TWI696678B - 真空熱成型用黏結劑組合物及適用其的真空熱成型用裝飾片 - Google Patents
真空熱成型用黏結劑組合物及適用其的真空熱成型用裝飾片 Download PDFInfo
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- TWI696678B TWI696678B TW105106405A TW105106405A TWI696678B TW I696678 B TWI696678 B TW I696678B TW 105106405 A TW105106405 A TW 105106405A TW 105106405 A TW105106405 A TW 105106405A TW I696678 B TWI696678 B TW I696678B
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- Adhesives Or Adhesive Processes (AREA)
Abstract
本發明提供真空熱成型用黏結劑組合物,上述真空熱成型用黏結劑組合物包含聚氨酯(polyurethane)聚合物及丙烯酸(acrylic)聚合物,熔融溫度與交聯溫度之差為30℃至60℃。並且,本發明提供真空熱成型用裝飾片,上述真空熱成型用裝飾片包括:黏結層;基材層,形成於上述黏結層的上部;印刷層,形成於上述基材層的上部;以及透明基材層,形成於上述印刷層的上部,上述黏結層由上述真空熱成型用黏結劑組合物形成。
Description
本發明涉及真空熱成型用黏結劑組合物及適用其的真空熱成型用裝飾片。
以往,汽車內置材料的裝潢用部件與其他汽車部件相比,不占很大比重,但隨著消費者的需要逐漸多樣化,按各個汽車進行設計及進行功能差別化,從而使對汽車內置材料用膜原材料的研究和發展也正在加速化。
最近,隨著對簡單的臨時裝飾、裝潢性的提高和對觸感性能賦予的需要(needs)增加,汽車內置用膜原材料使用三維表面臨時裝飾工藝的適用範圍擴大,並通過真空熱成型由裝飾片覆蓋注塑物的工藝。此時,為了使裝飾片好好熔敷於內置材料,當前,需要根據優秀的黏結力及高溫高壓條件,調節官能團的反應性,從而對當成型時具有柔韌性並可附著於內置材料的黏結層進行研究。
發明所欲解決之問題
本發明提供真空熱成型用黏結劑組合物,上述真空熱成型用黏結劑組合物包含聚氨酯(polyurethane)聚合物及丙烯酸(acrylic)聚合物,熔融溫度與交聯溫度之差為30℃至60℃。
並且,本發明提供真空熱成型用裝飾片,上述真空熱成型用裝飾片包括:黏結層;基材層,形成於上述黏結層的上部;印刷層,形成於上述基材層的上部;以及透明基材層,形成於上述印刷層的上部,上述黏結層由上述真空熱成型用黏結劑組合物形成。
但是,本發明所要解決的技術問題並不局限於以上所提及的問題,本發明所屬技術領域的普通技術人員能夠從以下記載內容中明確地理解未提及的其他問題。
解決問題之技術手段
本發明提供真空熱成型用黏結劑組合物,上述真空熱成型用黏結劑組合物包含聚氨酯聚合物及丙烯酸聚合物,熔融溫度與交聯溫度之差為30℃至60℃。
本發明可提供真空熱成型用黏結劑組合物,真空熱成型用黏結劑組合物中,上述熔融溫度為50℃至90℃,上述交聯溫度為110℃至150℃。
本發明可提供真空熱成型用黏結劑組合物,相對於100重量份的上述真空熱成型用黏結劑組合物的固體成分,包含1至10重量份的上述丙烯酸聚合物。
本發明可提供真空熱成型用黏結劑組合物,上述丙烯酸聚合物的重均分子量為200000至800000。
本發明可提供真空熱成型用黏結劑組合物,相對於100重量份的上述真空熱成型用黏結劑組合物的固體成分,包含90至99重量份的上述聚氨酯聚合物。
本發明可提供真空熱成型用黏結劑組合物,上述聚氨酯聚合物的重均分子量為1000至30000。
本發明可提供真空熱成型用黏結劑組合物,上述聚氨酯聚合物由異氰酸酯(isocyanate)化合物及多元醇(polyol)化合物製備而成。
本發明可提供真空熱成型用黏結劑組合物,上述多元醇化合物包含選自由聚酯(polyester)類多元醇、內酯(lactone)類多元醇、聚碳酸酯(polycarbonate)類多元醇、聚醚(polyether)類多元醇及它們的組合組成的組中的一種以上。
本發明可提供真空熱成型用黏結劑組合物,上述真空熱成型用黏結劑組合物還包括添加劑,上述添加劑包含選自由黏結性賦予樹脂、低分子量體、環氧(epoxy)樹脂、固化劑、紫外線穩定劑、抗氧化劑、調色劑、加固劑、消泡劑、表面活性劑、增塑劑、發泡劑、有機鹽及它們的組合組成的組中的至少一種。
