化高分子樹脂,從而氟化高分子樹脂層110與丙烯酸樹脂層120在熔融狀態下接合為一體,形成第一片材100。
上述共擠壓可透過利用管狀(tubula)或模具(die)的方法進行,較佳地,上述模具可使用適用進料塊型的平板形模具(例如,T模具、衣架(coat hanger)模具等)、直線形模具、圓形模具(十字頭(cross head)模具等)、分歧管型模具等,但並不限定於此。
可在本發明中使用的擠壓機不僅可以是單軸或多軸擠壓機,還可以是由多個擠壓機組成的串列式(tandem)擠壓機。並且,在以模具連通擠壓機的連接器(adapter)***非操作混合機或相當於其的裝置,可以維持均等的樹脂溫度。
製造複合片材的步驟
接著,透過層壓上述第一片材100與包括上述基材層230的第二片材200來製造複合片材11。
上述第一片材與第二片材的層壓可透過使用黏結劑來進行或者透過熱層壓程序來進行。上述黏結劑可使用常規黏結劑。
上述第一片材與第二片材的層壓可在60℃至160℃的溫度下進行。例如,在上述基材層為聚酯樹脂層或聚烯烴樹脂層的情況下,上述第一片材與第二片材的層壓可在60℃至90℃的溫度下進行。具體地,在上述基材層為聚酯樹脂層或聚烯烴樹脂層的情況下,上述第一片材與第二片材的層壓可使用黏結劑在60℃至90℃的溫度下進行。作為另一例,在上述基材層為聚氯乙烯樹脂層的情況下,上述第一片材與第二片材的層壓可在150℃至160℃溫度的情況下進行。具體地,在上述基材層為聚氯乙烯樹脂層的情況下,上述第一片材與第二片材的層壓也可在150℃至160℃的溫度下透過熱層壓來進行。
並且,在層壓上述第一片材與第二片材時,處於提升美觀性的目的,可以同時進行表面壓花處理,或者為了提高耐磨耗性可在氟化高分子樹脂層的上部面使用丙烯酸聚氨酯硬塗層。
層壓複合片材與鋼板的步驟
之後,層壓上述複合片材11與鋼板340。
根據一實例,上述複合片材與上述鋼板的層壓可在150℃以上的溫度下進行。
具體地,為了使複合片材與堅硬的鋼板相結合而需要高溫層壓程序。例如,上述複合片材與上述鋼板的層壓可在150℃以上、170℃以上或200℃以上的溫度下進行。更具體地,上述複合片材與上述鋼板的層壓可在150℃至300℃的溫度或170℃至230℃的溫度下進行。
上述複合片材與上述鋼板的層壓可透過穿過可調節溫度的鋼輥及橡膠輥來進行,而且,層壓的壓力可以在1kgf/m2
至10kgf/m2
的範圍內,之後可進行冷卻步驟。
並且,為了提高層間緊貼性、塗膜硬度、耐腐蝕性及耐化學性,上述複合片材與上述鋼板的層壓可透過在上述鋼板的一面形成預處理層、底漆塗膜層及黏結劑層中的至少一種層之後進行。例如,可透過在上述鋼板塗敷黏結劑之後進行。
根據上述層壓鋼板的製造方法,在上述氟化高分子樹脂層與鋼板之間***耐熱性良好的基材層,從而可防止耐熱性差的氟化高分子樹脂層在高溫層壓程序中的變形。
並且,根據層壓鋼板的製造方法,透過共擠壓來層壓上述丙烯酸樹脂層與氟化高分子樹脂層,因此在它們之間無需額外的黏結劑。並且,經共擠壓的膜的表面粗糙度幾乎沒有差異,因此可更確實地抑制在高溫下的變形。
一實例的片材可包括透過共擠壓丙烯酸樹脂與氟化高分子樹脂來形成的丙烯酸樹脂層及氟化高分子樹脂層。
上述丙烯酸樹脂層及氟化高分子樹脂層的相關內容與前面所述內容相同。
根據一實例,在以1500W/m2
及70℃的條件下,於波長為300nm至400nm的光下暴露96小時,上述片材具有3.0以下的色差(△E)。
實施例
以下,透過實施例更具體地說明本發明。以下實施例僅用於例示本發明,不能以此來限定本發明的範圍。
實施例1-1:聚偏氟乙烯/聚甲基丙烯酸甲酯共擠壓膜的製備
使用100重量份的均質聚偏氟乙烯樹脂(Kynar720,阿科瑪(Arkema)公司)作為聚偏氟乙烯樹脂層的原料,在97重量份的改性聚甲基丙烯酸甲酯樹脂(SKC公司)中添加3重量份的苯並***類紫外線吸收劑的混合物用作聚甲基丙烯酸甲酯樹脂層的原料,分別透過雙軸混煉機在230℃的溫度條件下進行混合從而製備各自的顆粒。
