TW201542366A - 複合體及其製造方法 - Google Patents
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Abstract
本發明的課題為提供一種複合體,其片層與硬化性樹脂層或膜層的密合性高,且強度高,為高透明。本發明提供的複合體於含有平均纖維寬度為2nm~1000nm的微細纖維的片層的單面或兩面,隔著被覆層而積層有硬化性樹脂層或膜層。
Description
本發明是有關於一種複合體及其製造方法,所述複合體為:於以微細纖維作為主成分的片層的單面或兩面具有硬化性樹脂層或膜層的複合體;於以微細纖維作為主成分的片層(不織布層)的單面或兩面,隔著被覆層(易黏接性層)而積層有硬化性樹脂層或膜層的複合體(不織布樹脂複合體)(以下稱為「複合體」);於以微細纖維作為主成分的片層的單面或兩面積層有被覆層的複合體(以下稱為「貼合用片」)及其製造方法。本發明進而有關於一種包含所述複合體的照明裝置、投影裝置、招牌或圖像顯示裝置、觸控面板或者太陽電池。
近年來,由於石油資源的代替以及環境意識的提高而關注可再生產的天然纖維的應用。天然纖維中纖維素纖維、特別是源自木材的纖維素纖維(紙漿)主要作為紙製品而廣泛使用。紙中使用的纖維素纖維的寬度在大部分的情況下為10μm~50μm。由此種纖維素纖維所獲得的紙(片)不透明,作為印刷用紙而廣泛利用。另一方面,若利用精磨機(refiner)或捏合機(kneader)、砂磨機(sand grinder)等對纖維素纖維進行處理(打漿(beating)、
粉碎),使纖維素纖維微細化(微原纖化(microfibrillating)),則獲得透明紙(玻璃紙(glassine paper)等)。另外,先前包含纖維素纖維的不織布添加上漿劑(sizing agent)或紙力增強劑(paper strengthening agent)等,作為紙而用於印刷用紙或書籍等。進而,正在研究利用對於氣體或液體等的透過性,將包含纖維素纖維的不織布用於過濾器、蓄電元件、電池或者電容器的隔膜等。
專利文獻1中揭示有一種複合體,其特徵在於:包含含有纖維素的不織布(a)及纖維素以外的樹脂(b),且(a)成分為0.1重量%以上、99重量%以下,(b)成分為1重量%以上、99.9重量%以下。專利文獻1中,含有纖維素的不織布(a)的空孔是由纖維素以外的樹脂(b)來填充。
專利文獻2中記載有一種帶有硬塗層的塑膠膜,其於透明塑膠膜上積層有底塗層及硬塗層。構成硬塗層的樹脂為含有5官能以上的(甲基)丙烯酸酯、單官能的(甲基)丙烯酸酯以及光聚合起始劑作為必需成分的樹脂組成物的硬化物。專利文獻2中使用的透明塑膠為聚酯膜,特別是聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)膜。
專利文獻3中記載有將平均纖維徑為0.1μm~20μm的纖維素纖維與平均纖維徑為小於100nm的纖維素奈米纖維進行製紙而成的不織布、以及包含該不織布的蓄電池元件用隔膜。
[現有技術文獻]
[專利文獻]
[專利文獻1]日本專利特開2006-316253號公報
[專利文獻2]日本專利特開平9-300549號公報
[專利文獻3]日本專利特開2012-36517號公報
本發明的課題在於可解決如下問題:提供一種樹脂層的密合性高、且為高透明的不織布與樹脂的複合體。
另外,本發明的課題在於可解決如下問題:提供高強度且透明性高的複合體,另外,以微細纖維素纖維作為主成分的片(片層)、與硬化性樹脂層或膜層的密合性高的複合體,以微細纖維素纖維作為主成分的片(片層)、與被覆層的密合性高的貼合用片。
本發明者們為了解決所述課題而進行積極研究。其結果為發現:藉由在含有平均纖維寬度為2nm~1000nm的微細纖維的不織布層的單面或兩面,隔著易黏接性層來積層樹脂層,可提供樹脂層的密合性高、且為高透明的不織布樹脂複合體,從而完成本發明。
詳細而言,本發明者們為了解決所述課題而進行積極研究。其結果為發現:1)於以平均纖維寬度為2nm~1000nm的微細纖維作為主成分的片(以下稱為「片層」)的單面或兩面積層有硬化性樹脂層或膜層的複合體為高強度且高透明。另外發現,2)於以平均纖維寬度為2nm~1000nm的微細纖維作為主成分的片層的
單面或兩面,隔著被覆層而積層有硬化性樹脂層或膜層的複合體,3)於以平均纖維寬度為2nm~1000nm的微細纖維作為主成分的片層的單面或兩面積層有被覆層的貼合用片的各層間的密合性高、高強度且高透明,從而完成本發明。
即,依據本發明來提供以下的發明。
(1)一種複合體,其於以平均纖維寬度為2nm~1000nm的微細纖維作為主成分的片層的單面或兩面具有硬化性樹脂層或膜層。
(2)如(1)所述的複合體,其中微細纖維的平均纖維寬度為2nm~100nm。
(3)如(1)或(2)所述的複合體,其中片層的密度為0.90g/cm3以上。
(4)如(1)至(3)中任一項所述的複合體,其中片層為不織布。
(5)如(1)至(4)中任一項所述的複合體,其中微細纖維為包含纖維素纖維的纖維。
(6)如(1)至(5)中任一項所述的複合體,其中隔著設置於片層的單面或兩面的被覆層而積層硬化性樹脂層或膜層。
(7)如(6)所述的複合體,其中片層的厚度為2μm~150μm,被覆層的厚度為0.1μm~30μm,硬化性樹脂層或膜層的厚度為0.2μm~100μm。
(8)如(6)或(7)所述的複合體,其中片層、與硬化性樹
脂層或膜層的密合性於依據JIS標準K5400的劃格試驗中,100塊中的剝離數為10以下。
(9)如(6)至(8)中任一項所述的複合體,其中全光線透過率為85%以上,霧度為10%以下。
(10)如(6)至(9)中任一項所述的複合體,其中被覆層為有機成分與無機成分的混成材。
(11)如(10)所述的複合體,其中有機成分與無機成分的混成材包含具有矽骨架的有機成分及無機成分。
(12)如(10)或(11)所述的複合體,其中有機成分為包含選自甲基、巰基、甲基丙烯酸基、丙烯醯基、乙烯基及胺基中的至少一種的成分。
(13)如(10)至(12)中任一項所述的複合體,其中有機成分與無機成分的混成材為倍半矽氧烷。
(14)如(6)至(9)中任一項所述的複合體,其中被覆層為選自熱硬化性樹脂、熱塑性樹脂、以及光硬化性樹脂中的至少一種。
(15)如(6)至(9)中任一項所述的複合體,其中被覆層為黏著劑。
(16)一種貼合用片,其於以平均纖維寬度為2nm~1000nm的纖維素微細纖維作為主成分的片層的單面或兩面具有被覆層。
(17)如(16)所述的片,其中被覆層為有機成分與無機成分的混成材。
(18)如(17)所述的片,其中有機成分為包含選自甲基、巰基、甲基丙烯酸基、丙烯醯基、乙烯基及胺基中的至少一種的成分。
(19)如(17)或(18)所述的片,其中有機成分與無機成分的混成材為倍半矽氧烷。
(20)一種複合體,其於如(16)~(19)的片上積層有硬化性樹脂層或膜層。
(21)一種複合體的製造方法,其包括:於以平均纖維寬度為2nm~1000nm的微細纖維作為主成分的片層的單面或兩面設置被覆層的步驟;以及於所述被覆層的與片層相反之側的表面上設置硬化性樹脂層或膜層的步驟。
(22)如(21)所述的複合體的製造方法,其中片層與被覆層藉由塗覆、或者貼合而積層。
(23)如(21)所述的複合體的製造方法,其中被覆層、與硬化性樹脂層或膜層藉由塗覆、或者貼合而積層。
