TWI785053B - 仿皮革片及纖維構造體 - Google Patents

仿皮革片及纖維構造體 Download PDF

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TWI785053B
TWI785053B TW107118219A TW107118219A TWI785053B TW I785053 B TWI785053 B TW I785053B TW 107118219 A TW107118219 A TW 107118219A TW 107118219 A TW107118219 A TW 107118219A TW I785053 B TWI785053 B TW I785053B
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fiber structure
dye
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藤澤道憲
安藤哲也
菱田弘行
村手靖典
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日商可樂麗股份有限公司
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Abstract

一種仿皮革片或纖維構造體，該仿皮革片包含纖維構造體及被賦予至前述纖維構造體的內部空隙之高分子彈性體，該纖維構造體包含經含有具有偶氮鍵的藍色陽離子染料之染料所染色的纖維，且該仿皮革片或該纖維構造體進一步包含具有陰離子性的多元酚衍生物。又，一種仿皮革片，其包含纖維構造體或被賦予至該纖維構造體的內部空隙之高分子彈性體，該纖維構造體包含經含有具有偶氮鍵的藍色陽離子染料之染料所染色的纖維，其中該仿皮革片在80℃、濕度90%、48小時之條件下濕熱處理時，濕熱處理前後之色差(△E)為△E≦2。

Description

仿皮革片及纖維構造體
本發明係關於經具有偶氮鍵的藍色陽離子染料所染色之仿皮革片及纖維構造體。
作為人工皮革等之仿皮革片中所包含的纖維構造體，從耐熱性或成形性優異之點來看，較佳使用聚酯纖維的不織布。以往，作為將聚酯纖維染色用的染料，從顯色性優異之點來看，廣泛使用分散染料。然而，分散染料有在熱或壓力、或者溶劑之存在下容易移染之問題。為了解決如此的問題，亦嘗試將已賦予對於陽離子染料的可染性之陽離子染料可染性聚酯纖維，以陽離子染料來染色。
例如，下述專利文獻1揭示一種經陽離子染料所染色的絨毛狀人工皮革，其包含具有0.07~0.9dtex的纖度之陽離子染料可染性聚酯纖維的不織布及被賦予至不織布之內部的高分子彈性體，該經陽離子染料所染色的絨毛狀人工皮革之L*值≦50，在荷重0.75kg/cm、50℃、16小時下的對於PVC的色移染性評價中之色差級數判定為4級以上，每厚度1mm的撕裂強度為30N以上，剝離強度為3kg/cm以上。
可是，於經陽離子染料中的藍色陽離子染料所染色的陽離子染料可染性纖維之纖維構造體有缺點。具體而言，藍色陽離子染料係難以顯色為鮮豔的藍色、或耐光堅牢度低，難以兼具鮮豔的藍色顯色與高耐光堅牢度。又，尤其纖度低的極細纖維若不大量吸盡藍色陽離子染料，則不顯色為鮮豔的藍色，且在此情況下有變得容易褪色之問題。
作為藍色陽離子染料，例如下述專利文獻2就染色芳香族聚醯胺纖維用的染料之一例而言，例示C.I.鹼性藍54當作偶氮系的藍色染料。
又，關於經陽離子染料所染色的纖維構造體，下述專利文獻3揭示一種經單寧酸系化合物所處理之全芳香族聚醯胺纖維構造物，其係經噻