在65mm的單軸第一擠壓機及90mm的單軸第二擠壓機分別放入之前製備的聚偏氟乙烯樹脂層與聚甲基丙烯酸甲酯樹脂層的原料的顆粒,在約230℃的溫度下熔融混煉,同時利用兩層進料塊方式的T-模具,進行聚偏氟乙烯/聚甲基丙烯酸甲酯樹脂層的共擠壓。此時,使所排出的共擠壓膜穿過加熱輥與經壓紋處理的橡膠輥之間,從而提高對加熱輥的抓地力並對共擠壓熔融表面賦予粗糙度。
經共擠壓的膜的總厚度為33µm,各層厚度中,聚偏氟乙烯樹脂層為8µm,聚甲基丙烯酸甲酯樹脂層為25µm。
比較例1-1:聚偏氟乙烯單層膜的製備
在97重量份的均質聚偏氟乙烯樹脂(Kynar720,阿科瑪(Arkema)公司出品)中添加3重量份的苯並***類紫外線吸收劑的混合物用作聚偏氟乙烯樹脂層的原料,透過雙軸混煉機在230℃的溫度條件下進行混合從而製備顆粒。在65mm的單軸擠壓機放入之前製備的顆粒,在約230℃的溫度下熔融混煉,同時利用T-模具擠壓聚偏氟乙烯膜。此時,使所排出的膜穿過加熱輥與經壓紋處理的橡膠輥之間,從而提高對加熱輥的抓地力並對熔融表面賦予粗糙度,由此製備了厚度為25µm的聚偏氟乙烯膜。
比較例1-2:聚甲基丙烯酸甲酯單層膜的製備
在65mm的單軸擠壓機放入改性聚甲基丙烯酸甲酯樹脂(SKC公司)顆粒,在約230℃的溫度下熔融混煉,同時利用T-模具擠壓聚甲基丙烯酸甲酯膜。此時,使所排出的膜穿過加熱輥與經壓紋處理的橡膠輥之間,從而提高加對熱輥的抓地力並對熔融表面賦予粗糙度,由此製備了厚度為50µm的聚甲基丙烯酸甲酯膜。
比較例1-3:聚甲基丙烯酸甲酯單層膜的製備
重複與上述比較例1-2相同的程序,但在97重量份的改性聚甲基丙烯酸甲酯樹脂(SKC公司)中添加3重量份的苯並***類紫外線吸收劑的混合物用作膜原料,從而製備了厚度為50µm的聚甲基丙烯酸甲酯膜。
試驗例1
針對在上述實施例及比較例中得到的膜,進行如下項目的評價並將其結果在表2示出。
(1)耐化學性(耐溶劑性)
在樣品表面滴加甲基乙基酮(MEK)並在25℃的溫度下維持24小時,之後觀察外觀。
O:外觀無變化
X:觀察到白化等外觀變形
(2)耐污染性
在樣品表面適用油性筆並在25℃的溫度下維持24小時,之後用碎布擦拭,確認是否很好地去除了油性筆跡。
O:油性跡筆容易去除
X:油性跡筆難以去除
(3)表面外觀
確認樣品表面是否溶出添加劑。
O:未在表面確認到溶出
X:在表面確認到溶出
如上述表2所示,上述實施例1-1的聚偏氟乙烯/聚甲基丙烯酸甲酯共擠壓膜的耐化學性、耐污染性及表面外觀特性均非常良好。反之,上述比較例1-1至1-3的聚偏氟乙烯或聚甲基丙烯酸甲酯單層膜的耐化學性、耐污染性及表面外觀特性中至少一個特性差。
實施例2-1:複合片材的製造
在經有色印刷的聚對苯二甲酸乙二醇酯膜塗敷5µm厚度的聚氨酯類黏結劑,然後在90℃以上的溫度進行乾燥,之後使用常規的乾燥層壓設備來對在上述實施例1-1中製備的聚偏氟乙烯/聚甲基丙烯酸甲酯共擠壓膜進行層壓,從而製備了複合片材。此時,層壓在約6kgf/m2
的壓力及30m/hr的速度條件下進行。
比較例2-1至比較例2-3:複合片材的製造
除了使用在比較例1-1至比較例1-3中製備的膜之外,以與上述實施例2-1相同的方法來製備了複合片材。
試驗例2
針對在上述實施例及比較例中得到的複合片材,按照上述試驗例1的方法來評價耐化學性、耐污染性及表面外觀以及按照如下方法來評價耐紫外線性,並將其結果示於表3。
耐紫外線性
對於樣品使用波長範圍為300nm至400nm的金屬鹵化物燈來在1500W/m2
及70℃的條件下照射96小時。利用色差計來測定樣品初始對比耐候性實驗之後的色差(△E)。