(24)一種照明裝置、投影裝置、招牌或圖像顯示裝置、觸控面板或者太陽電池,其包含如(1)至(20)中任一項所述的複合體。
[1]一種不織布樹脂複合體,其於不織布層的單面或兩面,隔著易黏接性層而積層有樹脂層,所述不織布層含有藉由對纖維原料進行化學性處理及原纖化處理而獲得的平均纖維寬度為2nm~1000nm的微細纖維。
[2]如[1]所述的不織布樹脂複合體,其中微細纖維的平均纖維寬度為2nm~100nm。
[3]如[1]或[2]所述的不織布樹脂複合體,其中不織布層的密度為0.90g/cm3以上。
[4]如[1]至[3]中任一項所述的不織布樹脂複合體,其中不織布層的厚度為2μm~150μm,易黏接性層的厚度為0.1μm~30μm,樹脂層的厚度為0.2μm~50μm。
[5]如[1]至[4]中任一項所述的不織布樹脂複合體,其中樹脂層的密合性於依據JIS標準K5400的劃格試驗中,100塊中的剝離數為10以下。
[6]如[1]至[5]中任一項所述的不織布樹脂複合體,其中全光線透過率為85%以上,霧度為10%以下。
[7]如[1]至[6]中任一項所述的不織布樹脂複合體,其中易黏接性層包含樹脂。
[8]如[1]至[7]中任一項所述的不織布樹脂複合體,其中易黏接性層包含聚酯樹脂或者倍半矽氧烷系樹脂。
[9]如[1]至[8]中任一項所述的不織布樹脂複合體,其中樹脂層為藉由利用紫外線處理或者熱處理,將硬化性樹脂前驅物進行硬化而獲得的樹脂層。
[10]如[1]至[9]中任一項所述的不織布樹脂複合體,其中微細纖維為包含纖維素纖維的纖維。
[11]一種製造如[1]至[10]中任一項所述的不織布樹脂複合體
的方法,其包括:於不織布層的單面或兩面設置易黏接性層的步驟。所述不織布層含有藉由對纖維原料進行化學性處理及原纖化處理而獲得的平均纖維寬度為2nm~1000nm的微細纖維;以及於所述易黏接性層的與不織布層相反之側的表面上設置樹脂層的步驟。
[12]一種照明裝置、投影裝置、招牌或圖像顯示裝置、觸控面板或者太陽電池,其包含如[1]至[10]中任一項所述的不織布樹脂複合體。
依據本發明,提供一種樹脂層的密合性高、且為高透明的不織布與樹脂的複合體。更詳細而言,依據本發明,提供:1)高強度且高透明的複合體;2)片層、與硬化性樹脂層或膜層的密合性高、高強度且高透明的複合體;3)片層與被覆層的密合性高、高強度且高透明的貼合用片。
1‧‧‧片層
2‧‧‧被覆層
3‧‧‧硬化性樹脂層或膜層
圖1表示硬化性樹脂層或膜層隔著被覆層而積層於片層的單面的複合體。
圖2表示硬化性樹脂層或膜層隔著被覆層而積層於片層的兩面的複合體。
以下,對本發明進一步進行詳細說明。此外,本說明書中記載的材料、方法及數值範圍等的說明並不意圖限定於該材料、方法及數值範圍等,另外,亦不排除其以外的材料、方法及數值範圍等的使用。數值範圍「x~y」包含兩端的值x及y。所謂主成分是指以質量為基準而含量最多的成分。
本發明的不織布樹脂複合體的特徵在於:於不織布層的單面或兩面,隔著易黏接性層而積層有樹脂層,所述不織布層含有藉由對纖維原料進行化學性處理及原纖化處理而獲得的平均纖維寬度為2nm~1000nm的微細纖維。即,本發明的不織布樹脂複合體為至少包含不織布層、易黏接性層及樹脂層的積層體。更詳細而言,本發明的複合體的特徵在於為:1)於以平均纖維寬度為2nm~1000nm的微細纖維作為主成分的片層的單面或兩面積層有硬化性樹脂層或膜層的複合體;2)於以平均纖維寬度為2nm~1000nm的微細纖維作為主成分的片層的單面或兩面,隔著被覆層而積層有硬化性樹脂層或膜層的複合體;3)於以平均纖維寬度為2nm~1000nm的微細纖維作為主成分的片層的單面或兩面積層有被覆層的貼合用片。即,本發明的複合體為:1)包括片層、及硬化性樹脂層或膜層的2層的複合體;2)包括片層、被覆層、及硬化性樹脂層或膜層的3層的複合體;3)包括片層及被覆層的2層的貼合用片。
硬化性樹脂層或膜層可積層於片層的單面或兩面。圖1表示硬化性樹脂層或膜層隔著被覆層而積層於片層的單面的情
況。圖2表示硬化性樹脂層或膜層隔著被覆層而積層於片層的兩面的情況。
[片層(不織布層)]
本發明的片層是以平均纖維寬度為2nm~1000nm的微細纖維作為主成分。微細纖維只要是平均纖維寬度為2nm~1000nm的微細纖維,則其種類並無特別限定,可為微細纖維素纖維,亦可為微細纖維素纖維以外的微細纖維,亦可為微細纖維素纖維、與微細纖維素纖維以外的微細纖維的混合物。微細纖維較佳為纖維素纖維。
後文對微細纖維素纖維的詳情進行說明。微細纖維素纖維以外的纖維例如可列舉:無機纖維、有機纖維、合成纖維等、半合成纖維、再生纖維,並無特別限定。無機纖維例如可列舉:玻璃纖維、岩右纖維(rock fiber)、金屬纖維等,但並不限定於該些纖維。有機纖維例如可列舉:碳纖維、幾丁質(chitin)、幾丁聚糖(chitosan)等源自天然物的纖維等,但並不限定於該些纖維。合成纖維例如可列舉:尼龍、維尼綸(vinylon)、亞乙烯基(vinylidene)、聚酯、聚烯烴(例如聚乙烯、聚丙烯等)、聚胺基甲酸酯、丙烯酸、聚氯乙烯、芳族聚醯胺等,但並不限定於該些纖維。半合成纖維可列舉:乙酸酯、三乙酸酯、普羅米克斯(Promix)等,但並不限定於該些纖維。再生纖維例如可列舉:嫘縈(rayon)、銅銨嫘縈(cuprammonium rayon)、高濕模數嫘縈(polynosic rayon)、萊賽爾(Lyocell)、天絲(Tencel)等,但並不限定於該
些纖維。於將微細纖維素纖維與微細纖維素纖維以外的微細纖維混合使用的情況下,微細纖維素纖維以外的微細纖維可視需要而實施化學性處理、原纖化處理等處理。微細纖維素纖維以外的微細纖維可與微細纖維素纖維進行混合後實施化學性處理、原纖化處理等處理,亦可對微細纖維素纖維以外的微細纖維進行化學性處理、原纖化處理等處理後與微細纖維素纖維混合。於混合微細纖維素纖維以外的微細纖維的情況下,微細纖維素纖維與微細纖維素纖維以外的微細纖維的合計量中的微細纖維素纖維以外的微細纖維的添加量並無特別限定,較佳為50質量%以下。所述微細纖維素纖維以外的微細纖維的添加量更佳為40質量%以下,尤佳為30質量%以下,特佳為20質量%以下。
<微細纖維素纖維>
本發明中,亦可使用藉由對纖維素原料進行化學性處理及原纖化處理而獲得的微細纖維素纖維作為微細纖維。
纖維素原料可列舉:製紙用紙漿,棉絨(cotton linter)或皮棉(cotton lint)等棉系紙漿,麻、麥稈、蔗渣(bagasse)等非木材系紙漿,自海鞘(sea squirt)或海草等中分離出的纖維素等,並無特別限定。該些纖維素原料中,就獲取的容易度的方面而言,較佳為製紙用紙漿,並無特別限定。製紙用紙漿可列舉:化學紙漿(chemical pulp)、半化學紙漿(semichemical pulp)、機械紙漿(mechanical pulp)、非木材紙漿、以及脫墨紙漿(deinked pulp),並無特別限定。化學紙漿可列舉:闊葉樹牛皮紙漿(hardwood kraft