Figure 107118219-A0202-12-0002-2
系藍色陽離子染料的C.I.鹼性藍9所染色。
先前技術文獻 專利文獻
專利文獻1 國際公開2016/147671號小冊
專利文獻2 日本特開2013-209776號公報
專利文獻3 日本特開2009-74197號公報
本發明者們已得知，於藍色陽離子染料之中，如C.I.鹼性藍54之具有偶氮鍵的藍色陽離子染料，係兼具鮮豔的藍色顯色性與耐光性之染料。然而，發覺 到具有偶氮鍵的藍色陽離子染料在高溫多濕的環境下係水解而變色，逐漸帶有紅色調之問題。因此，可認為例如在如高溫多濕的船之貨櫃運輸或倉庫等長期保管的狀況下，經含有具有偶氮鍵的藍色陽離子染料之染料所染色的纖維會變色。因此，發覺經含有具有偶氮鍵的藍色陽離子染料的染料所染色之仿皮革片或纖維構造體，雖然顯色性與耐光性優異，但在實用上必須改善耐濕熱變色性。
本發明之目的在於提供一種提高耐濕熱變色性之經具有偶氮鍵的藍色陽離子染料所染色之仿皮革片或纖維構造體。
本發明之一層面係一種仿皮革片，其包含纖維構造體及被賦予至纖維構造體的內部空隙之高分子彈性體，該纖維構造體包含經含有C.I.鹼性藍54等具有偶氮鍵的藍色陽離子染料之染料所染色的陽離子染料可染性纖維，且該仿皮革片進一步包含具有陰離子性的多元酚衍生物。此種經具有偶氮鍵的藍色陽離子染料所染色之仿皮革片係耐濕熱變色性優異。
又，作為具有偶氮鍵的藍色陽離子染料，C.I.鹼性藍54由於顯色性特別優異，從可得到兼具鮮豔的藍色顯色性、耐光性、耐濕熱變色性之仿皮革片之點來看較佳。
又，形成纖維構造體的纖維為如纖度0.05~1dtex的極細纖維時，從本發明的效果變得特別顯 著之點來看較佳。將纖維染色時，使用細的纖維之情況，由於纖維的總表面積比使用粗的纖維之情況大，若不使其吸盡更多的染料，則難以得到鮮豔的顯色。然而，於具有偶氮鍵的藍色陽離子染料之吸盡量多的情況，在濕熱條件下變得容易變色。因此，將細的纖維以具有偶氮鍵的藍色陽離子染料來染色之情況，相較於將粗的纖維染色之情況，在濕熱條件下變得容易顯著地變色。若依據本發明，則將如纖度0.05~1dtex的極細纖維以具有偶氮鍵的藍色陽離子染料來染色時，也顯示高耐濕熱變色性。又，作為纖維，從堅牢度、形態安定性特別優異之點來看，較佳為聚酯纖維。
又，從耐濕熱變色性特別優異之點來看，仿皮革片在80℃、濕度90%、48小時之條件下濕熱處理時，濕熱處理前後之色差(△E)較佳為△E≦2。
又，從本發明的效果變得特別顯著之點來看，仿皮革片較佳為具有在色座標空間(L*a*b*色空間)中L*≦35之表面。
又，仿皮革片較佳為表面經起毛處理的麂皮狀人工皮革。
又，本發明之另一層面為一種纖維構造體，其進一步包含：經含有具有偶氮鍵的藍色陽離子染料之染料所染色的纖維、及具有陰離子性的多元酚衍生物。
又，本發明之另一層面為一種仿皮革片，其包含纖維構造體及被賦予至纖維構造體的內部空隙之高分子彈性體，該纖維構造體包含經含有具有偶氮鍵的 藍色陽離子染料之染料所染色的纖維，且該仿皮革片在80℃、濕度90%、48小時之條件下濕熱處理時，濕熱處理前後之色差(△E)為△E≦2。
又，本發明之另一層面為一種纖維構造體，其係包含經含有具有偶氮鍵的藍色陽離子染料之染料所染色的聚酯纖維之纖維構造體，其在80℃、濕度90%、48小時之條件下濕熱處理時，濕熱處理前後之色差(△E)為△E≦2。
若依據本發明，可得到耐濕熱變色性優異之經具有偶氮鍵的藍色陽離子染料所染色的仿皮革片或纖維構造體。
用以實施發明的形態
以下，具體地說明本發明之合適的實施形態。
作為本實施形態所用之纖維構造體，可舉出包含陽離子可染性纖維的不織布、梭織物、針織物等。於此等之中，從可顯著得到本發明的效果之點來看，較佳為不織布，特佳為極細纖維的不織布。
