TWI786254B - 加飾成形用片、預成形之成形體、及加飾成形體 - Google Patents

加飾成形用片、預成形之成形體、及加飾成形體 Download PDF

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TWI786254B
TWI786254B TW108100649A TW108100649A TWI786254B TW I786254 B TWI786254 B TW I786254B TW 108100649 A TW108100649 A TW 108100649A TW 108100649 A TW108100649 A TW 108100649A TW I786254 B TWI786254 B TW I786254B
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Taiwan
Prior art keywords
decorative molding
molded body
molding sheet
preformed
resin
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TW108100649A
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English (en)
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TW201934337A (zh
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松田大輔
藤澤道憲
伊藤敏幸
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日商可樂麗股份有限公司
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Abstract

本發明使用：一種加飾成形用片，其具備具有仿皮革加工面的人工皮革基體、及在人工皮革基體之與仿皮革加工面相對的背面所形成之包含氯乙烯-乙酸乙烯酯共聚物的樹脂層，該人工皮革基體包含含有平均纖度0.001~1dtex的極細纖維的不織布與賦予至不織布的高分子彈性體；及一種預成形之成形體，其係將該加飾成形用片予以賦形為三次元形狀而成者。

Description

加飾成形用片、預成形之成形體、及加飾成形體
本發明關於用以將仿皮革的外觀賦予至樹脂成形體的表面之加飾成形用片、將其予以賦形而成之預成形之成形體、及加飾成形體。
作為行動電話、行動裝置、家電製品之殼體或車輛、飛機等的內部裝飾零件、建材、家具等之外部裝飾構件，已知有為了藉由真空成形、氣壓成形、熱壓成形、模內成形(亦稱為插入成形)等來裝飾樹脂成形體之表面所使用的加飾成形用片。
例如，下述專利文獻1揭示將背面塗布有氯乙烯-乙酸乙烯酯共聚物的不織布予以預形體成形，使用所得之預成形之成形體，藉由模內成形射出聚碳酸酯而製造加飾成形體。又，下述專利文獻2揭示將背面塗布有氯乙烯的極細纖維不織布予以預形體成形，使用所得之預成形之成形體，藉由模內成形而製造加飾成形體。
先前技術文獻 專利文獻
專利文獻1 日本特開2007-276366號公報
專利文獻2 日本特開2013-132783號公報
如上述，以往已知將包含不織布的片經預備成形而成之預成形之成形體，使用於模內成形，使其一體化於樹脂成形體之表面而成之加飾成形體。然而，以往之包含不織布的片經預備成形而成之預成形之成形體，係在製造預成形之成形體時缺乏賦形性，於預形體成形後難以正確地保持形狀，形態安定性低。因此，將預成形之成形體收容於模內成形所用的模具內時，有時無法正確地遵循模內成形模具的模腔的形狀。這時，預成形之成形體會被一體化在偏移出模內成形所成形的樹脂成形體之目的區域的位置，而有位置精度低之問題。