pulp)、針葉樹牛皮紙漿(softwood kraft pulp)、亞硫酸鹽紙漿(sulfite pulp,SP)、鈉鹼紙漿(soda pulp,AP)等。此處,闊葉樹牛皮紙漿可列舉:漂白牛皮紙漿(bleached Kraft Pulp)(闊葉樹漂白牛皮紙漿(Laubholz Bleached Kraft Pulp,LBKP))、未漂白牛皮紙漿(unbleached Kraft Pulp)(闊葉樹未漂白牛皮紙漿(laubholz unbleached kraft pulp,LUKP))、氧漂白牛皮紙漿(oxygen bleached kraft pulp)(闊葉樹氧漂白牛皮紙漿(hardwood oxygen-bleached kraft pulp,LOKP))等。另外,針葉樹牛皮紙漿可列舉:漂白牛皮紙漿(針葉樹漂白牛皮紙漿(needle bleached kraft pulp,NBKP))、未漂白牛皮紙漿(針葉樹未漂白牛皮紙漿(needle unbleached kraft pulp,NUKP))、氧漂白牛皮紙漿(針葉樹氧漂白牛皮紙漿(needle oxygen-bleached kraft pulp,NOKP))等。半化學紙漿可列舉:半化學紙漿(semichemical pulp,SCP)、化學磨木漿(chemi-ground wood pulp,CGP)等。機械紙漿可列舉:磨木漿(ground wood pulp,GP)、熱機械漿(熱機械漿(thermo-mechanical pulp,TMP)、漂白化學熱機械漿(bleached chemi-thermo-mechanical pulp,BCTMP))等。非木材紙漿可列舉以楮(paper mulberry)、三椏(paper bush)、麻、洋麻(kenaf)等作為原料的非木材紙漿。脫墨紙漿可列舉以廢紙作為原料的脫墨紙漿。該些紙漿中,就更容易獲取的方面而言,較佳為牛皮紙漿、脫墨紙漿、亞硫酸鹽紙漿,並無特別限定。纖維素原料可單獨使用一種,亦可將兩種以上混合使用。
微細纖維素纖維的(數量平均)纖維寬度為2nm~1000nm,更佳為數量平均纖維寬度為2nm~100nm。微細纖維素纖維亦可為較通常於製紙用途中使用的紙漿纖維細得多的纖維素纖維或者棒狀粒子。微細纖維素纖維為包含結晶部分的纖維素分子的聚集體,其結晶結構為I型(平行鏈)。微細纖維素纖維的數量平均纖維寬度可利用電子顯微鏡觀察來測定。若微細纖維素纖維的平均纖維寬度小於2nm,則作為纖維素分子而溶解於水中,因此變得不再表現出作為微細纖維素纖維的物性(強度或剛性、尺寸穩定性)。此處,微細纖維素纖維取得I型結晶結構的情況,可根據如下情況來鑑定:於繞射分佈(diffraction profile)中,於2θ=14°~17°附近及2θ=22°~23°附近的兩處位置具有典型的峰值。此處所謂的繞射分佈是根據使用以石墨而單色化的CuKα(λ=1.5418Ǻ)的廣角X射線繞射照片來獲得的繞射分佈。另外,以如下方式藉由電子顯微鏡觀察來測定微細纖維素纖維的纖維寬度測定。製備濃度為0.05質量%~0.1質量%的微細纖維素纖維的水系懸浮液,將該懸浮液流延於經親水化處理的碳膜被覆柵格上,作為穿透式電子顯微鏡(Transmission Electron Microscope,TEM)觀察用試樣。於包含寬度廣的纖維的情況下,亦可對流延於玻璃上的表面的掃描式電子顯微鏡(scanning electron microscope,SEM)像進行觀察。根據所構成的纖維的寬度,以1000倍、5000倍、10000倍或者50000倍的任一倍率來進行電子顯微鏡圖像的觀察。其中,試樣、觀察條件或倍率是以滿足下述條件的方式進行調整。
(1)於觀察圖像內的任意部位引一根直線X,相對於該直線X,20根以上的纖維交叉。
(2)於相同圖像內引與該直線垂直交叉的直線Y,相對於該直線Y,20根以上的纖維交叉。
對於滿足所述條件的觀察圖像,以目視來讀取與直線X、直線Y交錯的纖維的寬度。如此,至少觀察到三組以上不重疊的表面部分的圖像,對於各個圖像,讀取與直線X、直線Y交錯的纖維的寬度。以所述方式讀取至少20根×2×3=120根的纖維寬度。微細纖維素纖維的平均纖維寬度是以如上所述的方式讀取的纖維寬度的平均值。
微細纖維素纖維的纖維長並無特別限定,較佳為1μm~1000μm,尤佳為5μm~800μm,特佳為10μm~600μm。若纖維長小於1μm,則難以形成微細纖維片。若超出1000μm,則微細纖維的漿料黏度變得非常高,難以操作。纖維長可根據藉由TEM、SEM、原子力顯微鏡(atomic force microscope,AFM)的圖像分析來求出。
<化學性處理>
纖維素原料或者其他纖維原料(無機纖維、有機纖維、合成纖維等、半合成纖維、再生纖維等)的化學性處理的方法只要是可獲得微細纖維的方法,則並無特別限定。處理的方法可列舉例如臭氧處理、2,2,6,6-四甲基哌啶-1-氧基(2,2,6,6-tetramethylpiperidine-1-oxyl,TEMPO)氧化處理、酵素
處理、或者利用可與纖維素或纖維原料中的官能基形成共價鍵的化合物進行的處理等,但並不限定於該些處理。
臭氧處理的一例可列舉日本專利特開2010-254726號公報中記載的方法,並無特別限定。具體而言,將纖維進行臭氧處理後,分散於水中,對所得的纖維的水系分散液進行粉碎處理。
TEMPO氧化處理的一例可列舉「生物巨分子(Biomacromolecules)8」第2485頁~第2491頁2007年(齋藤(Saito)等人)中記載的方法,並無特別限定。
酵素處理的一例可列舉國際公開WO2013/176033(WO2013/176033的內容全部引用於本說明書中)中記載的方法,並無特別限定。具體而言為:至少於酵素的內葡聚醣酶(endoglucanase,EG)活性與纖維二糖水解酶I(cellobiohydrolase I,CBHI)活性的比為0.06以上的條件下,利用酵素對纖維原料進行處理的方法。
利用可與纖維素或纖維原料中的官能基形成共價鍵的化合物來進行的處理可列舉以下方法,並無特別限定。
(1)利用日本專利特開2011-162608中記載的具有四級銨基的化合物來進行的處理;(2)使用日本專利特開2013-136859(日本專利特開2013-136859的內容全部引用於本說明書中)中記載的羧酸系化合物的方法;以及(3)使用國際公開WO2013/73652(WO2013/73652的內容全
部引用於本說明書中)中記載的「選自結構中含有磷原子的含氧酸、聚含氧酸或者它們的鹽中的至少一種化合物」的方法:利用日本專利特開2011-162608號公報中記載的具有四級銨基的化合物來進行的處理是使纖維中的羥基與具有四級銨基的陽離子化劑進行反應,將該纖維進行陽離子改質的方法。
使用日本專利特開2013-136859中記載的羧酸系化合物的方法可以如下方式進行。藉由選自由具有兩個以上羧基的化合物、具有兩個以上羧基的化合物的酸酐、以及它們的衍生物所組成的組群中的至少一種羧酸系化合物,對纖維原料進行處理,於纖維原料中導入羧基。繼而,利用鹼溶液對導入有羧基的纖維原料進行處理。
利用國際公開WO2013/73652中記載的選自結構中含有磷原子的含氧酸、聚含氧酸或者它們的鹽中的至少一種化合物(以下稱為化合物A)來對纖維原料進行處理的方法可利用以下方法來進行。即,於纖維原料中混合化合物A的粉末或水溶液的方法、或者於纖維原料的漿料中添加化合物A的水溶液的方法等。化合物A可列舉:磷酸、多磷酸、亞磷酸、膦酸、多膦酸或者它們的酯,並無特別限定。另外,該些化合物亦可為鹽的形式。具有磷酸基的化合物可列舉:磷酸、磷酸的鈉鹽、磷酸的鉀鹽、磷酸的銨鹽等,並無特別限定。磷酸的鈉鹽可列舉:磷酸二氫鈉、磷酸氫二鈉、磷酸三鈉、焦磷酸鈉及偏磷酸鈉等。磷酸的鉀鹽可列舉:磷酸二氫鉀、磷酸氫二鉀、磷酸三鉀、焦磷酸鉀及偏磷酸鉀等。