作為陽離子染料可染性纖維，可舉出具有對陽離子染料中顯示易染性或可染性的陰離子性基之陽離子可染性聚酯纖維或聚醯胺纖維等。於此等之中，使 用陽離子可染性聚酯纖維作為人工皮革時，從堅牢度、形態安定性優異之點來看較佳。
作為陽離子可染性聚酯纖維之具體例，例如可舉出含有具有賦予陽離子可染性的陰離子性基之單體成分作為共聚合單元之聚酯纖維。作為賦予陽離子可染性用的單體成分之具體例，例如可舉出5-磺基間苯二甲酸的鹼金屬鹽(鋰鹽、鈉鹽、鉀鹽、銣鹽、銫鹽)、或磺基間苯二甲酸5-四丁基鏻、磺基間苯二甲酸5-乙基三丁基鏻等的磺基間苯二甲酸5-四烷基鏻、或磺基間苯二甲酸5-四丁基銨、磺基間苯二甲酸5-乙基三丁基銨等的磺基間苯二甲酸5-四烷基銨、或3,5-二羧基苯磺酸四烷基鏻鹽等。此等係可單獨使用，也可組合2種以上使用。
陽離子染料可染性纖維之纖度係沒有特別的限定，例如可為如超過1dtex的正規纖維，也可為如1dtex以下的極細纖維。從本發明之效果變得顯著之點來看，從著色成深色時的耐濕熱變色性之提高變得更顯著之點來看，較佳為0.05~1dtex，更佳為0.07~0.5dtex，特佳為0.1~0.4dtex。當纖維為細時，由於若沒有增多具有偶氮鍵的藍色陽離子染料之吸盡量，則變得難以充分地獲得藍色的顯色性，且當染料的吸盡量多時在濕熱環境下的變色容易變得顯著，而本發明之效果特別顯著。
又，於陽離子染料可染性纖維中，在不損害本發明的效果之範圍內，可視需要而摻合碳黑等的著色劑、耐光劑、防黴劑等。
作為本實施形態之仿皮革片，可舉出將高分子彈性體含浸賦予至上述纖維構造體的內部空隙而得之人工皮革或合成皮革等。
作為被含浸賦予至纖維構造體的內部空隙的高分子彈性體之具體例，例如可舉出聚胺甲酸酯、丙烯腈彈性體、烯烴彈性體、聚酯彈性體、聚醯胺彈性體、丙烯酸彈性體等。仿皮革片中所包含的高分子彈性體之比例係沒有特別的限定，但較佳為1~50質量%，更佳為5~30質量%左右。又，仿皮革片較佳為麂皮狀或牛巴戈(nubuck)狀的絨毛狀仿皮革片，該絨毛狀仿皮革片包含其表面的纖維藉由磨皮(buffing)處理等的起毛處理而起絨之纖維。
本實施形態之包含陽離子染料可染性纖維的仿皮革片或纖維構造體，係以含有具有偶氮鍵的藍色陽離子染料之染料而染色。具有偶氮鍵的藍色陽離子染料係藍色的顯色性與耐光性優異。
作為具有偶氮鍵的藍色陽離子染料之具體例，例如可舉出C.I.鹼性藍54或C.I.鹼性藍159等。另外，本實施形態中所謂的藍色陽離子染料，意指在顏色索引名稱(C.I.)中包含「鹼性藍」的藍色陽離子染料。於此等之中，從鮮豔的藍色顯色性優異之點來看，特佳為C.I.鹼性藍54。
於將本實施形態之仿皮革片或纖維構造體染色的染料中，除了具有偶氮鍵的藍色陽離子染料以外，亦可組合其它染料而摻合。作為具有偶氮鍵的藍色 陽離子染料以外之陽離子染料，例如可舉出C.I.鹼性藍3、C.I.鹼性藍6、C.I.鹼性藍10、C.I.鹼性藍12、C.I.鹼性藍75、C.I.鹼性藍96等之
Figure 107118219-A0202-12-0008-3
系藍色陽離子染料、或C.I.鹼性藍9等之噻
Figure 107118219-A0202-12-0008-4
系藍色陽離子染料、或C.I.鹼性黃40等之香豆素系染料、C.I.鹼性黃21等之次甲基系染料、C.I.鹼性黃28等之次甲基偶氮系染料、偶氮系紅色染料的C.I.鹼性紅29或C.I.鹼性紅46、
Figure 107118219-A0202-12-0008-5
系染料的C.I.鹼性紫11等。