本發明可提供真空熱成型用黏結劑組合物,上述真空熱成型用黏結劑組合物的黏度為800至7000cps。
本發明提供真空熱成型用裝飾片,上述真空熱成型用裝飾片包括:黏結層;基材層,形成於上述黏結層的上部;印刷層,形成於上述基材層的上部;以及透明基材層,形成於上述印刷層的上部,上述黏結層由如上所述的真空熱成型用黏結劑組合物形成。
本發明可提供真空熱成型用裝飾片,上述黏結層的厚度為10µm至50µm。
本發明可提供真空熱成型用裝飾片,上述基材層包含選自由聚甲基丙烯酸甲酯(PMMA,polymethyl methacrylate)、丙烯腈-丁二烯-苯乙烯(ABS,acrylonitrile-butadiene-styrene)、熱塑性聚烯烴(TPO,thermoplastic polyolefin)、聚氯乙烯(PVC,polyvinyl chloride)、聚碳酸酯(PC,polycarbonate)及它們的組合組成的組中的一種。
本發明可提供真空熱成型用裝飾片,在上述黏結層的下部還形成有離型膜層。
本發明可提供真空熱成型用裝飾片,上述離型膜層為聚對苯二甲酸乙二醇酯(PET,polyethylene terephthalate)膜。
本發明可提供真空熱成型用裝飾片,上述印刷層利用選自由凹版印刷、柔版印刷或旋轉篩印刷及它們的組合組成的組中的至少一種方法形成。
本發明可提供真空熱成型用裝飾片,在上述透明基材層的上部還形成有壓花層。
本發明可提供真空熱成型用裝飾片,上述壓花層利用壓紋工序形成。
對照先前技術之功效
本發明的真空熱成型用黏結劑組合物以規定比率包含特定重均分子量的聚氨酯聚合物及丙烯酸聚合物,來使熔融溫度與交聯溫度之差為30℃至60℃,從而使常溫條件下的劣化發生率少,且可具有高溫耐久性。
因此,具有由上述真空熱成型用黏結劑組合物形成的黏結層的裝飾片在通過真空熱成型工藝將上述裝飾片附著於注塑物時,可實現具有優秀的黏結能力及高溫耐久性的黏結層,從而可提高所製備的產品的耐久性及表面質感。
並且,使適用上述黏結層的裝飾片適用於汽車內置材料,從而可向車內賦予優秀的審美感。
本發明人們在研究通過真空熱成型工藝臨時裝飾汽車內置材料的方法的過程中確認如下:使黏結劑具有約50℃至約90℃的第一溫度區間及約110℃至約150℃的第二溫度區間,在第一溫度區間中,成分互相熔融並混合但官能團互相不進行反應,在第二溫度區間中,以化學方式交聯而進行黏結,由此,形成將用於真空熱成型工序的裝飾片的黏結層的黏結劑的熔融溫度與交聯溫度之差為約30℃至約60℃,且可具有優秀的高溫耐久性,從而完成了本發明。
以下,參照附圖詳細說明本發明的實施例,以使本發明所屬技術領域的普通技術人員可容易實施本發明。本發明能夠以多種不同的方式實現,並不局限於在此說明的實施例。
為了明確說明本發明,省略了與說明無關的部分,在說明書全文中,對於相同或類似的結構要素,標注相同的附圖標記。
在附圖中,為了明確表示多層及區域,放大示出了厚度。並且,在附圖中,為了便於說明,誇張示出了一部分層及區域的厚度。
以下,在基材的“上部(或下部)或基材的“上(或下)”形成任意結構不僅指任意結構與上述基材的上部面(或下部面)相接觸來形成,而且不局限於在上述基材與形成於基材上(或下)的任意結構之間不包括其他結構。
真空熱成型用黏結劑組合物
真空熱成型工藝是為了裝飾汽車、傢俱等的多種內置材料或外置材料而將裝飾片臨時裝飾於注塑物的工藝中之一。由於上述真空熱成型方法在高溫及真空條件下執行,因而在此過程中,實現具有優秀的黏結性並具有高溫耐久性的黏結層對可將上述裝飾片好好熔敷於注塑物非常重要。
上述真空熱成型工藝中,在放有表面上沒有任何圖案的注塑物的工作臺上升而附著於裝飾片之前,真空吸入後,點燃加熱器來拉伸裝飾片。此時,加熱器使裝飾片加熱至100℃至150℃,從而當形成裝飾片的黏結層的黏結劑熔融而使注塑物上升時,可使裝飾片容易附著。之後,熄滅加熱器,使放有注塑物的工作臺上升來壓接於裝飾片,並交聯黏結層來結束注塑物的表面臨時裝飾處理。
由此,本發明為了提供具有適合上述真空熱成型工序的熔融溫度和交聯溫度物性的黏結層的裝飾片,提供適合上述黏結層的真空熱成型用黏結劑組合物。
因此,本發明的真空熱成型用黏結劑組合物在約50℃至約90℃的第一溫度區間,黏結劑成分熔融而混合,但官能團不互相反應,只揮發溶劑來形成黏結層,在約110℃至約150℃的第二溫度區間,黏結劑以化學方式交聯來進行黏結。