磷酸的銨鹽可列舉:磷酸二氫銨、磷酸氫二銨、磷酸三銨、焦磷酸銨、偏磷酸銨等。
<原纖化處理>
纖維素原料或者其他纖維原料(無機纖維、有機纖維、合成纖維等、半合成纖維、再生纖維等)可藉由進行原纖化處理而微細化,獲得數量平均纖維寬度為2nm~1000nm的微細纖維。原纖化處理步驟中,可使用原纖化處理裝置,對所述化學性處理中獲得的原料進行原纖化處理而獲得微細纖維分散液。
原纖化處理裝置可適當使用進行濕式粉碎的裝置等。例如為:研磨機(石臼型粉碎機)、高壓均質機、超高壓均質機、高壓碰撞型粉碎機、球磨機、圓盤型精磨機(disk refiner)、錐形精磨機(conical refiner)、雙軸混練機、振動磨機(vibration mill)、高速旋轉下的均質混合機(homomixer)、超音波分散機、打漿機(beater)等。但,原纖化處理裝置並不限定於所述裝置。
本發明的片層是以微細纖維作為主成分。片層中使用的片例如可無特別限定地使用不織布、織布、紙、膜等。相對於片層的乾燥重量,片層中所含的微細纖維的含量較佳為50質量%以上,尤佳為60質量%以上,更佳為70質量%以上,特佳為80質量%以上。片層的微細纖維的含量越高,可獲得強度越高的片。
<片層的物性>
本發明中的片層的密度並無特別限定,較佳為0.90g/cm3以上,更佳為1.00g/cm3以上,尤佳為1.10g/cm3以上。片層的密度
的上限並無特別限定,通常為1.60g/cm3以下。
本發明中的片層的厚度並無特別限定,通常為1μm~300μm左右,較佳為2μm~150μm,更佳為5μm~100μm,尤佳為5μm~50μm。
此外,片層亦可為視目的而積層有多層片層者。於使用多層片層的情況下,多層片層的合計厚度以及合計密度較佳為在所述範圍內。
[片層的形成]
形成片層時,製備包含微細纖維的懸浮液。該懸浮液中亦可添加親水性高分子。親水性高分子例如可列舉:聚乙二醇、纖維素衍生物(羥基乙基纖維素、羧基乙基纖維素、羧基甲基纖維素等)、酪蛋白(casein)、糊精(dextrin)、澱粉、改質澱粉、聚乙烯醇、改質聚乙烯醇(乙醯乙醯基化聚乙烯醇等)、聚環氧乙烷、聚乙烯基吡咯啶酮、聚乙烯基甲醚、聚丙烯酸鹽類、聚丙烯醯胺、丙烯酸烷基酯共聚物、胺基甲酸酯系共聚物等,並無特別限定。
另外,亦可代替親水性高分子而使用親水性的低分子化合物。親水性的低分子化合物可列舉:甘油(glycerine)、丁四醇(erythritol)、木糖醇(xylitol)、山梨糖醇(sorbitol)、半乳糖醇(galactitol)、甘露糖醇(mannitol)、乙二醇、二乙二醇、丙二醇、二丙二醇、丁二醇等,並無特別限定。相對於微細纖維的固體成分100質量份,於添加親水性高分子、或者親水性的低分子化合物的情況下的添加量較佳為1質量份至200質量份,更佳為1質
量份至150質量份,尤佳為2質量份至120質量份,特佳為3質量份至100質量份,並無特別限定。
塗覆於基材上的含有微細纖維的懸浮液為包含微細纖維及分散介質的液體。分散介質可使用水、有機溶劑,就操作性或成本的方面而言,較佳為僅使用水,但並未特別限定。於使用有機溶劑的情況下,亦較佳為與水併用,但並未特別限定。與水併用的有機溶劑較佳為醇系溶劑、酮系溶劑、醚系溶劑、乙酸酯系溶劑等極性溶劑,但並不特別限定於該些溶劑。醇系溶劑可列舉甲醇、乙醇、丙醇、丁醇等。酮系溶劑可列舉丙酮、甲基乙基酮等。醚系溶劑可列舉二乙醚、乙二醇二甲醚、四氫呋喃等。乙酸酯系溶劑可列舉乙酸乙酯等。
懸浮液中所含的微細纖維的固體成分濃度並無特別限定,較佳為0.1質量%~20質量%,更佳為0.1質量%~10質量%,尤佳為0.5質量%~10質量%。若稀釋後的固體成分濃度為所述下限值以上,則原纖化處理的效率提高,若為所述上限值以下,則可防止原纖化處理裝置內的堵塞。
片層可藉由將含有微細纖維的懸浮液塗覆於基材上來製備。基材可使用膜、織布、不織布所代表的片狀者、板或者圓筒體,但並不特別限定於該些基材。基材的材質例如使用樹脂、金屬或者紙等,就可更容易製造含微細纖維的片的方面而言,較佳為樹脂或者紙,但並不特別限定於該些材質。樹脂可列舉:聚四氟乙烯、聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚氯乙烯、
聚偏二氯乙烯、聚苯乙烯、丙烯酸樹脂等,並無特別限定。金屬可列舉鋁、不鏽鋼、鋅、鐵、黃銅等,並無特別限定。紙基材例如可列舉:單面有光紙(one-side glazed paper)、道林紙(woodfree paper)、機械木漿紙(mechanical paper)、複印用紙、銅版紙(art paper)、塗佈紙(coated paper)、牛皮紙、紙板、白板紙、新聞用紙、粗糙紙(rough paper)等紙基材,並無特別限定。
塗覆含有微細纖維的懸浮液的塗覆機例如可使用:輥塗佈機、凹版塗佈機、模塗佈機、簾幕塗佈機、氣刮刀塗佈機等,並無特別限定。由於可使厚度更均勻,故而較佳為模塗佈機、簾幕塗佈機、噴霧塗佈機,更佳為模塗佈機,但並不特別限定於該些塗覆機。
塗覆溫度並無特別限定,較佳為10℃~80℃,尤佳為10℃~60℃。若塗覆溫度為所述下限值以上,則可容易塗覆含微細纖維的懸浮液,若為所述上限值以下,則可抑制塗覆中的分散介質的揮發。
藉由對塗覆於基材上的含有微細纖維的懸浮液進行乾燥而形成不織布層。乾燥方法並無特別限定,可為非接觸的乾燥方法,亦可為將片一邊加以約束一邊進行乾燥的方法的任一種,亦可將該些方法加以組合。
非接觸的乾燥方法並無特別限定,可應用:利用熱風、紅外線、遠紅外線或近紅外線進行加熱而乾燥的方法(加熱乾燥法)、形成真空而進行乾燥的方法(真空乾燥法)。亦可將加熱乾
燥法與真空乾燥法加以組合,通常應用加熱乾燥法。利用紅外線、遠紅外線或近紅外線的乾燥可使用紅外線裝置、遠紅外線裝置或近紅外線裝置來進行,並無特別限定。加熱乾燥法中的加熱溫度並無特別限定,較佳為設為40℃~120℃,更佳為設為40℃~105℃。若將加熱溫度設為所述下限值以上,則可使分散介質迅速揮發,若為所述上限值以下,則可抑制加熱所需要的成本以及微細纖維的因熱而引起的變色。
[被覆層(易黏接性層)]
構成被覆層的成分並無特別限定,可使用:無機成分與有機成分的混成材、熱硬化性樹脂、光硬化性樹脂、熱塑性樹脂等。所述樹脂可列舉:聚酯系樹脂、胺基甲酸酯系樹脂、丙烯酸系樹脂、烯烴系樹脂、氟系樹脂、氯乙烯系樹脂、苯乙烯系樹脂、環氧系樹脂、矽酮系樹脂等。構成被覆層的成分較佳為使用無機成分與有機成分的混成材。所述無機成分與有機成分的混成材、或者樹脂可單獨使用一種,亦可併用兩種以上。亦可將無機成分與有機成分的混成材以及樹脂併用。另外,亦可使用黏著劑、黏著片等作為被覆層。
作為無機成分與有機成分的混成材,例如,被覆層可列舉具有矽骨架的有機成分與無機成分的複合體。具有矽骨架的有機成分與無機成分的混成材例如可列舉倍半矽氧烷等。
倍半矽氧烷為具有(RSiO3/2)n所表示的結構的網路型聚合物或者多面體團簇(polyhedral cluster)(式中,R表示有機基)。
若於R中導入反應性取代基,則可利用該反應性取代基來製作有機成分與無機成分的混成材的硬化物。倍半矽氧烷的結構已知有無規型結構、完全籠型結構、不完全籠型結構、梯型結構等。倍半矽氧烷可使用:荒川化學工業公司製造的康帕賽蘭(Compoceran)SQ100系列、東亞合成股份有限公司製造的光硬化型SQ系列、小西化學工業股份有限公司製造的聚倍半矽氧烷SR系列等,並無特別限定。