又，藉由模內成形將樹脂成形體成形之際，當熔融樹脂與預成形之成形體接觸時，流動的熔融樹脂會對預成形之成形體的表面施予剪切力，因此例如在樹脂成形體之形成有熔合線的部分等，預成形之成形體收縮的方向上會被施力，而亦有發生皺紋之問題。再者，亦有預成形之成形體對於樹脂成形體的接著性不充分之問題。
本發明之目的在於提供加飾成形用片、將其予以賦形而成之預成形之成形體、及加飾成形體，其係在將包含不織布的片經預備成形而成之預成形之成形體使用於模內成形使其一體化於樹脂成形體的表面而製造加飾成形體時，可解決上述之預形體成形後的形態安定性、預成形之成形體對於樹脂成形體的位置精度、及預成形之成形體對於樹脂成形體的接著性之問題。
本發明之一局面為一種加飾成形用片，其具備具有仿皮革加工面的人工皮革基體、及在人工皮革基體之與仿皮革加工面相對的背面所形成之包含氯乙烯-乙酸乙烯酯共聚物的樹脂層，該人工皮革基體包含含有平均纖度0.001~1dtex的極細纖維的不織布與賦予至不織布的高分子彈性體。如此的加飾成形用片係預形體成形性及預形體成形後的形態安定性優異。又，進行預形體成形後而用於模內成形時，預成形之成形體對於樹脂成形體的位置精度、及預成形之成形體對於樹脂成形體的接著性優異。
又，從進行預形體成形時的形態安定性、將加飾成形體成形時的預成形之成形體的位置精度及接著性達到優異的平衡之點來看，氯乙烯-乙酸乙烯酯共聚物中的乙酸乙烯酯單元之含有率較佳為5~25莫耳%。
另外，從進行預形體成形時的形態安定性、將加飾成形體成形時的預成形之成形體之位置精度及接著性達到優異的平衡之點來看，氯乙烯-乙酸乙烯酯共聚物之玻璃轉移溫度較佳為65~85℃。
還有，從形態安定性、預成形之成形體之位置精度及接著性達到優異的平衡之點來看，樹脂層之單位面積重量較佳為50~100g/m2。
又，從製造預成形之成形體時的形態安定性特別優異之點來看，人工皮革基體較佳包含10~40質量%的高分子彈性體。
另外，從預成形之成形體的賦形性或形態安定性優異且維持優異的仿皮革之手感之點來看，高分子彈性體較佳為聚胺基甲酸酯。
還有，從得到皮革狀的外觀之點來看，作為仿皮革加工面，較佳為極細纖維經起毛的起毛面，或在人工皮革基體之表面所積層的樹脂層。
又，即使是極細纖維包含耐隆極細纖維時，在製造預成形之成形體時的形態安定性亦優異，從此點來看是較宜的。包含耐隆極細纖維之不織布，在具有柔軟的手感之點上是較宜的，但缺乏預形體成形時的形態安定性，賦形為困難。依照本發明，縱然使用包含含有耐隆極細纖維之不織布的人工皮革基體時，也得到形態安定性優異之預成形之成形體。
另外，本發明之另一局面為一種預成形之成形體，其係將上述加飾成形用片予以賦形為三次元形狀而成者。如此的預成形之成形體，由於形態安定性優異，故在模內成形時不易發生位置偏移，且與被射出成形的樹脂成形體之接著性亦優異，從此點來看是較宜的。
還有，本發明之其它一局面為一種加飾成形體，其具備樹脂成形體與在樹脂成形體之表面所配置的表皮層，表皮層為上述的加飾成形用片。
可得到：將包含人工皮革基體的加飾成形用片予以預形體成形且進行模內成形時，預成形之成形體的形態安定性、預成形之成形體對於樹脂成形體的位 置精度以及預成形之成形體對於樹脂成形體的接著性優異之加飾成形用片；將其予以賦形而成之預成形之成形體；及加飾成形體。
1‧‧‧不織布
2‧‧‧高分子彈性體
3‧‧‧人工皮革基體
6‧‧‧預成形之成形體
7‧‧‧不需要部分
8‧‧‧樹脂成形體
10‧‧‧加飾成形用片
20‧‧‧加飾成形體