本發明提供真空熱成型用黏結劑組合物,上述真空熱成型用黏結劑組合物包含聚氨酯聚合物及丙烯酸聚合物,熔融溫度與交聯溫度之差為約30℃至約60℃。
具體地,上述熔融溫度可以為約50℃至約90℃,上述交聯溫度可以為約110℃至約150℃。當利用以往的黏結劑時,為了在真空熱成型中,滿足高溫耐久性,成型時黏結溫度越高越好,但是,當成型膜時,因高熱而有可能使膜受損,並且存在加工性降低的憂慮。並且,若當真空熱成型時,考慮膜受損和加工性,將黏結溫度設為小於110℃,則當測試高溫耐久性時,導致注塑物與裝飾片之間的附著力降低的結果。
為了克服這些問題,在真空熱成型工藝中適用本發明的真空熱成型用黏結劑組合物,來在注塑物中使用裝飾片進行表面處理的情況下,例如,在約90℃溫度下熔融的黏結劑在約150℃溫度下進行交聯,從而可實現適合本工序的黏結層。
相對於100重量份的上述真空熱成型用黏結劑組合物的固體成分,可包含約1至約10重量份的上述丙烯酸聚合物。
上述丙烯酸聚合物可由丙烯酸酯(acrylate)單體或低聚物聚合而成。此時,作為上述丙烯酸酯單體可使用多種丙烯酸酯單體,可例舉1,2-乙二醇二丙烯酸酯(1,2-ethylene glycol diacrylate)、1,12-十二硫醇丙烯酸酯(1,12-dodecanethiol acrylate)、1,4-丁二醇二(甲基)丙烯酸酯(1,4-butanediol di(meth)acrylate)、1,6-己二醇二(甲基)丙烯酸酯(1,6-hexanediol di(meth)acrylate)、新戊二醇二(甲基)丙烯酸酯(neopentyl glycol di(meth)acrylate)、聚乙二醇二(甲基)丙烯酸酯(polyethylene glycol di(meth)acrylate)、新戊二醇己二酸二(甲基)丙烯酸酯(neopentyl glycol adipate di(meth)acrylate)、羥基新戊酸新戊二醇二(甲基)丙烯酸酯(hydroxyl puivalic acid neopentyl glycol di(meth)acrylate)、二環戊烯基二(甲基)丙烯酸酯(dicyclopentanyl di(meth)acrylate)、己內酯改性二環戊烯基二(甲基)丙烯酸酯(caprolactone-modified dicyclopentenyl di(meth)acrylate)、環氧乙烷改性二(甲基)丙烯酸酯(ethylene oxide-modified di(meth)acrylate)、二(甲基)丙烯醯氧基乙基異氰脲酸酯(di(meth)acryloxy ethyl isocyanurate)、烯丙基化環己基二(甲基)丙烯酸酯(allylated cyclohexyl di(meth)acrylate)、三環癸二甲醇(甲基)丙烯酸酯(tricyclodecane dimethanol(meth)acrylate)、二羥甲基二環戊烷二(甲基)丙烯酸酯(dimethylol dicyclopentane di(meth)acrylate)或9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]氟(9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorine)等、環氧乙烷改性六氫鄰苯二甲酸二(甲基)丙烯酸酯(ethylene oxide-modified hexahydrophthalic acid di(meth)acrylate)、三環癸烷二甲醇(甲基)丙烯酸酯(tricyclodecane dimethanol(meth)acrylate)、新戊二醇改性三甲基丙烷二(甲基)丙烯酸酯(neopentyl glycol-modified trimethyl propane di(meth)acrylate)、金剛烷二(甲基)丙烯酸酯(adamantane di(meth)acrylate)的二官能型丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯(trimethylol propane tri(meth)acrylate)、二季戊四醇三(甲基)丙烯酸酯(dipentaerythritol tri(meth)acrylate)、丙酸改性二季戊四醇三(甲基)丙烯酸酯(propionic acid-modified dipentaerythritol tri(meth)acrylate)、季戊四醇三(甲基)丙烯酸酯(pentaerythritol