染色方法係沒有特別的限定，例如可舉出使用噴射式染色機、經軸染色機、捲染機等的染色機進行染色之方法。作為染色加工之條件，可為在高壓下的染色，但本實施形態之纖維構造體由於可在常壓下染色，而在常壓下的染色從環境負荷低、可減低染色成本之點來看亦較佳。在常壓下染色時，作為染色溫度較佳為60~100℃，更佳為80~100℃。又，染色時，亦可使用如乙酸或芒硝的染色助劑。
使用陽離子染料進行染色時，染料液中的陽離子染料之濃度雖然亦取決於陽離子染料可染性纖維的纖度，但從顯色性與染料的耐移染性之平衡優異之點來看，相對於陽離子染料可染性纖維較佳為0.5~20%owf，特佳為1.0~15%owf。纖維所吸盡的陽離子染料之濃度過高時，未固定於染位而被吸盡的陽離子染料之量變多，有染料容易移染之傾向。又，染料中被吸盡的陽離子染料之濃度過低時，有變得難以顯色為深色之傾向。
又，於本實施形態中，較佳為藉由在含有陰離子系界面活性劑的熱水浴中，將經陽離子染料所染色的仿皮革片或纖維構造體進行洗淨處理，而去除結合力低的陽離子染料。藉由如此的洗淨處理，而充分地去除結合力低的陽離子染料，變得不易從經染色的仿皮革片或纖維構造體移染至其它物品。作為陰離子系界面活性劑之具體例，例如可舉出日成化成(股)製之Sordine R、SENKA(股)製之Senkanol A-900、明成化學工業(股)製之Meisanol KHM等。
在含有陰離子系界面活性劑的熱水浴中之洗淨處理，較佳在50~100℃、更佳在60~80℃的熱水浴中進行。又，作為洗淨時間，較佳為10~30分鐘左右，更佳為15~20分鐘左右。又，可將此洗淨重複1次以上，較佳為重複2次以上。
藉由對於經含有具有偶氮鍵的藍色陽離子染料的染料所染色之仿皮革片或纖維構造體，賦予具有陰離子性的多元酚衍生物，可提高耐濕熱變色性。作為如此之具有陰離子性的多元酚衍生物，可舉出作為經酸性染料所染色的尼龍纖維之濕潤堅牢度提高劑使用的具有磺酸基等陰離子性基之多元酚衍生物，更具體而言，可舉出芳香族衍生物磺化物的福馬林縮合物之明成化學工業(股)製的Dimafix。仿皮革片或纖維構造體之具有陰離子性的多元酚衍生物之含量係沒有特別的限定，但從充分改善耐濕熱變色性之點來看，相對於染料附著量較佳為70~200%左右。
又，於仿皮革片或纖維構造體中，視需要亦可摻合耐光劑。作為耐光劑之具體例，可舉出苯并***系耐光劑、三
Figure 107118219-A0202-12-0010-6
系耐光劑、二苯基酮系耐光劑等。此等係可單獨或組合2種以上使用。
本實施形態之經含有具有偶氮鍵的藍色陽離子染料之染料所染色的仿皮革片或纖維構造體，從本發明的效果變得特別顯著之點來看，較佳為染色成深色，具體而言，作為L*a*b*表色系統中的L*值，較佳為L*≦35，更佳為L*≦30。
如此地，得到本實施形態之經含有具有偶氮鍵的藍色陽離子染料之陽離子染料所染色的仿皮革片或纖維構造體。本實施形態之仿皮革片或纖維構造體例如在80℃、濕度90%、48小時之條件下濕熱處理時，較佳為具有如色差(△E)為△E≦2、更佳為△E≦1.4、特佳為△E≦1的高耐濕熱變色性。特別地，即使在使用如纖度0.05~1dtex的極細纖維之纖維構造體的情況，在80℃、濕度90%、48小時之條件下濕熱處理時，亦較佳為具有如色差(△E)為△E≦2、更佳為△E≦1.4、特佳為△E≦1之高耐濕熱變色性。
實施例
以下，藉由實施例，更具體地說明本發明。另外，本發明之範圍完全不受實施例所限定。首先，在以下彙總顯示實施例所用的各種染料。
(染料)
‧C.I.鹼性藍54：Nichilon Blue-GL(具有偶氮鍵的藍色陽離子染料)(日成化成(股)製)
‧C.I.鹼性藍159：Nichilon Blue-AZN(具有偶氮鍵的藍色陽離子染料)(日成化成(股)製)
‧C.I.鹼性藍3：Nichilon Blue-7G(
