TW202041356A - 具有毛狀體的樹脂薄片及其成形品 - Google Patents
具有毛狀體的樹脂薄片及其成形品 Download PDFInfo
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- TW202041356A TW202041356A TW109110233A TW109110233A TW202041356A TW 202041356 A TW202041356 A TW 202041356A TW 109110233 A TW109110233 A TW 109110233A TW 109110233 A TW109110233 A TW 109110233A TW 202041356 A TW202041356 A TW 202041356A
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- resin sheet
- trichomes
- resin
- less
- hair
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Abstract
本發明之目的在於提供能展現特定的觸感性之薄片及其成形品。
一種樹脂薄片,其特徵為:具有在含有熱塑性樹脂的基底層之至少一面上規則排列的毛狀體,於具有毛狀體的面中依照KES法測定的摩擦係數為0.5以上1.0以下,且依照KES法測定的摩擦係數之變動為0.010以上0.025以下,而且依照KES法測定的粗糙度之變動為0.2以上1.5以下。
Description
本發明係關於具有毛狀體的樹脂薄片及其成形品。
自以往以來,使用紙材、高分子材料的薄片作為汽車的內裝材料或附屬零件的殼體、電子機器或家電的殼體、壁紙等之建材用、玩具或遊戲機的殼體、生活用品的構件用。又,作為將良好觸感性賦予至薄片表面之方法,例如專利文獻1中提案一種樹脂薄片,其具有在表面上規則排列的毛狀體。
[先前技術文獻]
[專利文獻]
專利文獻1:國際公開第2018/016562號
[發明欲解決之課題]
另一方面,要求提供具有配合用途的特定觸感性之薄片。
本發明之目的在於提供能展現特定的觸感性之樹脂薄片及其成形品。
[用以解決課題之手段]
即,本發明者檢討各式各樣的手段的結果,發現:
一種樹脂薄片,其具有在包含熱塑性樹脂的基底層之至少一面上規則排列的毛狀體,其中藉由調整成:於具有毛狀體的面中依照KES法測定的摩擦係數為0.5以上1.0以下,且依照KES法測定的摩擦係數之變動為0.010以上0.025以下,而且依照KES法測定的粗糙度之變動為0.2以上1.5以下,而展現特定的觸感性,遂而完成本發明。
解決上述課題的本發明係由下述所構成。
(1)一種樹脂薄片,其特徵為:具有在含有熱塑性樹脂的基底層之至少一面上規則排列的毛狀體,於具有毛狀體的面中依照KES法測定的摩擦係數為0.5以上1.0以下,且依照KES法測定的摩擦係數之變動為0.010以上0.025以下,而且依照KES法測定的粗糙度之變動為0.2以上1.5以下。
(2)如(1)記載之樹脂薄片,其中毛狀體的平均高度為30μm以上500μm以下,毛狀體的平均直徑為1μm以上50μm以下,毛狀體的平均間隔為20μm以上200μm以下。
(3)如(1)或(2)記載之樹脂薄片,其中前述依照KES法測定的粗糙度之變動為0.22以上1.0以下。
(4)如(1)至(3)中任一項記載之樹脂薄片,其中於具有毛狀體的面中,依照KES法測定的摩擦係數與依照KES法測定的摩擦係數之變動之比(MIU/MMD)為40以上且小於55。
(5)如(1)至(4)中任一項記載之樹脂薄片,其中使用氙燈式促進耐候性試驗機,於黑色面板溫度63℃、放射照度60W/m2
下照射500小時之際之試驗前後的毛狀體及基底層之色差ΔE為10以下。
(6)如(1)至(5)中任一項記載之樹脂薄片,其中熱塑性樹脂含有聚碳酸酯系的胺基甲酸酯系彈性體。