圖1係實施形態之加飾成形用片的示意剖面圖。
圖2係說明將加飾成形用片予以預形體成形之步驟的說明圖。
圖3係說明使用預形體成形，進行模內成形之步驟的說明圖。
以下，說明本發明之加飾成形用片、將其予以賦形而成之預成形之成形體及加飾成形體之較佳實施形態。
圖1係本實施形態之加飾成形用片10的示意剖面圖。圖1中，1為包含極細纖維的不織布，2為賦予至不織布的高分子彈性體，3為具有仿皮革加工面M的人工皮革基體，4為在人工皮革基體3之與仿皮革加工面M相對的背面所形成之包含氯乙烯-乙酸乙烯酯共聚物的樹脂層。仿皮革加工面M例如係形成不織布1的纖維經起毛的麂皮狀或牛巴戈狀起毛面，或施予積層有皮革的粒面狀樹脂層之加工。
從成形時的延伸性優異之點來看，形成人工皮革基體的不織布之極細纖維的纖度較佳為平均纖度0.001~1dtex，更佳為0.002~0.8dtex，尤佳為0.003~0.5dtex。
形成極細纖維的樹脂，只要是在成形時具有熱軟化性的樹脂，則沒有特別的限定。作為如此的樹脂之具體例，例如可舉出聚對苯二甲酸乙二酯(PET)、改質聚對苯二甲酸乙二酯(改質PET)、聚對苯二甲酸丁二酯(PBT)等之聚酯；耐隆6、耐隆6.6、耐隆6.10、耐隆6.12等之耐隆；聚丙烯、聚乙烯等之聚烯烴等。
於此等之中，從成為柔軟的手感之點來看，特佳為耐隆。
賦予至不織布的高分子彈性體，只要是以往含浸賦予至人工皮革基體的高分子彈性體，則可無特別限定地使用。作為如此的高分子彈性體之具體例，從預成形之成形體的賦形性或形態安定性優異、維持優異的仿皮革手感之點來看，較宜使用例如聚胺基甲酸酯或丙烯酸系彈性體。
從預成形之成形體的形態安定性特別優異之點來看，賦予至不織布的高分子彈性體之含有率較佳為1~50質量%，更佳為5~45質量%，特佳為10~40質量%。若高分子彈性體之含有率過低，則在製造預成形之成形體時，難以維持形態，尤其當使用耐隆纖維的不織布時，有難以保持預形體成形後的形態之傾向。又，高分子彈性體之含有率過高時，有預形體成形的賦形性及模內成形的成形性降低之傾向。
於人工皮革基體之成為加飾成形體的表面之側的仿皮革加工面M，以形成有不織布的纖維經起毛之麂皮狀或牛巴戈狀起毛面、或積層有皮革的粒面狀樹 脂層之方式施予使其像皮革表面之加工。於人工皮革基體的仿皮革加工面M上形成起毛面時，變成絨毛狀人工皮革，積層粒面狀樹脂層時，變成粒面狀人工皮革。作為形成絨毛狀人工皮革之方法，可舉出藉由打磨(buffing)將人工皮革基體之表面，加工成麂皮狀或牛巴戈狀之方法。打磨係以砂紙或刷子等磨擦人工皮革基體之表面，使纖維起毛之處理。又，作為形成粒面狀人工皮革之方法，可舉出在人工皮革基體之表面上，藉由乾式造面法或直接塗布法等之方法，積層包含聚胺基甲酸酯等高分子彈性體的粒面狀樹脂層之方法。作為形成粒面狀樹脂層的高分子彈性體，可使用以往用於粒面狀樹脂層之形成的聚胺基甲酸酯或丙烯酸系彈性體等。
然後，在加飾成形用片之與仿皮革加工面相對的背面，形成包含氯乙烯-乙酸乙烯酯共聚物的樹脂層。
氯乙烯-乙酸乙烯酯共聚物中的乙酸乙烯酯單元之含有率為5~25莫耳%，尤其8~20莫耳%者，預形體成形時的形態安定性、成形為加飾成形體時的預成形之成形體之位置精度及接著性達到優異的平衡，從此點來看是較宜的。乙酸乙烯酯單元之含有率過高時，有預成形之成形體的形態安定性及預成形之成形體的位置精度、熔合線附近的平滑性難以升高之傾向。又，乙酸乙烯酯單體之含有率過低時，有預成形之成形體對於樹脂成形體的接著性難以升高之傾向。再者，氯乙烯-乙酸乙烯酯共聚物中的乙酸乙烯酯單元之含有率例如可使用FT-IR測定。