Figure 107118219-A0202-12-0011-7
系藍色陽離子染料)(日成化成(股)製)
‧C.I.鹼性藍75：Nichilon Blue-350(
Figure 107118219-A0202-12-0011-8
系藍色陽離子染料)(日成化成(股)製)
‧C.I.鹼性黃28：Nichilon Golden Yellow-GL(次甲基偶氮系黃色陽離子染料)(日成化成(股)製)
‧C.I.鹼性紅29：Nichilon Red-GL(偶氮系紅色陽離子染料)(日成化成(股)製)
[實施例1]
將自乳化型水系聚胺甲酸酯樹脂含浸至以陽離子染料可染性聚酯纖維作為島成分，且以水溶性聚乙烯醇作為海成分的海島型複合纖維之不織布後，藉由萃取海成分，而得到人工皮革坯布，其包含平均纖度0.2dtex的陽離子染料可染性聚酯纖維之不織布，且聚胺甲酸酯比率為10質量%。然後，藉由切割人工皮革坯布，將處理表面進行磨皮處理，而整理加工成厚度0.78mm、表觀密度0.49g/cm3。
然後，如表1所示，將人工皮革坯布以包含Nichilon Blue-GL 4%owf、Nichilon Golden Yellow-GL 2%owf、Nichilon Red-GL 2%owf之染料液，在120℃×40分鐘之條件下染色。然後，藉由使用2g/L的Sordine R溶液，於70℃×20分鐘之條件下進行2次皂洗，而得到著色成藏青色的人工皮革。
然後，將具有陰離子性的多元酚衍生物(明成化學工業(股)製：Dimafix ESH，芳香族衍生物磺化物的福馬林縮合物)在浴比1：20、80℃×30分鐘之條件下賦予6%owf至經染色的人工皮革，進行乾燥。如此地，得到經賦予具有陰離子性的多元酚衍生物之麂皮狀人工皮革。
然後，如以下地評價麂皮狀人工皮革之色座標、耐濕熱變色性及耐光性。
(色座標)
使用分光光度計(MINOLTA公司製：CM-3700)，色度測量麂皮狀人工皮革的麂皮狀表面之L*a*b*表色系統的座標值。值係從試驗片中到處選擇平均的位置，作為所測定的3點之平均值而算出。
(耐濕熱變色性)
將麂皮狀人工皮革進行在80℃×90%的濕熱條件下放置48小時的處理後，進行風乾。然後，色度測量濕熱處理後的麂皮狀表面之色座標。然後，求出麂皮狀表面之濕熱處理前的色座標與濕熱處理後的色座標之色差△E及△a*、△b*、△L*。
(耐光性)
使用Q-PANEL公司製加速耐光試驗機QUV/se(45℃，照度0.78W/m2)，對於麂皮狀人工皮革進行24小時UV照射。然後，測定24小時UV照射後的麂皮狀表面之色座標。然後，將24小時UV照射前後的麂皮狀表面之褪色，使用DATACOLOR公司製的型號600，以G37 UV Color Change模式進行級數判定。
下述表1中顯示結果。
Figure 107118219-A0202-12-0014-1
[實施例2]
除了於實施例1中，將陰離子性多元酚衍生物賦予12%owf代替賦予6%owf以外，同樣地得到麂皮狀人工皮革，進行評價。表1中顯示結果。
[實施例3]
除了於實施例1，將陰離子性的多元酚衍生物賦予3%owf代替賦予6%owf以外，同樣地得到麂皮狀人工皮革，進行評價。表1中顯示結果。
[實施例4]
除了如表1所示，以僅包含Nichilon Blue-GL 4%owf之染料液染色成寶藍色以外，與實施例1同樣地得到麂皮狀人工皮革，進行評價。表1中顯示結果。
[實施例5]
除了如表1所示，以僅包含Nichilon Blue-AZN 4%owf之染料液染色成帶黃色的藍色以外，與實施例1同樣地得到麂皮狀人工皮革，進行評價。表1中顯示結果。
[比較例1]