O:△E≤3
X:△E>3(發生黃變)
如上述表3所示,與上述比較例2-1至比較例2-3相比,上述實施例2-1的複合片材的耐紫外線性、耐化學性、耐污染性及表面外觀特性均非常良好。
尤其,上述實施例2-1的複合片材的耐紫外線性評價結果△E測定為約0.66,相反地,上述比較例2-2的複合片材的△E測定為約30.06,因此表現出顯著之差異。
具體地,使用在上述實施例1-1製備的聚偏氟乙烯/聚甲基丙烯酸甲酯共擠壓膜來製造實施例2-1的複合片材,透過共擠壓來使聚偏氟乙烯樹脂層與聚甲基丙烯酸甲酯樹脂層相接合,因而上述膜相互之間具有非常強的相容性,因此可以使在表面的緊貼和相互作用最大化,並可以實現高結合力。與分開製備聚偏氟乙烯膜與聚甲基丙烯酸甲酯膜之後再透過黏結劑來貼合的情況相比,如上所述的共擠壓的膜的層間結合力顯著地高。在使用黏結劑來貼合聚偏氟乙烯膜與聚甲基丙烯酸甲酯膜的情況下,大致在長時間的保管過程中,暴露於高溫或紫外線時,黏結劑的性能下降,由此可導致層間局部翹起或相互剝離,或者可因黏結劑的黃變而給產品品質帶來不良影響。
然而,如上述實施例2-1所述,在對聚偏氟乙烯樹脂層與聚甲基丙烯酸甲酯樹脂層的兩層共擠壓的情況下,可以解決如上所述的問題。尤其,透過聚偏氟乙烯樹脂層來保護聚甲基丙烯酸甲酯樹脂層,從而可使耐候性最大化,在聚甲基丙烯酸甲酯樹脂層添加紫外線吸收劑的情況下,可以更有效地防止聚甲基丙烯酸甲酯樹脂層變色及變形。因此,上述實施例2-1的複合片材的耐紫外線性良好,可有效防止現有印刷層的變性。並且,包括耐熱特性良好的聚甲基丙烯酸甲酯,因此在後續程序中,即使在熱層壓程序中其耐化學性、耐污染性及表面外觀特性也良好。
相反地,如比較例2-1的複合片材,在使用聚偏氟乙烯單層膜的情況下,在後續程序中無法進行熱層壓,且其耐污染性及表面外觀差。並且,如比較例2-1所述,在聚偏氟乙烯單層膜添加紫外線吸收劑的情況下,根據時間流逝,紫外線吸收劑向表面移動(migration),從而可使表面外觀特性下降。
並且,在如比較例2-2的聚甲基丙烯酸甲酯單層膜的情況下,因紫外線而可導致下部黏結劑及基材膜(聚對苯二甲酸乙二醇酯膜)黃變或變形。為了解決此問題,如比較例2-3所述,在聚甲基丙烯酸甲酯單層膜添加紫外線吸收劑的情況下,雖然可改善紫外線性能,但仍存在聚甲基丙烯酸甲酯本身耐化學性及耐污染性低的問題。
實施例3-1:層壓鋼板的製造
在透過預處理(堿處理)1mm的熔融鍍鉛鋼板來去除表面的雜質之後,在其上形成厚度為5µm的聚酯類底漆塗膜層。在上述底漆塗膜層上塗敷厚度為5µm的黏結劑組合物,以賦予層間黏結力,之後進行乾燥。此時,上述黏結劑組合物由60重量%的聚酯樹脂以及40重量%的甲苯溶劑組成。
使經過以上程序的鋼板與在上述實施例2-1製造的複合片材穿過能夠調至低溫的鋼輥及橡膠輥之間來進行層壓。此時,層壓在約200℃的鋼板表面溫度、約7kgf/m2
以內的壓力及30m/hr的速度條件下進行。
比較例3-1至比較例3-3:層壓鋼板的製造
除了使用在比較例2-1至比較例2-3中製造的複合片材之外,以與上述實施例3-1相同的方法來製造層壓鋼板。
試驗例3
針對在上述實施例及比較例中得到的層壓鋼板,按照上述試驗例1及試驗例2的方法來評價耐化學性、耐污染性、表面外觀及耐紫外線性,以及按照如下方法來評價表面耐久性,並將其結果示於表4。
〈表面耐久性〉
將上述鋼板的表面交叉切割(Cross-cut)成十字形,以8mm進行杯突(Erichsen)試驗之後,在紫外線(UVB)下放置1000小時,之後確認鋼板表面是否剝離。
O:表面未剝離
X:表面已剝離
如上述表4所示,與上述比較例3-1至比較例3-3相比,上述實施例3-1的層壓鋼板的耐紫外線性、耐化學性、耐污染性、表面外觀及表面耐久性均非常良好。