tri(meth)acrylate)、環氧丙烷改性三羥甲基丙烷三(甲基)丙烯酸酯(propylene oxide-modified trimethylol propane tri(meth)acrylate)、三(甲基)丙烯醯氧基乙基異氰脲酸酯(tris(meth)acryloxy ethyl isocyanurate)等的三官能型丙烯酸酯、二甘油四(甲基)丙烯酸酯(diglycerin tetra(meth)acrylate)或季戊四醇四(甲基)丙烯酸酯(pentaerythritol tetra(meth)acrylate)等的四官能型丙烯酸酯、丙酸改性二季戊四醇五(甲基)丙烯酸酯(propionic acid-modified dipentaerythritol penta(meth)acrylate)等的五管能型丙烯酸酯以及二季戊四醇六(甲基)丙烯酸酯(dipentaerythritol hexa(meth)acrylate)、己內酯改性二季戊四醇六(甲基)丙烯酸酯(caprolactone-modified dipentaerythritol hexa(meth)acrylate)等的六官能型丙烯酸酯等,但並不局限於此。
在黏結劑中,相對於100重量份的真空熱成型用黏結劑組合物的固體成分,包含約1至約10重量份的上述丙烯酸聚合物,從而向黏結劑賦予間接效果,並可將熔融溫度與交聯溫度之差調節為約40℃。在包含1重量份以下的丙烯酸聚合物的情況下,存在基材中沒有初期附著性的問題,在包含大於10重量份的丙烯酸聚合物的情況下,還在高溫條件下可發揮黏結力的聚氨酯聚合物的含量減少,結果存在高溫條件下黏結劑的黏結力下降的憂慮。
並且,上述丙烯酸聚合物的重均分子量可以為200000至800000。丙烯酸聚合物的重均分子量維持上述範圍,從而可調節黏結劑的熔融溫度範圍及交聯溫度範圍,並提供實現優秀的高溫耐久性及黏結力的黏結劑。
接著,上述真空熱成型用黏結劑組合物包含聚氨酯聚合物,相對於100重量份的上述真空熱成型用黏結劑組合物的固體成分,可包含約90至約99重量份的上述聚氨酯聚合物。
上述聚氨酯聚合物由具有活性羥基(hydroxyl group)的乙醇(alcohol)和具有異氰酸酯基(isocyanate group)的異氰酸酯進行聚合反應而產生反應熱來形成。由於包含上述聚氨酯聚合物,當成型於黏結劑時,可賦予延伸的柔韌性的物性,具體地,相對於100重量份的上述真空熱成型用黏結劑組合物的固體成分,包含約90至約99重量份,從而可實現柔韌性和黏結性。若小於或大於上述範圍,則有可能產生在柔韌性及高溫條件下達不到高的黏結強度的問題。
並且,上述聚氨酯聚合物的重均分子量可以為約1000至約30000,優選地,上述聚氨酯聚合物的重均分子量可以為約3000至約10000。本發明的真空熱成型用黏結劑組合物包含上述重量範圍的聚氨酯聚合物,從而可具有柔韌性及高的黏結強度的效果。
上述聚氨酯聚合物可由異氰酸酯化合物、多元醇化合物製備而成。
上述異氰酸酯化合物作為每個分子具有兩個以上的異氰酸酯基的化合物,可使用芳香族二異氰酸酯(diisocyanate)及其衍生物。上述異氰酸酯化合物可以為選自由甲苯二異氰酸(toluene diisocyanate)、二苯基甲烷二異氰酸酯(diphenyl methane diisocyanate)、改性二苯基甲烷二異氰酸酯、萘二異氰酸酯(naphthalene diisocyanate)、苯二異氰酸酯(phenylene diisocyanate)、六亞甲基二異氰酸酯(hexamethylene diisocyanate)、賴氨酸異氰酸酯(lysine isocyanate)、環己烷二異氰酸酯(cyclohexane diisocyanate)、異佛爾酮二異氰酸酯(isophorone diisocyanate)、亞甲基二苯基異氰酸酯(methylene diphenyl isocyanate)、二甲苯二異氰酸酯(xylene diisocyanate)、四甲基二甲苯二異氰酸酯(tetramethyl xylene diisocyanate)、降冰片烯二異氰酸酯(norbornene diisocyanate)、三苯基甲烷三異氰酸酯(triphenylmethane triisocyanate)、聚苯基聚亞甲基聚異氰酸酯(polyphenyl polymethylene polyisocyanate)、包含碳二亞胺基(carbodiimide group)的聚異氰酸酯、包含脲基甲酸酯基(allophanate group)的聚異氰酸酯、包含異氰脲酸酯基(isocyanurate group)的聚異氰酸酯及它們的組合組成的組中的一種以上的化合物,但並不局限於此。