氯乙烯-乙酸乙烯酯共聚物之玻璃轉移溫度(℃)較佳為50~95℃，更佳為65~85℃，特佳為68~76℃。玻璃轉移溫度過低時，有預成形之成形體的形態安定性，預成形之成形體的位置精度，接著性及熔合線附近的平滑性難以升高之傾向。又，玻璃轉移溫度過高時，有預成形之成形體與樹脂成形體的接著性難以升高之傾向。
包含氯乙烯-乙酸乙烯酯共聚物的樹脂層之相對於其形成面的每單位面積之量(樹脂單位面積重量)，較佳為25~200g/m2，特佳為50~100g/m2。樹脂單位面積重量過少時，有預成形之成形體的形態安定性或在將加飾成形體成形時的熔合線附近之平滑性難以升高之傾向，尤其當使用柔軟手感的耐隆纖維之不織布時，有形態安定性難以升高之傾向。
包含氯乙烯-乙酸乙烯酯共聚物的樹脂層，係藉由在加飾成形用片之與仿皮革加工面相對的背面，塗布氯乙烯-乙酸乙烯酯共聚物的乳液或溶液後，進行乾燥而形成。
接著，作為本實施形態之加飾成形體之製造方法，參照圖式，說明將加飾成形用片預備成形為符合射出成形所用的模具之模腔的形狀，製造預成形之成形體後，於模具之模腔內收容預成形之成形體，藉由射出成形的模內成形之製造方法。
圖2係說明將加飾成形用片的預成形之成形體予以成形用的熱壓成形之各步驟的說明圖。圖2 中，10為加飾成形用片，21為熱壓用的公模，22為熱壓用的母模，21a為公模21的模芯，22a為母模22的模腔。又，5為修剪處理前的預成形之成形體，6為預成形之成形體，7為經修剪處理的加飾成形用片10之不需要部分。
首先，如圖2(a)所示，將加飾成形用片10配置於母模22與公模21之間。此時，母模22與公模21係被加熱到可使加飾成形用片10軟化的指定溫度。然後，如圖2(b)所示，以指定的壓力將母模22與公模21閉模。此時，加飾成形用片10係被夾於公模21的模芯21a或母模22的模腔22a之間而賦形。
然後，如圖2(c)所示，將母模22與公模21開模，藉由冷卻而得到修剪處理前的預成形之成形體5。然後，從母模22及公模21中取出修剪處理前的預成形之成形體5，藉由修剪加飾成形用片10的不需要部分7，得到預成形之成形體6。
再者，於本實施形態中，代表性地說明藉由熱壓成形將預成形之成形體予以成形之例，但是將預成形之成形體予以成形之方法係不限於熱壓成形，只要是真空成形、氣壓成形、真空氣壓成形等之能將片賦形為立體形狀之成形方法，則可無特別限定地使用。
如此所得之預成形之成形體係用於模內成形，一體化於樹脂成形體之表面而成為加飾成形體。參照圖3而說明藉由模內成形將預成形之成形體6一體化於被射出成形的樹脂成形體8所得到之加飾成形體20之製造方法。
圖3中，6為預成形之成形體，12a為活動側模，12b為固定側模，13為射出成形機的射出部本體，13a為噴嘴，13b為料筒，13c為同軸螺桿(in-line screw)，14為樹脂流入口，8為樹脂成形體，8a為熔融樹脂，20為加飾成形體。活動側模12a與固定側模12b係成為一對，構成形成模腔c的射出成形模具12。再者，於本實施形態中，活動側模12a為射出成形模具的母模，固定側模12b為射出成形模具的公模。
首先，如圖3(a)所示，於活動側模12a之形成模腔用的凹部，收容預成形之成形體6。
其次，如圖3(b)所示，將活動側模12a與固定側模12b閉模。然後，如圖3(c)所示，於將活動側模12a與固定側模12b在閉模狀態下形成的模腔c內，填充熔融樹脂8a。詳細而言，使射出成形機的射出部13前進，使噴嘴13a抵接於在固定側模12b所形成的樹脂流入口14，藉由同軸螺桿13c射出料筒13b內的熔融樹脂8a，以指定的填充壓力將熔融樹脂8a填充於模腔c。
射出成形條件係按照被射出的樹脂之熱特性或熔融黏度、樹脂成形體之形狀及樹脂厚度，適宜設定條件(樹脂溫度、模具溫度、射出壓力、射出速度、射出後之保持壓力、冷卻時間)。