具體地,即使在高溫層壓程序中,上述實施例3-1的層壓鋼板也不會產生聚偏氟乙烯樹脂層變形的問題,因此表面耐久性良好。
10‧‧‧層壓鋼板
11‧‧‧複合片材
20‧‧‧擠壓機
100‧‧‧第一片材
110‧‧‧氟化高分子樹脂層
120‧‧‧丙烯酸樹脂層
200‧‧‧第二片材
210‧‧‧黏結劑層
220‧‧‧功能層
230‧‧‧基材層
310‧‧‧黏結劑層
320‧‧‧底漆塗膜層
330‧‧‧預處理層
340‧‧‧鋼板
圖1示出一實例的層壓鋼板的層結構。
圖2示出一實例的層壓鋼板的製造方法。
圖3示出一實例的層壓鋼板的製造方法。
圖4示出透過共擠壓來製造第一片材的程序例。
無。
10‧‧‧層壓鋼板
100‧‧‧第一片材
110‧‧‧氟化高分子樹脂層
120‧‧‧丙烯酸樹脂層
200‧‧‧第二片材
210‧‧‧黏結劑層
220‧‧‧功能層
230‧‧‧基材層
310‧‧‧黏結劑層
320‧‧‧底漆塗膜層
330‧‧‧預處理層
340‧‧‧鋼板
Claims (15)
- 一種層壓鋼板,其特徵在於,包括: 鋼板,以及 設置於上述鋼板上的第一片材; 上述第一片材包括丙烯酸樹脂層以及直接形成於上述丙烯酸樹脂層的一面的氟化高分子樹脂層。
- 如請求項1所述的層壓鋼板,其中,上述層壓鋼板在上述鋼板和上述第一片材之間還包括第二片材,上述第二片材包括選自由聚酯樹脂層、聚烯烴樹脂層、聚氯乙烯樹脂層、鋁箔層以及其所組合之群中的基材層。
- 如請求項1所述的層壓鋼板,其中,上述氟化高分子樹脂層配置於上述層壓鋼板的最週邊層。
- 如請求項1所述的層壓鋼板,其中,上述第一片材透過共擠壓形成。
- 如請求項1所述的層壓鋼板,其中,上述丙烯酸樹脂層與上述氟化高分子樹脂層的表面粗糙度Ra分別為0.01µm至2.0µm。
- 如請求項5所述的層壓鋼板,其中,上述丙烯酸樹脂層的表面粗糙度Ra與上述氟化高分子樹脂層的表面粗糙度Ra之差為0.3µm以下。
- 如請求項2所述的層壓鋼板,其中,上述第二片材還包括形成於上述基材層的至少一面的至少一個功能層。
- 如請求項7所述的層壓鋼板,其中,上述功能層選自由印刷層、著色層、圖案層以及鋁蒸鍍層所組成之群。
- 如請求項1所述的層壓鋼板,其中, 上述層壓鋼板由鋼板、預處理層、底漆塗膜層、黏結劑層、基材層、功能層、黏結劑層、丙烯酸樹脂層以及氟化高分子樹脂層的順序層壓而成, 上述基材層選自由聚酯樹脂層、聚烯烴樹脂層、聚氯乙烯樹脂層、鋁箔層以及其所組合之群, 上述功能層選自由印刷層、著色層、圖案層以及鋁蒸鍍層所組成之群。
- 一種層壓鋼板的製造方法,其特徵在於,包括: 透過共擠壓丙烯酸樹脂與氟化高分子樹脂來製造第一片材的步驟; 透過層壓上述第一片材與包括基材層的第二片材來製造複合片材的步驟,上述基材層選自由聚酯樹脂層、聚烯烴樹脂層、聚氯乙烯樹脂層、鋁箔層以及其所組合之群;以及 層壓上述複合片材和鋼板的步驟。
- 如請求項10所述的層壓鋼板的製造方法,其中,上述複合片材與上述鋼板的層壓在150℃以上的溫度下進行。
- 一種片材,其特徵在於,包括透過共擠壓丙烯酸樹脂與氟化高分子樹脂來形成的丙烯酸樹脂層以及氟化高分子樹脂層。
- 如請求項12所述的片材,其中, 上述氟化高分子樹脂層的厚度為3µm至15µm, 上述丙烯酸樹脂層的厚度為10µm至50µm。
- 如請求項12所述的片材,其中, 上述丙烯酸樹脂層與上述氟化高分子樹脂層的表面粗糙度Ra分別為0.01µm至2.0µm, 上述丙烯酸樹脂層的表面粗糙度Ra與上述氟化高分子樹脂層的表面粗糙度Ra之差為0.7µm以下。
- 如請求項12所述的片材,其中,在上述片材在1500W/m2 及70℃溫度的條件下,於波長為300nm至400nm的光下暴露96小時的情況下,上述片材具有3.0以下的色差△E。
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