並且,上述多元醇化合物可以為選自由聚酯類多元醇、內酯類多元醇、聚碳酸酯類多元醇、聚醚類多元醇及它們的組合組成的組中的一種以上,更優選地,上述多元醇化合物可以為聚酯類多元醇或聚醚類多元醇。聚酯類多元醇的耐水解性、低溫柔韌性、耐酸性和耐鹼性、電絕緣性等的性質優秀,聚醚類多元醇可賦予柔韌性、高收縮率等的性質。
具體地,聚酯多元醇與聚醚多元醇的重量比沒有特別限制,但聚酯多元醇與聚醚多元醇的重量比可優選為1:9至9:1。維持上述範圍的含量,從而可實現柔韌性、耐酸性和耐鹼性、高收縮率等的特性。
上述真空熱成型用黏結劑組合物為了以交聯溫度區間達成約110℃至約150℃,可使用由阻隔劑阻隔異氰酸酯基的一部分或全部的阻隔型異氰酸酯固化劑。並且,上述阻隔劑可使用ε-己內醯胺(ε-caprolactam)、甲基乙基酮肟(methyl ethyl ketone oxime)、1,2-吡唑(1,2-pyrazole)、二異丙胺(diisopropylamine)或3,5-二甲基吡唑(3,5-dimethylpyrazole)等。
為了形成聚氨酯聚合物,可添加氨基甲酸乙酯(urethane)反應催化劑、聚合引發劑等。上述氨基甲酸乙酯反應催化劑為在氨基甲酸乙酯反應中少量添加的催化劑,作為其的優選例可包含環烷酸銅(copper naphthenate)、環烷酸鈷(cobalt naphthenate)、環烷酸鋅(zinc naphthenate)、n-月桂酸丁基錫(n-butyltinlaurate)、三乙胺(tristhylamine)或2-甲基三乙烯二醯胺(2-methyl triethylene diamide)。
上述聚合引發劑的優選例可由二月桂酸二丁基錫(DBTDL,dibutyltin dilaurate)、對苯二酚(hydroquinone)、氫醌單乙醚(hydroquinone monoethyl ether)、對苯醌(para-benzoquinone)、吩噻嗪(phenothiazine)及它們的混合物形成。根據所使用的催化劑的使用量,除了反應性之外,有可能對反應混合物的流動性和參與生成物的表面層形成的工序的各種事項和得到的生成物產生影響,因此,優選地,上述聚氨酯聚合物包含約0.01至0.03重量百分比的催化劑。
上述真空熱成型用黏結劑組合物還可包含添加劑,上述添加劑包含選自由黏結性賦予樹脂、低分子量體、環氧樹脂、固化劑、紫外線穩定劑、抗氧化劑、調色劑、加固劑、消泡劑、表面活性劑、增塑劑、發泡劑、有機鹽及它們的組合組成的組中的至少一種。
上述真空熱成型用黏結劑組合物包含固化劑。上述固化劑阻隔異氰酸酯基,從而若受到規定的熱,則阻隔劑解離,(-NCO)的反應性增加,從而進行固化反應,以防止異氰酸酯基(-NCO)在常溫條件下與羥基(-OH)或氨基(-NH)進行反應。固化劑的解離溫度為100℃以上,優選地,固化劑的解離溫度為110℃至130℃。
上述真空熱成型用黏結劑組合物的黏度可以為約800cps至約7000cps,優選地,上述真空熱成型用黏結劑組合物的黏度可以為約1000cps至約5000cps。通過維持上述範圍的黏度,上述黏結劑可具有優秀的高溫耐久性及黏結能力,從而使用於臨時裝飾注塑物的表面的裝飾片可在不被擠或不受損的情況下,穩定地附著於注塑物。
真空熱成型用裝飾片
本發明提供真空熱成型用裝飾片,上述真空熱成型用裝飾片包括:黏結層;基材層,形成於上述黏結層的上部;印刷層,形成於上述基材層的上部;以及透明基材層,形成於上述印刷層的上部,上述黏結層由上述的真空熱成型用黏結劑組合物形成。
圖1簡要表示上述真空熱成型用裝飾片100的截面。參照圖1,上述真空熱成型用裝飾片100可以為依次層疊有黏結層10、基材層20、印刷層30及透明基材層40的結構。
上述真空熱成型用裝飾片100用於臨時裝飾各種內置材料或外置材料的表面,能夠以真空熱成型方法附著於這些內置材料或外置材料。此時,上述黏結層10的結構由上述的黏結劑組合物形成,從而具有適合真空熱成型的熔融溫度和交聯溫度,並具有優秀的高溫耐久性,由於不發生劣化,可附著於表面能低的基材。
具體地,上述黏結層10的厚度可以為約10μm至約50μm。上述黏結層10的厚度滿足上述範圍,從而對具有彎曲的表面也可表示優秀的附著性,在真空熱成型過程中可容易實現優秀的黏結性。