被成形的射出成形體之樹脂的種類係沒有特別的限定。作為其具體例，例如可舉出ABS樹脂、PMMA樹脂般的丙烯酸系樹脂、聚苯乙烯系樹脂、聚碳酸酯、聚丙烯等之聚烯烴、聚對苯二甲酸乙二酯(PET) 或聚對苯二甲酸丁二酯(PBT)等之聚酯、各種耐隆、COP樹脂等。
又，被成形的射出成形體之厚度亦沒有特別的限定，可按照用途或成形性而適宜選擇。例如，用於家電製品之殼體時，選擇0.3~2mm，尤其0.5~1.5mm，作為較佳的範圍。
然後，於冷卻步驟中，將活動側模12a與固定側模12b在閉模狀態下形成的模腔c內所成形的樹脂成形體8與積層於樹脂成形體8之預成形之成形體6經一體化而成的積層體，冷卻指定的時間後，如圖3(d)所示，將活動側模12a與固定側模12b開模，取出加飾成形體20，其係所成形的樹脂成形體8與積層於樹脂成形體8之加飾成形用片的預成形之成形體6經一體化而成。
實施例
接著，藉由實施例更具體地說明本發明。再者，本發明之範圍完全不受實施例所限定。
[實施例1]
碎片摻合50質量份的耐隆6(Ny6)(島成分)與50質量份的高流動性低密度聚乙烯(海成分)，藉由混合熔融紡絲而製造海島型複合纖維。然後，將海島型複合纖維在70℃的熱水中延伸至2.5倍，對於經延伸的海島型複合纖維，給予纖維油劑，施予機械捲縮，更乾燥後，切割成51mm，得到4dtex的短纖維。使用此短纖維，形成 單位面積重量600g/m2的纖網(web)，接著從兩面交替地合計進行約500扎/cm2的針扎，更加熱至120℃，以壓光輥加壓而作成表面平滑的纏結不織布。於此纏結不織布，含浸聚四亞甲基醚系聚胺基甲酸酯二甲基甲醯胺溶液(濃度13%)，並浸於DMF/水=15/85的混合液之中，使聚胺基甲酸酯濕式凝固成多孔質狀後，在熱甲苯中溶出而去除海島型複合纖維中的海成分，藉此產生纖度0.004dtex的極細纖維。如此地，得到厚度1.4mm的人工皮革基體。
將厚度1.4mm的人工皮革基體予以裁半，藉由打磨切面而調整厚度，再藉由打磨反切面而形成麂皮狀起毛面，得到聚胺基甲酸酯含有率40質量%、單位面積重量221g/m2、表觀密度0.368g/cm3、厚度0.60mm之麂皮狀人工皮革。
然後，藉由在麂皮狀人工皮革之與麂皮狀的起毛面相對的背面，凹版塗布如表1所示的共聚合比及特性之氯乙烯-乙酸乙烯酯共聚物的乳液，進行乾燥，形成樹脂單位面積重量99g/m2之氯乙烯-乙酸乙烯酯共聚物的樹脂層。如此地，得到加飾成形用片，其具備：包含含有平均纖度0.004dtex的極細纖維之不織布與40質量%的聚胺基甲酸酯之麂皮狀人工皮革；及在與起毛面相對的背面所形成之包含氯乙烯-乙酸乙烯酯共聚物的樹脂層。所得之加飾成形用片係單位面積重量320g/m2、表觀密度0.516g/cm3、厚度0.62mm。
然後，將加飾成形用片在模具溫度100℃、加壓壓力100kg/cm2下，使用加壓模具，藉由進行熱壓成形而形成預成形之成形體，該加壓模具係用於賦形為對應於後述射出成形模具之形狀。然後，依照以下之基準，判定預成形之成形體之形態安定性。
(形態安定性)
算出所得之預成形之成形體的高度保持率，且目視外觀，用以下之基準判定。
A：高度保持率為95%以上，角的賦形亦良好。
B：高度保持率為90~95%，角的賦形亦良好。
C：高度保持率為80~90%，角的賦形稍微不明確。
D：高度保持率為50~80%，角的賦形不明確。
E：高度保持率為0~50%，僅留下角的賦形痕跡。
接著，使用所得之預成形之成形體，進行模內成形。具體而言，搭載於電動式射出成形機(住友重機械工業(股)製的SE-100)，於將射出成形模具的活動側模與固定側模開模之狀態下，在形成活動側模的模腔之凹部內配置預成形之成形體。然後，將活動側模與固定側模閉模。再者，射出成形模具係模腔形狀為厚度1.6mm、縱100mm、橫150mm、高度5.0mm之一面開放的箱狀，以2點澆口在中央部形成熔合線之模具。