構成無機成分與有機成分的混成材的有機成分可列舉具有甲基、巰基、甲基丙烯酸基、丙烯醯基、乙烯基、胺基的成分,包含至少一種以上的成分。具體的有機成分可列舉胺等。
藉由使用構成所述被覆層的成分,可製造片層、與硬化性樹脂層或膜層(1:片層與硬化性樹脂層、2:片層與膜層)的密合性高的複合體。
所述無機成分與有機成分的混成材中所含的有機成分容易與硬化性樹脂層或膜層黏接,另一方面,混成材中所含的無機成分容易與片層黏接,因此片層、與硬化性樹脂層或膜層的黏接性變得良好。藉由使用無機成分與有機成分的混成材作為被覆層的成分,可製造強度高、且難以破裂的複合體。
使片層與被覆層黏接的方法並無特別限制,可列舉塗佈、貼合等方法。於藉由塗佈而使片層與被覆層黏接的情況下,可藉由將包含構成所述被覆層的成分的溶液塗覆於片層上,視需要使其硬化而形成被覆層。硬化方法例如可列舉:藉由熱而硬化
的方法、藉由放射線照射而硬化的方法等,但並不限定於該些方法。放射線可列舉紅外線、可見光線、紫外線等,但並不限定於該些放射線。於藉由熱而硬化的方法的情況下,例如亦可使用熱聚合起始劑,只要是可進行硬化的方法,則可無特別限制地使用。另外,亦可使用黏著劑、包括黏著劑及剝離片的黏著劑(使用時將覆蓋黏著劑的剝離片剝離而使用黏著劑;(例)商品名:無載體膠帶(Non-Carrier Tape))、黏著片等,將片層與被覆層貼合。
本發明的被覆層的厚度並無特別限定,通常為0.1μm~50μm左右,較佳為0.1μm~30μm,更佳為0.2μm~20μm,尤佳為0.5μm~10μm。
被覆層亦可設為2層以上。於設為多層被覆層的情況下,多層被覆層的合計厚度較佳為在所述範圍內。
[硬化性樹脂層或膜層(樹脂層)]
構成硬化性樹脂層或膜層的成分並無特別限定,可使用熱塑性樹脂、熱硬化性樹脂、光硬化性樹脂等。構成硬化性樹脂層或膜層的成分理想為使用對濕度、水、熱、氣體等具有阻擋能力的成分。硬化性樹脂層或膜層亦可積層至少兩層以上。
熱塑性樹脂可列舉:苯乙烯系樹脂、丙烯酸系樹脂、芳香族聚碳酸酯系樹脂、脂肪族聚碳酸酯系樹脂、芳香族聚酯系樹脂、脂肪族聚酯系樹脂、脂肪族聚烯烴系樹脂、環狀烯烴系樹脂、聚醯胺系樹脂、聚苯醚系樹脂、熱塑性聚醯亞胺系樹脂、聚縮醛系樹脂、聚碸系樹脂、非晶性氟系樹脂等,並無特別限制。
熱硬化性樹脂可列舉:環氧樹脂、丙烯酸樹脂、氧雜環丁烷樹脂、酚樹脂、脲樹脂、三聚氰胺樹脂、不飽和聚酯樹脂、矽樹脂、聚胺基甲酸酯樹脂、烯丙基酯樹脂、鄰苯二甲酸二烯丙酯樹脂等,並無特別限制。
光硬化性樹脂可列舉:環氧樹脂、丙烯酸樹脂、氧雜環丁烷樹脂等的前驅物,但並不限定於該些樹脂。
樹脂可單獨使用,亦可使用兩種以上的不同樹脂。
此外,所述熱塑性樹脂、熱硬化性樹脂以及光硬化性樹脂中,最佳為光硬化性樹脂。
熱硬化性樹脂的硬化劑例如可列舉:多官能胺、聚醯胺、酸酐、酚樹脂等,但並不特別限定於該些化合物。另外,熱硬化性樹脂的硬化觸媒例如可列舉咪唑等,但並不特別限定於該些化合物。所述硬化劑、硬化觸媒可單獨使用,亦可使用兩種以上。
使片層與硬化性樹脂層或膜層黏接的方法、以及使片層與硬化性樹脂層或膜層隔著被覆層而黏接的方法並無特別限制,可列舉塗佈、貼合等方法。於藉由塗佈而於片層上黏接硬化性樹脂層或膜層的情況下,可藉由將包含樹脂前驅物及硬化劑的溶液塗覆於片層上,使其硬化而形成硬化性樹脂層或膜層。硬化方法例如可列舉:藉由熱而硬化的方法、藉由放射線照射而硬化的方法等,但並不限定於該些方法。放射線可列舉紅外線、可見光線、紫外線,但並不限定於該些放射線。於藉由熱而硬化的方法的情
況下,例如亦可使用熱聚合起始劑,只要是可進行硬化的方法,則可無特別限制地使用。
另外,於藉由塗佈,隔著被覆層而於片層上黏接硬化性樹脂層或膜層的情況下,可於在片層上塗覆被覆層後,利用與所述相同的方法,於被覆層上形成硬化性樹脂層或膜層。
亦可使用黏著劑、包括黏著劑及剝離片的黏著劑(使用時將覆蓋黏著劑的剝離片剝離而使用黏著劑;(例)商品名:無載體膠帶(Non-Carrier Tape))、黏著片等來作為被覆層,使片層與硬化性樹脂層或膜層貼合。
本發明的硬化性樹脂層或膜層的厚度並無特別限定,通常為0.1μm~100μm左右,較佳為0.2μm~50μm,更佳為0.5μm~20μm,尤佳為1μm~10μm。
硬化性樹脂層或膜層亦可為視目的而積層有多層的硬化性樹脂層或膜層者。於使用多層硬化性樹脂層或膜層的情況下,多層硬化性樹脂層或膜層的合計厚度較佳為在所述範圍內。
利用所述方法,於片層上積層例如對水具有阻擋能力的硬化性樹脂層或膜層,可提高片層對水的阻擋能力。
[複合體(不織布與樹脂的複合體)]
本發明的複合體為:1)於片層上積層有硬化性樹脂層或膜層的複合體(2層);2)片層與硬化性樹脂層或膜層隔著被覆層來積層而成的複合體(3層);3)於片層上積層有被覆層的貼合用片(2層)。
1)於片層上積層有硬化性樹脂層或膜層的複合體(2層)具有高強度且高透明的特徵。2)片層與硬化性樹脂層或膜層隔著被覆層來積層而成的複合體(3層)具有高強度且高透明,並且片層與硬化性樹脂層或膜層的密合性高的特徵。3)於片層上積層有被覆層的貼合用片(2層)具有高強度且高透明,並且片層與被覆層的密合性高的特徵。
所述複合體、以及貼合用片的各層間的密合性較佳為:於以下的實驗例中記載的依據JIS標準K5400的劃格試驗中,100塊中的剝離數為10以下,更佳為5以下,尤佳為3以下。
另外,本發明的複合體、以及貼合用片的特徵在於透明性高。本發明的複合體的全光線透過率較佳為70%以上,更佳為80%以上,尤佳為85%以上,尤佳為90%以上。全光線透過率的上限並無特別限定,可為100%,亦可為99%以下。本發明的複合體的霧度較佳為10%以下,更佳為5%以下,尤佳為3%以下。
[複合體的用途(不織布樹脂複合體的用途)]
本發明的複合體、以及貼合用片可用於液晶顯示器、電漿顯示器、有機電致發光(electroluminescent,EL)顯示器、場發射顯示器、背投影電視機等圖像顯示裝置等。進而,本發明的複合體亦可用於照明裝置、投影裝置。進而,本發明的複合體、以及貼合用片可用於觸控面板或太陽電池(矽系太陽電池、色素增感太陽電池等)的配線基板或前面板、彩色濾光片基板等。於作為基板的用途中,亦可與阻隔膜、氧化銦錫(indium tin oxide,ITO)、
薄膜電晶體(thin film transistor,TFT)等積層。
藉由以下的實驗例來對本發明進一步進行詳細說明,但本發明並不限定於該些實驗例。
[實施例]
(實驗例1)
(1)片層(A)(有時亦稱為不織布層(A))的成膜
使用不織布作為片,利用下述方法製作片層(不織布層)。
使265g的磷酸二氫鈉二水合物、以及197g的磷酸氫二鈉溶解於538g的水中,獲得磷酸系化合物的水溶液(以下稱為「磷酸化試劑」)。
以含水率達到80質量%的方式,利用離子交換水將針葉樹漂白牛皮紙漿(王子製紙股份有限公司製造,水分為50質量%,依據JIS P8121來測定的加拿大標準游離度(Canada standard freeness,CSF)為700ml)進行稀釋,獲得紙漿懸浮液。於500g的該紙漿懸浮液中添加210g的所述磷酸化試劑,利用105℃的鼓風乾燥機,一邊偶爾混練一邊乾燥至質量成為恆量為止。繼而,利用150℃的鼓風乾燥機,一邊偶爾混練一邊進行1小時加熱處理,於纖維素中導入磷酸基。