上述真空熱成型用裝飾片100中,在上述黏結層10上部可形成有基材層20。上述基材層20起到上述真空熱成型用裝飾片的中心基材的作用,在真空熱成型過程中,確保優秀的耐熱性,且可同時表示優秀的耐久性。
具體地,上述基材層20可包含選自由聚甲基丙烯酸甲酯、丙烯腈-丁二烯-苯乙烯、熱塑性聚烯烴、聚氯乙烯、聚碳酸酯及它們的組合組成的組中的一種。例如,上述基材層20可包含丙烯腈-丁二烯-苯乙烯,在此情況下,可同時確保優秀的成型性及耐熱性。
上述基材層20的厚度可以為約0.5mm至約3mm。上述基材層的厚度滿足上述範圍,從而作為中心基材確保優秀的耐久性,並在上述裝飾片的真空熱成型過程中,可確保優秀的耐熱性。
上述真空熱成型用裝飾片100中,在上述基材層20上部可形成有印刷層30。上述印刷層30可根據需要選擇多種原料及印刷方法來形成印刷圖案而製備,並起到通過上述裝飾片直接賦予美感效果的作用。
具體地,上述印刷層30可利用選自由凹版印刷、柔版印刷或旋轉篩印刷及它們的組合組成的組中的至少一種方法形成。例如,上述基材層20可包含可進行熱成型的聚碳酸酯、聚對苯二甲酸乙二醇酯、丙烯腈-丁二烯-苯乙烯,在此情況下,在上述基材層的上部,在無基材受損的情況下,直接利用印刷工藝來形成印刷層,從而與以往的轉印方式相比,可通過簡化工序來節減費用,並減少不良率。
上述印刷層30的厚度可以為約1μm至約40μm。上述印刷層的厚度滿足上述範圍,從而表示鮮明的印刷圖案,並同時可確保可形成於上部的壓花層2和優秀的相容性。
上述真空熱成型用裝飾片100中,在上述印刷層30上部可形成有透明基材層40。具體地,上述透明基材層40可包含聚甲基丙烯酸甲酯,但並不局限於此。包括上述透明基材層40,從而具有保護印刷層20,並提高光澤和耐磨性的效果。
並且,代替上述透明基材層40,在上述印刷層30正上方可塗敷表面處理劑。即,上述真空熱成型用裝飾片100中,在壓花層2與印刷層30之間,代替上述透明基材層40,還可形成有通過上述表面處理劑的塗敷層。
圖2簡要表示本發明另一實例的真空熱成型用裝飾片200的截面。
上述真空熱成型用裝飾片200中,在上述黏結層10的下部還可形成有離型膜層1。上述離型膜層1是上述裝飾片利用為真空熱成型之前剝離的,起到使上述裝飾片100的流通及運輸變得容易的作用。
具體地,上述離型膜層1可包含聚對苯二甲酸乙二醇酯,更具體地,上述離型膜層1可使用塗敷有矽塗敷劑的聚對苯二甲酸乙二醇酯膜。在此情況下,當在上述離型膜層1正上方形成黏結層10時,可確保優秀的塗敷性及剝離性。
上述離型膜層1的厚度可以為約20μm至約100µm。上述離型膜層1的厚度維持上述範圍,從而可容易剝離,並在上述離型膜層1上部形成黏結層10的過程中可確保優秀的加工性。
並且,上述真空熱成型用裝飾片200中,在透明基材層40的上部還形成有壓花層2。具體地,上述壓花層2可利用壓紋工序來形成。
上述壓花層包括由上述壓花團形成的凹部和凸部,從而可向上述印刷層的印刷圖案賦予更優秀的美感效果,並通過外部來實現。
以下,提出用於幫助理解本發明的優選實施例。但是,以下實施例僅屬於更容易地理解本發明,本發明的內容不限定於以下實施例。
實施例1
1.黏結劑組合物的製備
1)丙烯酸聚合物的合成
在設置冷卻裝置,以使氮氣回流,並容易調節溫度的2L的反應器中,相對於20重量份的丙烯酸異辛酯(2-EHA,2-ethylhexyl acrylate)、40重量份的丙烯酸正丁酯(n-BA,n-butyl acrylate)、30重量份的丙烯酸異冰片酯(IBOA,isobornyl acrylate)、10重量份的2-羥基乙基丙烯酸酯(HEA,2-hydroxyethyl acrylate)、0.05重量份的分子量調節劑n-十二烷基硫醇(n-dodecyl mercaptan)投入單體混合物,並作為溶劑投入甲基乙基酮(MEK,methyl ethyl ketone),來製備了重均分子量為60萬,玻璃化轉變溫度為-26℃的丙烯酸聚合物。
2)聚氨酯聚合物的合成
在設置冷卻裝置,以使氮氣回流,並容易調節溫度的2L的反應器中,使900g的聚丙二醇(polypropylene glycol)、500g的馬來酸酐(maleic anhydride)和500g的苯酐(phthalic anhydride)進行縮合反應。若縮合反應結束,則添加甲基乙基酮來降低黏度。其中,投入0.5摩爾的二甲苯二異氰酸酯(xylene diisoeyanate)和巴辛頓(Baxenden)公司的阻隔型異氰酸酯B17990,來合成了單組分聚氨酯聚合物。
配合95重量份的上述聚氨酯聚合物和5重量份的上述丙烯酸聚合物,來製備了黏結劑組合物。