然後，於樹脂溫度230℃、模具溫度40℃之條件下，射出ABS樹脂而填充於模腔內。然後，於填充後，在冷卻後開模。如此地，得到在ABS樹脂的樹脂 成形體之表面上一體化有預成形之成形體之加飾成形體。
然後，對於所得之加飾成形體，依照以下之基準，評價預成形之成形體對於樹脂成形體的位置精度、預成形之成形體表面之熔合線附近的平滑性、及預成形之成形體對於樹脂成形體的接著性。
(預成形之成形體對於樹脂成形體的位置精度)
目視觀察加飾成形體的預成形之成形體與樹脂成形體之位置偏移，用以下之基準判定。
A：對於樹脂成形體之目的範圍，預成形之成形體係在0.2mm以內偏移，正確地配置。
B：對於樹脂成形體之目的範圍，預成形之成形體係在0.2~0.5mm中位置偏移而配置。
C：對於樹脂成形體之目的範圍，預成形之成形體係超過0.5mm的位置偏移而配置。
(熔合線附近的平滑性)
目視加飾成形體的預成形之成形體表面之樹脂成形體的形成熔合線之附近，用以下之基準判定。
A：預成形之成形體之表面為平滑，完全沒有熔合線痕跡。
B：雖然預成形之成形體之表面為平滑，但看到熔合線痕跡為1cm以下。
C：預成形之成形體之表面不平滑，看到熔合線痕跡為1cm以上。
(預成形之成形體對於樹脂成形體的接著性)
使用拉伸試驗機(Tensilon ORIENTEC(股))，如以下地評價加飾成形體中之預成形之成形體對於樹脂成形體的接著強力。具體而言，從加飾成形體切出寬度25mm×長度100mm，作成試驗片。然後，以從端部起層間剝離長度40mm左右之方式，剝離試驗片的加飾成形體之樹脂成形體與預成形之成形體。然後，將各自的端部，以初期間隔設定在50mm的拉伸試驗機之上下各自的夾頭夾住，以拉伸速度100mm/分鐘進行拉伸試驗，得到拉伸時間-剝離強力的曲線。然後，從所得之曲線中抽出最大值與最小值的各5點，將平均值當作接著強力。求出3條樣品的平均值，如以下地分等級。
A：4Kg/cm以上
B：3~4Kg/cm
C：2~3Kg/cm
D：1~2Kg/cm
E：0~1Kg/cm
下述表1中顯示結果。
Figure 108100649-A0305-02-0018-1
[實施例2~4]
除了如表1所示地變更氯乙烯-乙酸乙烯酯共聚物的樹脂層中之氯乙烯-乙酸乙烯酯共聚物的共聚合比或樹脂單位面積重量以外，與實施例1同樣地製造加飾成形用片及加飾成形體，進行評價。表1中顯示結果。
[實施例5]
將實施例1所得之人工皮革基體予以裁半，藉由打磨切面而調整厚度後，於打磨反切面而起毛的面上，藉由乾式造面法，黏著並積層聚胺基甲酸酯之粒面狀樹脂層，得到粒面狀人工皮革。於實施例1中，除了使用粒面狀人工皮革來代替麂皮狀人工皮革以外，與實施例1同樣地製造加飾成形用片及加飾成形體，進行評價。表1中顯示結果。
[實施例6]
藉由熔融紡絲法，調製由60質量份的耐隆6.12(Ny6.12)(島成分)與40質量份的高流動性低密度聚乙烯(海成分)所成之海島型複合纖維。然後，將海島型複合纖維在70℃的熱水中延伸至2.5倍，對於經延伸的海島型複合纖維，給予纖維油劑，施予機械捲縮，更乾燥後，切割成51mm，得到4dtex的短纖維。使用此短纖維，形成單位面積重量600g/m2的纖網，接著從兩面交替地合計進行約1500扎/cm2的針扎，使面積收縮率成為 20%，更加熱至120℃，以壓光輥加壓而作成表面平滑的纏結不織布。於此纏結不織布，含浸聚四亞甲基醚系聚胺基甲酸酯二甲基甲醯胺溶液(濃度13%)，於熱甲苯中溶出而去除海島型複合纖維中的海成分，產生纖度0.004dtex的極細纖維。如此地，得到厚度1.4mm的人工皮革基體。除了於實施例1中，使用上述人工皮革基體以外，與實施例1同樣地製造加飾成形用片及加飾成形體，進行評價。表1中顯示結果。
[實施例7~10]