繼而,於導入有磷酸基的纖維素中添加5000ml的離子交換水,攪拌洗滌後進行脫水。利用5000ml的離子交換水將脫水後的紙漿進行稀釋,一邊攪拌,一邊逐次少量地添加1N的氫氧化鈉水溶液,至pH值達到12~13為止,獲得紙漿懸浮液。然後,
將該紙漿懸浮液進行脫水,添加5000ml的離子交換水進行洗滌。將該脫水洗滌進而重複1次。
於洗滌脫水後獲得的紙漿中添加離子交換水,形成1.0質量%的紙漿懸浮液。以1200巴(bar)的操作壓力,使該紙漿懸浮液於高壓均質機(尼魯索爾維(NiroSoavi)公司製造的「潘德普拉斯(Panda Plus)2000」)中通過5次,獲得微細纖維狀纖維素懸浮液(1)。進而,以245MPa的壓力,使所述微細纖維狀纖維素懸浮液(1)於濕式微粒化裝置(速技能機械(Sugino Machine)公司製造的「阿提莫麥哲(Ultimaizer)」)中通過5次,獲得微細纖維狀纖維素懸浮液(2)。微細纖維狀纖維素的平均纖維寬度為4.2nm。
於微細纖維狀纖維素懸浮液(2)中,以相對於100質量份的微細纖維狀纖維素100質量份而成為15質量份的方式添加聚乙二醇(和光純藥公司製造:分子量為4000000)。此外,以固體成分濃度成為0.5質量%的方式進行濃度製備。以不織布的加工基重成為37.5g/m2的方式計量懸浮液,於市售的丙烯酸板上展開,於50℃的烘箱中進行乾燥。此外,為了達到既定的基重,於丙烯酸板上配置攔截用的板,所得的不織布成為四角形。藉由以上的順序,獲得不織布層(A)(不織布層中所含的微細纖維狀纖維素的含量為86.9質量%)。所得的不織布層(A)的厚度為25μm,密度為1.49g/cm3。
(2)被覆層(B)的成膜
將76重量份作為聚酯系樹脂的UV塗佈增黏劑(荒川化學工業公司製造的阿拉克特(Aracoat)AP2510,固體成分為30質量%)、10重量份的硬化劑(荒川化學工業公司製造的阿拉克特(Aracoat)CL2502,固體成分為20質量%)以及14重量份的甲基乙基酮進行混合,獲得易黏接性塗覆液。繼而,使用邁爾棒(Mayer bar),於不織布層(A)的單面塗覆易黏接性塗覆液。然後,於100℃下乾燥3分鐘而使易黏接性塗覆液硬化,成膜為厚度1μm的被覆層(B)。藉由以上的順序,獲得包括不織布層(A)及被覆層(B)的複合體。
(3)樹脂層(C)的成膜
將80重量份的丙烯酸樹脂組成物(荒川化學工業公司製造的「畢木賽特(Beam Set)381」)、以及20重量份的甲基乙基酮進行混合,獲得硬化性樹脂前驅物溶液。於不織布層(A).被覆層(B)複合體的被覆層(B)上,使用邁爾棒來塗覆所述硬化性樹脂前驅物溶液。繼而,使用UV輸送裝置(岩琦(EyeGraphics)公司製造的「ECS-4011GX」)來照射300mJ/cm2的紫外線,使硬化性樹脂前驅物溶液硬化,成膜為厚度2.5μm的樹脂層(C)。藉由以上的順序,獲得於不織布層(A)的單面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例2)
(1)被覆層(B)的成膜
於實驗例1的(2)中,於不織布層(A)的單面成膜為被覆
層(B)後,於相反側的面上,亦以相同的順序成膜為厚度1.0μm的被覆層(B),獲得包括不織布層(A)及被覆層(B)的複合體。
(2)樹脂層(C)的成膜
於包括不織布層(A)及被覆層(B)的複合體的單面,以與實驗例1的(3)相同的順序成膜為2.5μm的樹脂層(C)。進而,於相反側的面上,亦以相同的順序成膜為厚度2.5μm的樹脂層(C)。藉由以上的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例3)
將50重量份的丙烯酸胺基甲酸酯樹脂組成物(荒川化學工業公司製造的「畢木賽特(Beam Set)575CB」)、以及50重量份的甲基乙基酮進行混合,獲得硬化性樹脂前驅物溶液。於實驗例2的(1)中獲得的包括不織布層(A)及被覆層(B)的複合體的單面,使用邁爾棒來塗覆所述硬化性樹脂前驅物溶液。繼而,於80℃下乾燥3分鐘後,使用UV輸送裝置(岩琦(EyeGraphics)公司製造的「ECS-4011GX」)來照射300mJ/cm2的紫外線,使硬化性樹脂前驅物溶液硬化,成膜為厚度2.5μm的樹脂層(C)。進而,於相反側的面上,亦以相同的順序成膜為厚度2.5μm的樹脂層(C)。藉由以上的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例4)
將40重量份的丙烯酸樹脂組成物(艾迪科(Adeka)公司製
造的「艾迪科歐普托瑪(Adeka Optomer)HC500-60」)、以及60重量份的甲基乙基酮進行混合,獲得硬化性樹脂前驅物溶液。於實施例2的(1)中獲得的包括不織布層(A)及被覆層(B)的複合體的單面,使用邁爾棒來塗覆所述硬化性樹脂前驅物溶液。繼而於100℃下乾燥2分鐘後,使用UV輸送裝置(岩琦(EyeGraphics)公司製造的「ECS-4011GX」)來照射300mJ/cm2的紫外線,使硬化性樹脂前驅物溶液硬化,成膜為厚度2.5μm的樹脂層(C)。進而,於相反側的面上,亦以相同的順序成膜為厚度2.5μm的樹脂層(C)。藉由以上的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例5)
於實驗例4中,將不織布層(A)的厚度設為50μm(密度為1.47g/cm3)。除了所述以外,以與實驗例4相同的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例6)
於實驗例4中,將不織布層(A)的厚度設為75μm(密度為1.46g/cm3)。除了所述以外,以與實驗例4相同的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例7)
於實驗例6中,將成膜於包括不織布層(A)及被覆層(B)
的複合體的兩面的樹脂層(C)的厚度設為10μm。除了所述以外,以與實驗例6相同的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例8)
於實驗例6中,將成膜於包括不織布層(A)及被覆層(B)的複合體的兩面的樹脂層(C)的厚度設為20μm。除了所述以外,以與實驗例6相同的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例9)
(1)被覆層(B)的成膜
將26重量份的倍半矽氧烷(荒川化學工業公司製造的「康帕賽蘭(Compoceran)SQ107」)、14重量份的硬化劑(荒川化學工業公司製造的「HBSQ201」)、60重量份的異丙醇進行混合,獲得黏接性塗覆液。繼而,使用邁爾棒,於實驗例1的(1)中獲得的不織布層(A)的單面塗覆黏接性塗覆液。然後,於100℃下乾燥3分鐘後,使用UV輸送裝置(岩琦(EyeGraphics)公司製造的「ECS-4011GX」)來照射300mJ/cm2的紫外線,使黏接性塗覆液硬化,成膜為厚度2.5μm的被覆層(B)。進而,於相反側的面上,亦以相同的順序成膜為厚度2.5μm的被覆層。藉由以上的順序,獲得包括不織布層(A)及被覆層(B)的複合體。
(2)樹脂層(C)的成膜
將40重量份的丙烯酸樹脂組成物(艾迪科(Adeka)公司製