(7)一種如(1)至(6)中任一項記載之樹脂薄片之成形品。
(8)如(7)記載之成形品,其係文具構件。
(9)如(7)記載之成形品,其係被真空加壓成形於汽車內裝材料、電子機器、電子機器外裝材料、化妝品容器或容器構件之表面。
[發明之效果]
依照本發明,可提供展現特定的觸感性之薄片。
[用以實施發明的形態]
以下,說明樹脂薄片之各種實施形態,接著說明樹脂薄片之製造方法,但針對一實施形態所記載的特定說明亦適用於其它實施形態時,在其它實施形態中省略其說明。
[第一實施形態]
本發明之第一實施形態的樹脂薄片係一種樹脂薄片,其具有在含有熱塑性樹脂的基底層之至少一面上規則排列的毛狀體,其特徵為:於具有毛狀體的面中依照KES法測定的摩擦係數為0.5以上1.0以下,且依照KES法測定的摩擦係數之變動為0.010以上0.025以下,而且依照KES法測定的粗糙度之變動為0.2以上1.5以下。
<基底層>
基底層(1a)係成為毛狀體的基底之層,於符號1之中,指表面的毛狀體1b以外之部分。基底層的厚度係指從毛狀體的根部到基底層的相反側的表面為止之厚度。基底層的平均厚度較佳為15μm~1000μm,更佳為150μm~800μm。由於設為15μm以上,能充分展現毛狀體的高度。又,由於設為1000μm以下,可有效率地形成毛狀體。基底層與毛狀體之間無結構上的邊界,可形成連續相。所謂無結構上的邊界,就是意指基底層與毛狀體係形成一體型,在此等之間無結構上明確的邊界部。又,所謂形成連續相,就是指在基底層與毛狀體之間無接縫,且非不連續(成為連續相)狀態。此點係與在基底層植入毛狀體的結構不同。基底層及毛狀體可為相同組成,於基底層與毛狀體之鍵結中可包含共價鍵。所謂共價鍵係指藉由在2個原子共用電子對而形成的化學鍵,但在單體連接成的鏈狀分子之熱塑性樹脂中,各個聚合物係藉由共價鍵而鍵結,比在聚合物分子間作用的凡得瓦鍵或氫鍵更強地鍵結。
又,基底層及毛狀體亦可來自非分開的相同固體之熱塑性樹脂薄片。所謂來自相同固體之熱塑性樹脂薄片,例如就是意指毛狀體及基底層係以相同之樹脂薄片為基礎而直接或間接地獲得。
另外,基底層及毛狀體亦可由相同固體之熱塑性樹脂薄片所形成。所謂由相同固體之熱塑性樹脂薄片所形成,就是意指毛狀體及基底層係藉由加工一個樹脂薄片而直接形成。
藉由在基底層與毛狀體之間無結構上的邊界,形成連續相,可抑制因外在刺激而毛狀體從基底層分離,成為觸感性良好之薄片。又,能以比植入毛狀體的情況更少的步驟來製造。
基底層及毛狀體係由以熱塑性樹脂為主成分的相同樹脂組成物所成。所謂以熱塑性樹脂為主成分,就是意指含有50質量%以上、60質量%以上、70質量%以上、80質量%以上或90質量%以上的熱塑性樹脂。作為熱塑性樹脂,可使用包含苯乙烯系樹脂、烯烴系樹脂、聚氯乙烯樹脂、熱塑性彈性體、氟系樹脂之至少1種類以上的樹脂。
作為苯乙烯系樹脂,可使用苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、二甲基苯乙烯、對第三丁基苯乙烯、氯苯乙烯等之苯乙烯系單體的均聚物或共聚物、彼等苯乙烯系單體與其它單體之共聚物,例如苯乙烯-丙烯腈共聚物(AS樹脂),或前述苯乙烯系單體與更其它的聚合物,例如在聚丁二烯、苯乙烯-丁二烯共聚物、聚異戊二烯、聚氯平(polychloroprene)等二烯系橡膠質聚合物之存在下接枝聚合的接枝聚合物,例如高衝擊聚苯乙烯(HIPS樹脂)、苯乙烯-丙烯腈接枝聚合物(ABS樹脂)等之聚苯乙烯。又,亦可使用苯乙烯系的熱塑性彈性體。
聚烯烴系樹脂係意指由包含α-烯烴作為單體的聚合物所成之樹脂,包含聚乙烯系樹脂及聚丙烯系樹脂。作為聚乙烯系樹脂,可使用高密度聚乙烯、低密度聚乙烯、直鏈狀低密度聚乙烯、直鏈狀中密度聚乙烯等,還有不僅單體,而且亦可使用具有彼等結構之共聚物或接枝物或摻合物。作為後者之樹脂,例如可舉出乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、乙烯-甲基丙烯酸酯共聚物、乙烯-乙酸乙烯酯-氯乙烯共聚物,或如更與酸酐的3元共聚物等摻合者,將在聚乙烯鏈中具有極性基的樹脂共聚合及摻合者。