除了如表1所示地變更氯乙烯-乙酸乙烯酯共聚物的樹脂層中之氯乙烯-乙酸乙烯酯共聚物的共聚合比或樹脂單位面積重量以外，與實施例1同樣地製造加飾成形用片及加飾成形體，進行評價。表1中顯示結果。
[比較例1]
除了不形成氯乙烯-乙酸乙烯酯共聚物的樹脂層以外，與實施例1同樣地製造加飾成形用片及加飾成形體，進行評價。表1中顯示結果。
[比較例2]
除了形成乙酸乙烯酯均聚物的樹脂層來代替氯乙烯-乙酸乙烯酯共聚物的樹脂層以外，與實施例1同樣地製造加飾成形用片及加飾成形體，進行評價。表1中顯示結果。
[比較例3]
除了不形成氯乙烯-乙酸乙烯酯共聚物的樹脂層以外，與實施例5同樣地製造加飾成形用片及加飾成形體，進行評價。表1中顯示結果。
[比較例4]
除了形成氯乙烯均聚物的樹脂層來代替氯乙烯-乙酸乙烯酯共聚物的樹脂層以外，與實施例5同樣地製造加飾成形用片及加飾成形體，進行評價。表1中顯示結果。
[比較例5]
除了於實施例6的人工皮革基體之製造中，省略含浸賦予聚胺基甲酸酯之步驟以外，與實施例1同樣地製造加飾成形用片及加飾成形體，進行評價。表1中顯示結果。
如表1所示，使用實施例1~10之含有耐隆極細纖維不織布的人工皮革基體作為加飾成形用片時，預成形之成形體的形態安定性皆為C以上。另一方面，於未形成氯乙烯-乙酸乙烯酯共聚物的樹脂層之比較例1及比較例3之情況，預成形之成形體的形態安定性為E。又，形成有乙酸乙烯酯均聚物的樹脂層來代替氯乙烯-乙酸乙烯酯共聚物的樹脂層之比較例2之情況，形態安定性為D。又，形成有氯乙烯均聚物的樹脂層來代替氯 乙烯-乙酸乙烯酯共聚物的樹脂層之比較例4之情況，雖然形態安定性為C，但是接著性為D。又，使用在不織布中未含浸聚胺基甲酸酯的加飾成形用片之比較例5之情況，雖然亦形態安定性為C，但是熔合線附近的平滑性及接著性為C。
[實施例11]
製造海島型複合纖維的纏結不織布，其包含乙烯改質聚乙烯醇作為海成分的熱塑性樹脂，且包含改質PET(間苯二甲酸單元之含有比例6.0莫耳%的間苯二甲酸改質聚對苯二甲酸乙二酯)作為島成分的熱塑性樹脂。然後，於海島型複合纖維的纏結不織布中含浸聚碳酸酯/醚系聚胺基甲酸酯的乳液後，藉由加熱乾燥，得到含浸賦予有聚胺基甲酸酯之海島型複合纖維的纏結不織布。
然後，將含浸賦予有聚胺基甲酸酯之海島型複合纖維的纏結不織布，在90℃的熱水中浸漬20分鐘而萃取去除海成分，藉由乾燥而得到包含12質量%的聚胺基甲酸酯與平均纖度0.08dtex的極細纖維之不織布的1.4mm之人工皮革基體。將厚度1.4mm的人工皮革基體予以裁半，藉由打磨切面而調整厚度，再藉由打磨反切面而形成麂皮狀起毛面，得到聚胺基甲酸酯含有率12質量%、單位面積重量253g/m2、表觀密度0.496g/cm3、厚度0.51mm之麂皮狀人工皮革。
然後，藉由在麂皮狀人工皮革之與麂皮狀的起毛面相對的背面，凹版塗布如表2所示的共聚合比及特性之氯乙烯-乙酸乙烯酯共聚物的乳液，進行乾燥，而形成樹脂單位面積重量50g/m2之氯乙烯-乙酸乙烯酯共聚物的樹脂層。如此地，得到加飾成形用片，其具備：包含含有平均纖度0.08dtex的改質PET極細纖維之不織布與12質量%聚胺基甲酸酯之麂皮狀人工皮革；及在與起毛面相對的背面所形成之包含氯乙烯-乙酸乙烯酯共聚物的樹脂層。所得之加飾成形用片係單位面積重量303g/m2、表觀密度0.541g/cm3、厚度0.56mm。
然後，將加飾成形用片在模具溫度100℃、加壓壓力100kg/cm2下，使用加壓模具，藉由進行熱壓成形而形成預成形之成形體，與實施例1同樣地評價形態安定性，該加壓模具係用以賦形為與實施例1相同的對應於射出成形模具之形狀。
然後，使用所得之預成形之成形體，與實施例1同樣地進行模內成形，得到在ABS樹脂的樹脂成形體之表面上一體化有預成形之成形體之加飾成形體。