2.真空熱成型用裝飾膜的製備
在厚度為0.15mm的丙烯腈-丁二烯-苯乙烯基材層上部,通過凹版印刷方法形成了厚度為20µm的印刷層。在上述印刷層上部形成厚度為10μm的聚甲基丙烯酸甲酯透明基材層,在上述透明基材層上部通過紫外線(UV)壓印方法形成了壓花層。另一方面,準備了厚度為50µm的聚對苯二甲酸乙二醇酯離型膜層,在上述離型膜層上部塗敷在上述實施例及比較例中製備的黏結劑組合物,來製備了厚度為35µm的黏結層。接著,進行熱貼合,以使上述黏結層附著於上述基材層下部,來結束了真空熱成型用裝飾片的製備。
實施例
2
除了配合90重量份的上述聚氨酯聚合物和10重量份的上述丙烯酸聚合物來製備黏結劑組合物之外,以與上述實施例1相同的方法製備了裝飾片。
比較例
1
除了配合80重量份的上述聚氨酯聚合物和20重量份的上述丙烯酸聚合物來製備黏結劑組合物之外,以與上述實施例1相同的方法製備了裝飾片。
比較例
2
除了配合100重量份的上述聚氨酯聚合物來製備黏結劑組合物之外,以與上述實施例1相同的方法製備了裝飾片。
比較例
3
在聚氨酯合成過程中除了巴辛頓公司的阻隔型異氰酸酯BI7990製備後,配合90重量份的上述聚氨酯聚合物和10重量份的上述丙烯酸聚合物來製備黏結劑組合物,除此之外,以與上述實施例1相同的方法製備了裝飾片。
實驗例
通過以下方法評價,並在表1中表示結果。
1)剝離力的評價
以25mm×20cm(橫向×縱向)的大小裁剪真空熱成型用裝飾片來製備了試片。之後,去除上述試片的離型膜,並在丙烯腈-丁二烯-苯乙烯基材面利用加熱至130℃的壓膜機進行熱壓膜後附著,接著在經過30分鐘的時間點,使用拉伸試驗機在剝離速度為300mm/min且剝離角度為180°的條件下測定了剝離力。
2)高溫耐久性的評價
在實施例及比較例中製備的真空熱成型用裝飾片中去除離型膜,並通過真空熱成型方法製備了樣品。高溫耐久性的評價通過以下方法進行:在80℃溫度下,在烘箱中放置通過真空熱成型方法製備而成的樣品300小時,並觀察成型品和薄片的邊緣部分是否收尾及翹起,並根據以下基準進行了評價。
評價基準
○:未觀察到翹起
×:觀察到翹起
3)附著性的評價
根據JIS K 5600-5-6執行附著性評價。如圖3及圖4所示,橫切實施例及比較例的試片的表面。之後,用軟毛刷整理表面,並牢固地附著規定的膠帶(JIS Z 1522)後,以90°角度拉膠帶的一邊拆下來。根據圖3及圖4所示的基準判斷。
評價基準
○:無受橫切影響的剝離損傷
△:受橫切影響的剝離的5-15%剝離
×:受橫切影響的剝離全部脫落
4)成型性的評價
成型條件將膜實測溫度設為150℃來進行真空熱成型。確認在彎曲的部分上的成型性是否良好,並評價成型品和膜在邊緣(Edge)部分上卷向內側的程度是否良好。
評價基準
○:在彎曲的部分上的成型性良好,在邊緣部分上卷向內側的程度良好
×:成型性差,邊緣部分的卷度也不足
如上述表1所示,可知與上述比較例1、比較例2及比較例3相比,上述實施例的裝飾片具有優秀的成型性、高溫耐久性、附著性及剝離力。尤其,在不包含丙烯酸聚合物的比較例2的黏結劑的情況下,表示整體物性明顯下降。並且,在不使用阻隔型異氰酸酯的比較例3的情況下,交聯溫度非常低,物性也下降。因此,包含本發明範圍內的聚氨酯聚合物及丙烯酸聚合物,並形成熔融溫度與交聯溫度之差為30℃以上的黏結劑,從而可實現優秀的高溫耐久性、成型性、附著性及剝離力。
100、200‧‧‧真空熱成型用裝飾片
10‧‧‧黏結層
20‧‧‧基材層
30‧‧‧印刷層
40‧‧‧透明基材層
1‧‧‧離型膜層
2‧‧‧壓花層
圖1簡要表示本發明一實施例的真空熱成型用裝飾片的截面。 圖2簡要表示本發明另一實施例的真空熱成型用裝飾片的截面。 圖3表示橫切實施例的表面的示意圖。 圖4表示比較例的試片的表面的示意圖。 圖5表示將膜實測溫度設為150℃來進行真空熱成型的成型例的示意圖。
100‧‧‧真空熱成型用裝飾片
10‧‧‧黏結層
20‧‧‧基材層
30‧‧‧印刷層
40‧‧‧透明基材層
Claims (13)
- 一種真空熱成型用黏結劑組合物,其中,包含聚氨酯(polyurethane)聚合物及丙烯酸(acrylic)聚合物,熔融溫度與交聯溫度之差為30℃至60℃,該熔融溫度為50℃至90℃,該交聯溫度為110℃至150℃,相對於100重量份的該真空熱成型用黏結劑組合物的固體成分,包含90至99重量份的該聚氨酯聚合物,相對於100重量份的該真空熱成型用黏結劑組合物的固體成分,包含1至10重量份的該丙烯酸聚合物,該聚氨酯聚合物由異氰酸酯(isocyanate)化合物及多元醇(polyol)化合物製備而成。