又,作為聚丙烯系樹脂,可使用均聚丙烯、無規聚丙烯、嵌段聚丙烯等。使用均聚丙烯時,該均聚丙烯之結構可為同排、雜排、對排之任一者。使用無規聚丙烯時,作為與丙烯共聚合的α-烯烴,較佳為碳數2~20,更佳為碳數4~12者,例如可使用乙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯。使用嵌段聚丙烯時,可使用嵌段共聚物(嵌段聚丙烯)、含有橡膠成分的嵌段共聚物或接枝共聚物等。除了單獨使用此等烯烴系樹脂以外,還可併用其它的烯烴系樹脂。
作為聚氯乙烯系樹脂,可使用氯乙烯均聚物或氯乙烯與其它的共聚單體之共聚物。聚氯乙烯為共聚物時,可為無規共聚物,也可為接枝共聚物。作為接枝共聚物之一例,例如可舉出將乙烯-乙酸乙烯酯共聚物或熱塑性胺基甲酸酯聚合物當作主幹聚合物,將氯乙烯接枝聚合於其者。本實施形態之聚氯乙烯系樹脂係表示能擠出成形的軟質聚氯乙烯,為含有高分子塑化劑等添加物之組成物。作為高分子塑化劑,可使用眾所周知的高分子塑化劑,例如可舉出乙烯-乙酸乙烯酯-一氧化碳共聚物、乙烯-(甲基)丙烯酸酯-一氧化碳共聚物、乙酸乙烯酯含量多的乙烯-乙酸乙烯酯共聚物等之乙烯共聚物高分子塑化劑作為較佳例。
作為熱塑性彈性體,包含具有將軟質高分子物質與硬質高分子物質組合成之結構者。具體而言,可舉出苯乙烯系彈性體、烯烴系彈性體、氯乙烯系彈性體、聚酯系彈性體、聚醯胺系彈性體、聚胺基甲酸酯系彈性體等。關於聚胺基甲酸酯系彈性體,作為原料的異氰酸酯與多元醇之組合,可選擇異氰酸酯為MDI系、H12
MDI系、HDI系且多元醇為聚醚系、聚酯系、聚碳酸酯系之任一組合,另外亦可組合複數。此等彈性體可從一般市售者之中選擇而使用。
作為氟系樹脂,可使用偏二氟乙烯的均聚物及以偏二氟乙烯為主成分的偏二氟乙烯共聚物。聚偏二氟乙烯(PVDF)樹脂係顯示α型、β型、γ型、αp型等各式各樣的結晶構造之結晶性樹脂,作為偏二氟乙烯共聚物,例如可舉出偏二氟乙烯-六氟丙烯共聚物、偏二氟乙烯-四氟乙烯共聚物、偏二氟乙烯-氯三氟乙烯共聚物、偏二氟乙烯-三氟乙烯共聚物、偏二氟乙烯-四氟乙烯-六氟丙烯三元共聚物、偏二氟乙烯-氯三氟乙烯-六氟丙烯三元共聚物及此等的2種以上之混合物。
作為聚酯系樹脂,可使用聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚2,6-萘二甲酸乙二酯、聚對苯二甲酸甲二酯,及作為共聚合成分,例如可使用二乙二醇、新戊二醇、聚烷二醇等二醇成分或己二酸、癸二酸、鄰苯二甲酸、間苯二甲酸、2,6-萘二甲酸等二羧酸成分等共聚合成的聚酯樹脂等。
作為尼龍系樹脂,可使用己內醯胺、月桂內醯胺等之內醯胺聚合物、6-胺基己酸、11-胺基十一酸、12-胺基十二酸等之胺基羧酸的聚合物、六亞甲基二胺、十亞甲基二胺、十二亞甲基二胺、2,2,4-或2,4,4-三甲基六亞甲基二胺等之脂肪族二胺、1,3-或1,4-雙(胺基甲基)環己烷、雙(對胺基環己基甲烷)等之脂環式二胺、m-或p-苯二甲基二胺等之芳香族二胺等的二胺單元、與己二酸、辛二酸、癸二酸等之脂肪族二羧酸、環己烷二羧酸等之脂環式二羧酸、對苯二甲酸、間苯二甲酸等之芳香族二羧酸等之二羧酸單元的聚縮合物、及此等之共聚物等。例如有尼龍6、尼龍9、尼龍11、尼龍12、尼龍66、尼龍610、尼龍611、尼龍612、尼龍6T、尼龍6I、尼龍MXD6、尼龍6/66、尼龍6/610、尼龍6/6T、尼龍6I/6T等,其中較佳為尼龍6、尼龍MXD6。
熱塑性樹脂之190℃至300℃下的熔體質量流動速率較佳為4g/10分鐘以上。由於設為4g/10分鐘以上,可提高毛狀體的形狀之轉印性。還有,熔體質量流動速率係依據JIS K 7210,在試驗溫度190℃至300℃之溫度範圍中,於荷重(2.16Kg至10.0Kg)之條件下所測定的值。