然後，對於所得之加飾成形體，與實施例1同樣地評價。下述表2中顯示結果。
Figure 108100649-A0202-12-0022-2
[實施例12]
將實施例11所得之人工皮革基體予以裁半，藉由打磨切面而調整厚度後，於打磨反切面而起毛的面上，藉由乾式造面法，黏著並積層聚胺基甲酸酯之粒面狀樹脂層，得到粒面狀人工皮革。於實施例11中，除了使用粒面狀人工皮革來代替麂皮狀人工皮革以外，與實施例11同樣地製造加飾成形用片及加飾成形體，進行評價。表2中顯示結果。
[實施例13~16]
除了如表2所示地變更氯乙烯-乙酸乙烯酯共聚物的樹脂層中之氯乙烯-乙酸乙烯酯共聚物的共聚合比或樹脂單位面積重量以外，與實施例11同樣地製造加飾成形用片及加飾成形體，進行評價。表2中顯示結果。
[比較例6]
除了於實施例11的人工皮革基體之製造中，省略含浸賦予聚胺基甲酸酯之步驟，且變更厚度以外，與實施例11同樣地製造加飾成形用片及加飾成形體，進行評價。表2中顯示結果。
[比較例7]
除了於實施例11的人工皮革基體之製造中，省略含浸賦予聚胺基甲酸酯之步驟，且變更厚度，再者，不形成氯乙烯-乙酸乙烯酯共聚物的樹脂層以外，與實施例11同樣地製造加飾成形用片及加飾成形體，進行評價。表2中顯示結果。
如表2所示，使用實施例11~16之含有改質PET極細纖維不織布的人工皮革基體作為加飾成形用片時，預成形之成形體的形態安定性為C以上，預成形之成形體對於樹脂成形體的接著性亦為C以上。另一方面，使用在不織布中未含浸聚胺基甲酸酯的加飾成形用片之比較例6之情況，形態安定性、位置精度、平滑性皆比實施例11更差。又，未形成氯乙烯-乙酸乙烯酯共 聚物的樹脂層之比較例7之情況，尤其接著性評價項目為E，比實施例11顯著較差。
產業上的利用可能性
本發明之加飾成形用片及加飾成形體宜使用在將成形品的表面裝飾成仿皮革之用途，該成形品係行動電話、行動裝置、家電製品的殼體、或車輛、飛機等的內部裝飾零件、建材、家具等的外部裝飾構件。
1‧‧‧不織布
2‧‧‧高分子彈性體
3‧‧‧人工皮革基體
4‧‧‧樹脂層
10‧‧‧加飾成形用片

Claims (11)

  1. 一種加飾成形用片，其具備具有仿皮革加工面的人工皮革基體、及在該人工皮革基體之與該仿皮革加工面相對的背面所形成之包含氯乙烯-乙酸乙烯酯共聚物的樹脂層，該人工皮革基體包含含有平均纖度0.001~1dtex的極細纖維的不織布與賦予至該不織布的高分子彈性體，該樹脂層之單位面積重量為25~200g/m2。
  2. 如請求項1之加飾成形用片，其中該氯乙烯-乙酸乙烯酯共聚物中的乙酸乙烯酯單元之含有率為5~25莫耳%。
  3. 如請求項1之加飾成形用片，其中該氯乙烯-乙酸乙烯酯共聚物之玻璃轉移溫度為65~85℃。
  4. 如請求項1之加飾成形用片，其中該樹脂層之單位面積重量為50~100g/m2。
  5. 如請求項1之加飾成形用片，其中該人工皮革基體包含10~40質量%的該高分子彈性體。
  6. 如請求項1之加飾成形用片，其中該高分子彈性體為聚胺基甲酸酯。
  7. 如請求項1之加飾成形用片，其中該仿皮革加工面為該極細纖維經起毛之起毛面。
  8. 如請求項1之加飾成形用片，其中該仿皮革加工面係在該人工皮革基體之表面所積層的樹脂層。
  9. 如請求項1之加飾成形用片，其中該極細纖維包含耐 隆極細纖維。
  10. 一種預成形之成形體，其係將如請求項1至9中任一項之加飾成形用片予以賦形為三次元形狀而成者。
  11. 一種加飾成形體，其具備樹脂成形體與在該樹脂成形體之表面所配置的表皮層，該表皮層為如請求項1至9中任一項之加飾成形用片。
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