- 如請求項1之真空熱成型用黏結劑組合物,其中,該丙烯酸聚合物的重均分子量為200000至800000。
- 如請求項1之真空熱成型用黏結劑組合物,其中,該聚氨酯聚合物的重均分子量為1000至30000。
- 如請求項1之真空熱成型用黏結劑組合物,其中,該多元醇化合物包含選自由聚酯(polyester)類多元醇、內酯(lactone)類多元醇、聚碳酸酯(polycarbonate)類多元醇、聚醚(polyether)類多元醇及它們的組合組成的組中的一種以上。
- 如請求項1之真空熱成型用黏結劑組合物,其中,還包括添加劑,該添加劑包含選自由黏結性賦予樹脂、低分子量體、環氧(epoxy)樹脂、固化劑、紫外線穩定劑、抗氧化劑、調色劑、加固劑、消泡劑、表面活性劑、增塑劑、發泡劑、有機鹽及它們的組合組成的組中的至少一種。
- 一種真空熱成型用裝飾片,其中,包括:黏結層;基材層,形成於該黏結層的上部; 印刷層,形成於該基材層的上部;以及透明基材層,形成於該印刷層的上部,該黏結層由請求項1至5中任一項所述的真空熱成型用黏結劑組合物形成。
- 如請求項6之真空熱成型用裝飾片,其中,該黏結層的厚度為10μm至50μm。
- 如請求項6之真空熱成型用裝飾片,其中,該基材層包含選自由聚甲基丙烯酸甲酯(PMMA,polymethyl methacrylate)、丙烯腈-丁二烯-苯乙烯(ABS,acrylonitrile-butadiene-styrene)、熱塑性聚烯烴(TPO,thermoplastic polyolefin)、聚氯乙烯(PVC,polyvinyl chloride)、聚碳酸酯(PC,polycarbonate)及它們的組合組成的組中的一種。
- 如請求項6之真空熱成型用裝飾片,其中,在該黏結層的下部還形成有離型膜層。
- 如請求項9之真空熱成型用裝飾片,其中,該離型膜層包括聚對苯二甲酸乙二醇酯(PET,polyethylene terephthalate)膜。
- 如請求項6之真空熱成型用裝飾片,其中,該印刷層利用選自由凹版印刷、柔版印刷或旋轉篩印刷及它們的組合組成的組中的至少一種方法形成。
- 如請求項6之真空熱成型用裝飾片,其中,在該透明基材層的上部還形成有壓花層。
- 如請求項12之真空熱成型用裝飾片,其中,該壓花層利用壓紋工序形成。
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KR102314948B1 (ko) * | 2018-11-23 | 2021-10-21 | 주식회사 엘지화학 | 윈도우 데코 필름용 점착 시트 및 이를 포함하는 윈도우 데코 필름 |
KR102296592B1 (ko) * | 2018-11-23 | 2021-09-01 | 주식회사 엘지화학 | 윈도우 데코 필름용 점착 시트 및 이를 포함하는 윈도우 데코 필름 |
CN109705756A (zh) * | 2018-12-21 | 2019-05-03 | 江苏杰立胶粘材料科技有限公司 | 一种印刷泡棉胶带及其生产工艺 |
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WO2016140452A3 (ko) | 2016-10-27 |
KR20160108702A (ko) | 2016-09-20 |
CN107406733B (zh) | 2021-01-08 |
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JP2018512477A (ja) | 2018-05-17 |
US20180051195A1 (en) | 2018-02-22 |
KR101981937B1 (ko) | 2019-05-28 |
US10344193B2 (en) | 2019-07-09 |
TW201632602A (zh) | 2016-09-16 |
EP3266846A2 (en) | 2018-01-10 |
JP6657246B2 (ja) | 2020-03-04 |
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CN107406733A (zh) | 2017-11-28 |
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