造的「艾迪科歐普托瑪(Adeka Optomer)HC500-60」)、以及60重量份的甲基乙基酮進行混合,獲得硬化性樹脂前驅物溶液。於包括不織布層(A)及被覆層(B)的複合體的單面,使用邁爾棒來塗覆所述硬化性樹脂前驅物溶液。繼而於100℃下乾燥2分鐘後,使用UV輸送裝置(岩琦(EyeGraphics)公司製造的「ECS-4011GX」)來照射300mJ/cm2的紫外線,使硬化性樹脂前驅物溶液硬化,成膜為厚度2.5μm的樹脂層(C)。進而,於相反側的面上,亦以相同的順序成膜為厚度2.5μm的樹脂層(C)。藉由以上的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例10)
於實驗例9中,將成膜於不織布層(A)的兩面的被覆層(B)的厚度設為5.0μm,另外將成膜於包括不織布層(A)及被覆層(B)的複合體的兩面的樹脂層(C)的厚度設為10μm。除了所述以外,以與實驗例9相同的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例11)
於實驗例10中,將不織布層(A)的厚度設為130μm(密度為1.42g/cm3)。除了所述以外,以與實驗例10相同的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例12)
於實驗例11中,將成膜於包括不織布層(A)及被覆層(B)的複合體的兩面的樹脂層(C)的厚度設為40μm。此外,於樹脂層(C)的成膜中,為了增加硬化性樹脂前驅物溶液的塗覆量來形成既定的膜厚,使用膜敷料器進行塗覆。除了所述以外,以與實驗例11相同的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例13)
於實驗例12中,將成膜於不織布層(A)的兩面的被覆層(B)的厚度設為25μm。此外,於被覆層(B)、以及樹脂層(C)的成膜中,為了增加易黏接性塗覆液、以及硬化性樹脂前驅物溶液的塗覆量來形成既定的膜厚,使用膜敷料器進行塗覆。除了所述以外,以與實驗例12相同的順序,獲得於不織布層(A)的兩面隔著被覆層(B)而積層有樹脂層(C)的複合體。
(實驗例14)
於實驗例1的(1)中獲得的不織布層(A)的單面,以與實驗例1的(3)相同的順序成膜為2.5μm的樹脂層(C)。進而,於相反側的面上,亦以相同的順序成膜為厚度2.5μm的樹脂層(C)。藉由以上的順序,獲得於不織布層(A)的兩面直接積層有樹脂層(C)的複合體。
(實驗例15)
於實驗例1的(1)中獲得的不織布層(A)的單面,使用邁爾棒來塗覆將40重量份的丙烯酸樹脂組成物(艾迪科(Adeka)
公司製造的「艾迪科歐普托瑪(Adeka Optomer)HC500-60」)、以及60重量份的甲基乙基酮進行混合而獲得的硬化性樹脂前驅物溶液。繼而於100℃下乾燥2分鐘後,使用UV輸送裝置(岩琦(EyeGraphics)公司製造的「ECS-4011GX」)來照射300mJ/cm2的紫外線,使硬化性樹脂前驅物溶液硬化,成膜為厚度2.5μm的樹脂層(C)。進而,於相反側的面上,亦以相同的順序成膜為厚度2.5μm的樹脂層(C)。藉由以上的順序,獲得於不織布層(A)的兩面直接積層有樹脂層(C)的複合體。
(實驗例16)
於實驗例1的(1)中,以相對於100質量份的微細纖維狀纖維素而成為150質量份的方式添加聚乙二醇(和光純藥公司製造:分子量為4000000),除此以外,以與實驗例1的(1)相同的方式獲得不織布層(A)(不織布層中所含的微細纖維狀纖維素的含量為40質量%)。繼而,以與實驗例1的(3)相同的順序成膜為2.5μm的樹脂層(C)。進而,於相反側的面上,亦以相同的順序成膜為厚度2.5μm的樹脂層(C)。藉由以上的順序,獲得於不織布層(A)的兩面直接積層有樹脂層(C)的複合體。
<評價方法>
依據以下的評價方法,對於所述實驗例中製作的複合體進行評價。將所述的評價結果示於表1中。
(1)密合性的評價(劃格試驗)
依據JIS標準K5400,於複合體的面上形成100個1mm2的劃
格,於其上貼附玻璃紙膠帶(米其邦(Nichiban)公司製造),以1.5k g/cm2的荷重按壓後,向90°方向剝離。根據所剝離的塊數來評價不織布層(A)與樹脂層(C)的密合性。
(2)複合體的全光線透過率
依據JIS標準K7105,使用霧度計(斯加試驗機(Suga Test Instruments)公司製造的「HM-150」)來測定C光的全光線透過率。
(3)複合體的霧度
依據JIS標準K7136,使用霧度計(斯加試驗機公司製造的「HM-150」)來測定C光的霧度值。
(4)拉伸彈性模數
依據JIS標準P8113,使用拉伸試驗機(L & W公司製造的「破裂韌性試驗機(fracture toughness tester)SE-064」)來測定拉伸彈性模數。
如表1所明示,於不織布層(A)上隔著被覆層(B)而積層有樹脂層(C)的實驗例1~實驗例13中,獲得不織布層(A)與樹脂層(C)的密合性高且高透明(全光線透過率高,霧度低)的複合體。另外,於微細纖維狀纖維素的含量為86.9質量%的不織布層(A)上直接積層有樹脂層(C)的實驗例(實驗例14及實驗例15)中,與在微細纖維狀纖維素的含量為40質量%的不織布層(A)上直接積層有樹脂層(C)的實驗例(實驗例16)相比較,獲得高強度且高透明的複合體。
(實驗例17)
於實驗例1中,製作於不織布層(A)上成膜有被覆層(B)且未成膜有樹脂層(C)的複合體。即,製作包括不織布層(A)及被覆層(B)此兩層的貼合用片(複合體)。對不織布層(A)與被覆層(B)的密合性進行評價。除此以外,全部利用與實驗例1相同的方法進行試驗。將結果示於表2中。
(實驗例18)
於實驗例17中,於不織布層的單面成膜為被覆層後,於不織布層的相反側的面上,亦以相同的順序成膜為厚度1.0μm的被覆層,除此以外,全部利用與實驗例17相同的方法進行試驗。將結果示於表2中。
如表2所明示,於不織布層(片層)上積層有被覆層的貼合用片(實驗例17及實驗例18)的不織布層與被覆層的密合性高且為高透明。
(實驗例19)
利用下述方法對實驗例1中製作的複合體的破裂容易度進行評價(以下稱為「破裂性的評價」)。將結果示於表3中。
<破裂性的評價>
用手將複合體(縱10cm×橫10cm)彎折,基於下述基準,以目視來評價不織布複合體上是否產生龜裂。
○:未產生龜裂。
×:產生龜裂。
(實驗例20)
以與實驗例19相同的方法,對實驗例2中製作的複合體的破裂容易度進行評價。將結果示於表3中。
(實驗例21)
於實驗例1中,代替聚酯系樹脂而使用倍半矽氧烷(荒川化學工業公司製造的「康帕賽蘭(Compoceran)SQ107」)來作為被覆層,除此以外,全部利用與實驗例1相同的方法進行試驗。以與實驗例19相同的方法,對所製作的複合體的破裂容易度進行評價。將結果示於表3中。
(實驗例22)
於實驗例2中,除了代替聚酯系樹脂而使用倍半矽氧烷(荒川化學工業公司製造的「康帕賽蘭(Compoceran)SQ107」)來作為被覆層以外,全部利用與實驗例2相同的方法進行試驗。以與實驗例19相同的方法,對所製作的複合體的破裂容易度進行評價。將結果示於表3中。
與使用聚酯系樹脂作為被覆層的複合體(實驗例19、實驗例20)相比較,使用倍半矽氧烷作為被覆層的複合體(實驗例21、實驗例22)未產生龜裂(裂縫)。
(實驗例23)