除了於實施例1中，省略賦予陰離子性的多元酚衍生物之步驟以外，同樣地得到麂皮狀人工皮革，進行評價。表1中顯示結果。
[比較例2]
除了於實施例4中，省略賦予陰離子性的多元酚衍生物之步驟以外，同樣地得到麂皮狀人工皮革，進行評價。表1中顯示結果。
[比較例3]
除了於實施例5中，省略賦予陰離子性的多元酚衍生物之步驟以外，同樣地得到麂皮狀人工皮革，進行評價。表1中顯示結果。
[比較例4]
除了如表1所示，以包含Nichilon Blue-7G 4%owf之染料液染色，進一步省略賦予陰離子性的多元酚衍生物之步驟以外，與實施例1同樣地得到麂皮狀人工皮革，進行評價。表1中顯示結果。
[比較例5]
除了如表1所示，以包含Nichilon Blue-350 4%owf之染料液染色，進一步省略賦予陰離子性的多元酚衍生物之步驟以外，與實施例1同樣地得到麂皮狀人工皮革，進行評價。表1中顯示結果。
若參照表1，則於以包含為具有偶氮鍵的藍色陽離子染料的C.I.鹼性藍54之染料染色成藏青色的人工皮革中，賦予有具有陰離子性的多元酚衍生物之實 施例1~3的人工皮革之濕熱處理後之色差△E為0.8~1.4，相較於未賦予具有陰離子性的多元酚衍生物之比較例1的人工皮革之濕熱處理後之色差△E=2.9，耐濕熱變色性顯著較高。同樣地，於以包含C.I.鹼性藍54之染料染色成寶藍色的人工皮革中，賦予有具有陰離子性的多元酚衍生物之實施例4的人工皮革之濕熱處理後之色差△E為0.8，相較於未賦予具有陰離子性的多元酚衍生物之比較例2的人工皮革之濕熱處理後之色差△E=1.5，耐濕熱變色性顯著較高。
又，於以包含為具有偶氮鍵的藍色陽離子染料的C.I.鹼性藍159之染料染色成L*=37之帶黃色的藍色之人工皮革中，賦予有具有陰離子性的多元酚衍生物之實施例5的人工皮革之濕熱處理後之色差△E為0.5，相較於未賦予具有陰離子性的多元酚衍生物之比較例3的人工皮革之濕熱處理後之色差△E=0.8，耐濕熱變色性較高。
又，以包含為
Figure 107118219-A0202-12-0017-9
系藍色陽離子染料的C.I.鹼性藍3之染料染色成L*=37的翡翠綠色之比較例4的人工皮革係耐光性低。又，以包含C.I.鹼性藍75之染料染色成L*=52的土耳其藍色之比較例5的人工皮革並未顯色為深色的藍色。

Claims (10)

  1. 一種仿皮革片，其包含纖維構造體及被賦予至該纖維構造體的內部空隙之高分子彈性體，該纖維構造體包含經含有具有偶氮鍵的藍色陽離子染料之染料所染色的聚酯纖維，且該仿皮革片進一步包含具有磺酸基的多元酚衍生物。
  2. 如請求項1之仿皮革片，其中該具有偶氮鍵的藍色陽離子染料包含C.I.鹼性藍54。
  3. 如請求項1之仿皮革片，其中該纖維為纖度0.05~1dtex。
  4. 如請求項1之仿皮革片，其在80℃、濕度90%、48小時之條件下濕熱處理時，濕熱處理前後之色差(△E)為△E≦2。
  5. 如請求項1之仿皮革片，其具有在色座標空間(L*a*b*色空間)中L*≦35之表面。
  6. 如請求項1之仿皮革片，其係表面經起毛處理的麂皮狀人工皮革。
  7. 一種纖維構造體，其特徵係包含：經含有具有偶氮鍵的藍色陽離子染料之染料所染色的聚酯纖維、及具有磺酸基的多元酚衍生物。
  8. 如請求項7之纖維構造體，其中該具有偶氮鍵的藍色陽離子染料包含C.I.鹼性藍54。
  9. 如請求項7之纖維構造體，其中該纖維具有0.05~1dtex的纖度。
  10. 如請求項7之纖維構造體，其具有在80℃、濕度90%之條件下48小時濕熱處理時之色差(△E)為△E≦2之表面。
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