對於實驗例1中獲得的不織布層(A),貼合後UV型黏著劑(新達可化成(New Tac Kasei)製造的「DC011」,厚度為25μm)作為被覆層(B)。進而,於被覆層(B)的上表面貼合PET膜(東麗製造的「露米勒(Lumirror)S10」,厚度為25μm)作為膜層(C)。然後,使用UV輸送裝置(岩琦(EyeGraphics)公司製造的「ECS-4011GX」),自膜層(C)側照射250mJ/cm2的紫外線6次,使被覆層(B)硬化。藉由以上的順序,獲得於不織布層(A)的單面隔著被覆層(B)而積層有膜層(C)的複合體。將結果示於表4中。
(實驗例24)
於實驗例23中,於片層(A)的單面積層被覆層(B)、以及膜層(C)後,於相反側的面上,亦以相同的順序積層被覆層(B)、以及膜層(C)。藉由以上的順序,獲得於片層(A)的兩面隔著被覆層(B)而積層有膜層(C)的複合體。將結果示於表4中。
關於使用黏著劑作為被覆層的複合體(實驗例23、實驗例24),不織布層(片層)與樹脂層的密合性亦良好。
1‧‧‧片層
2‧‧‧被覆層
3‧‧‧硬化性樹脂層或膜層
Claims (24)
- 一種複合體,其於以平均纖維寬度為2nm~1000nm的微細纖維作為主成分的片層的單面或兩面具有硬化性樹脂層或膜層。
- 如申請專利範圍第1項所述的複合體,其中所述微細纖維的平均纖維寬度為2nm~100nm。
- 如申請專利範圍第1項或第2項所述的複合體,其中所述片層的密度為0.90g/cm3以上。
- 如申請專利範圍第1項至第3項中任一項所述的複合體,其中所述片層為不織布。
- 如申請專利範圍第1項至第4項中任一項所述的複合體,其中所述微細纖維為包含纖維素纖維的纖維。
- 如申請專利範圍第1項至第5項中任一項所述的複合體,其中隔著設置於所述片層的單面或兩面的被覆層,而積層有所述硬化性樹脂層或所述膜層。
- 如申請專利範圍第6項所述的複合體,其中所述片層的厚度為2μm~150μm,所述被覆層的每一層的厚度為0.1μm~30μm,所述硬化性樹脂層或所述膜層的每一層的厚度為0.2μm~100μm。
- 如申請專利範圍第6項或第7項所述的複合體,其中所述片層與所述硬化性樹脂層或所述膜層的密合性於依據JIS標準K5400的劃格試驗中,100塊中的剝離數為10以下。
- 如申請專利範圍第6項至第8項中任一項所述的複合體,其中全光線透過率為85%以上,霧度為10%以下。
- 如申請專利範圍第6項至第9項中任一項所述的複合體,其中所述被覆層為有機成分與無機成分的混成材。
- 如申請專利範圍第10項所述的複合體,其中所述有機成分與所述無機成分的所述混成材包含具有矽骨架的有機成分及無機成分。
- 如申請專利範圍第10項或第11項所述的複合體,其中所述有機成分為包含選自甲基、巰基、甲基丙烯酸基、丙烯醯基、乙烯基及胺基中的至少一種的成分。
- 如申請專利範圍第10項至第12項中任一項所述的複合體,其中所述有機成分與所述無機成分的所述混成材為倍半矽氧烷。
- 如申請專利範圍第6項至第9項中任一項所述的複合體,其中所述被覆層為選自熱硬化性樹脂、熱塑性樹脂、以及光硬化性樹脂中的至少一種。
- 如申請專利範圍第6項至第9項中任一項所述的複合體,其中所述被覆層為黏著劑。
- 一種貼合用片,其於以平均纖維寬度為2nm~1000nm的纖維素微細纖維作為主成分的片層的單面或兩面具有被覆層。
- 如申請專利範圍第16項所述的片,其中所述被覆層為有機成分與無機成分的混成材。
- 如申請專利範圍第17項所述的片,其中所述有機成分為包含選自甲基、巰基、甲基丙烯酸基、丙烯醯基、乙烯基及胺基中的至少一種的成分。
- 如申請專利範圍第17項或第18項所述的片,其中所述有機成分與所述無機成分的所述混成材為倍半矽氧烷。
- 一種複合體,其於如申請專利範圍第16項至第19項的片上積層硬化性樹脂層或膜層。
- 一種複合體的製造方法,其包括:於以平均纖維寬度為2nm~1000nm的微細纖維作為主成分的片層的單面或兩面上設置被覆層的步驟;以及於所述被覆層的與所述片層相反之側的表面上設置硬化性樹脂層或膜層的步驟。
- 如申請專利範圍第21項所述的複合體的製造方法,其中所述片層與所述被覆層藉由塗覆、或者貼合而積層。
- 如申請專利範圍第21項所述的複合體的製造方法,其中所述被覆層、與所述硬化性樹脂層或所述膜層藉由塗覆、或者貼合而積層。
- 一種照明裝置、投影裝置、招牌或圖像顯示裝置、觸控面板、或者太陽電池,其包括如申請專利範圍第1項至第20項中任一項所述的複合體。
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2015
- 2015-04-20 JP JP2016514920A patent/JP6686880B2/ja active Active
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- 2015-04-20 EP EP15782224.8A patent/EP3135488B1/en active Active
- 2015-04-20 WO PCT/JP2015/061981 patent/WO2015163281A1/ja active Application Filing
- 2015-04-20 CN CN201580021073.1A patent/CN106457798A/zh active Pending
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US10808361B2 (en) | 2015-11-30 | 2020-10-20 | Oji Holdings Corporation | Sheets and method for producing sheets |
US11426763B2 (en) | 2016-01-20 | 2022-08-30 | Oji Holdings Corporation | Laminate and method for producing laminate |
Also Published As
Publication number | Publication date |
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JP2020104525A (ja) | 2020-07-09 |
EP3135488C0 (en) | 2023-12-06 |
CN106457798A (zh) | 2017-02-22 |
EP3135488A4 (en) | 2017-11-08 |
JPWO2015163281A1 (ja) | 2017-04-13 |
JP6950778B2 (ja) | 2021-10-13 |
WO2015163281A1 (ja) | 2015-10-29 |
JP6686880B2 (ja) | 2020-04-22 |
KR20160145608A (ko) | 2016-12-20 |
US10532545B2 (en) | 2020-01-14 |
EP3135488B1 (en) | 2023-12-06 |
EP3135488A1 (en) | 2017-03-01 |
US20170043565A1 (en) | 2017-02-16 |
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