熱塑性樹脂係在不妨礙本發明的效果之範圍內,可與上述各熱塑性樹脂以任意之比例摻合。再者,亦可含有其它的添加物。作為其它的添加物,在不妨礙本發明的效果之範圍內,可添加如撥水・撥油劑、顏料、染料等之著色劑、矽油或烷酯系等之脫模劑、玻璃纖維等之纖維狀強化劑、作為填充劑的滑石、黏土、矽石等之粒狀微粒子或雲母等之鱗片狀微粒子、磺酸與鹼金屬等之鹽化合物等的低分子型抗靜電劑或聚醚酯醯胺等之高分子型抗靜電劑、紫外線吸收劑、難燃劑、抗菌劑、抗病毒劑、熱安定劑之添加劑等。又,亦可混合使用樹脂薄片製程中所產生的廢料樹脂。
作為撥水・撥油劑,可舉出矽系撥水劑、棕櫚蠟、氟系撥水撥油劑。作為矽,可舉出有機聚矽氧烷、二甲基聚矽氧烷、甲基苯基聚矽氧烷、甲基氫聚矽氧烷等,其中較宜使用二甲基聚矽氧烷。作為市售品,例如可舉出在樹脂中摻合有矽之「Clinbell CB50-PP」、「Clinbell CB-30PE」、「Clinbell CB-1」、「Clinbell CB-50AB」(富士化學公司製)等。棕櫚蠟係可舉出市售品的「Carnauba 1號」(NIKKO RICA公司製)等,氟系撥水撥油劑係可舉出具有全氟烷基的界面活性劑,作為市售品,可舉出「Surflon KT-PA」(AGC SEIMI化學公司製)等。撥水・撥油劑之添加量較佳為0.5質量%至25質量%。小於0.5質量%時,有得不到充分的撥水・撥油性效果之虞,超過25質量%時,有成形性變差之虞。
作為抗靜電劑,可舉出聚醚酯醯胺系高分子型抗靜電劑、離子聚合物系高分子型抗靜電劑等。聚醚酯醯胺系高分子型抗靜電劑係可舉出市售品的「Pelestat 230」、「Pelestat 6500」、「Pelectron AS」、「Pelectron HS」(三洋化成公司製)等。離子聚合物系高分子型抗靜電劑係可舉出市售品的「Entira SD100」、「Entira MK400」(三井-杜邦聚化學公司製)等。抗靜電劑之添加量較佳為5質量%至30質量%。小於5質量%時,有得不到充分的抗靜電性之虞,超過30質量%時,生產成本上升。
作為抗菌劑,可添加無機系、有機系中之任一者。若考慮分散性,則較佳為無機系。具體而言,可舉出金屬離子(Ag、Zn、Cu)的無機系抗菌劑、貝殼燒成鈣系抗菌劑等。作為金屬離子的無機系抗菌劑之市售品,可舉出「Bactekiller BM102VT」(富士化學公司製)、「Novaron VZF200」、「Novaron (AG300)」(東亞合成公司製)、「KM-10D-G」、「IM-10D-L」(Sinanen Zeomic公司製)等。作為貝殼燒成鈣系抗菌劑,可舉出「Scallow」(FID公司製)等。抗菌劑之添加量較佳為0.5質量%~5質量%。小於0.5質量%時,有得不到充分抗菌性之虞,超過5質量%時,生產成本上升。
作為紫外線吸收劑,可使用無機系或有機系的紫外線吸收劑。
作為無機系紫外線吸收劑,例如可使用氧化鈦、氧化鋅、氧化銫、氧化鐵及其它許多種類者。其中,尤其氧化鋅係在透明性或紫外線不穿透性之點上優異而良好。作為市售品,例如可使用三系紫外線吸收劑「TINUVIN 1600」(BASF公司製)等。
使用無機系紫外線吸收劑的情形,相對於樹脂組成物之合計100質量份,其添加量較佳為1~5質量份。添加量小於1質量份時,有抑制因紫外線所致的薄片之劣化的效果變低之虞,超過5質量份時,生產成本變高。
又,亦可使用預先將無機系紫外線吸收劑摻合至熱塑性樹脂中而成的母料等。例如,作為以胺基甲酸酯系熱塑性彈性體為基底之母料的市售品,可舉出「耐候母料UNS(聚酯系)」(FIC公司製)、「耐候母料UNE(聚醚系)」(FIC公司製),若考慮生產效率,則較佳為使用母料者。相對於樹脂組成物100質量份,母料之添加量較佳為1~5質量份。
另外,作為有機系紫外線吸收劑,例如可使用三系、苯并三唑系、草酸系、二苯基酮系、受阻胺系及其它許多種類者。為了使薄膜之製造時或使用時的揮發成為最小限度,宜使用分子量為300以上的高分子量型紫外線吸收劑。
使用有機系紫外線吸收劑時,相對於樹脂組成物之合計100質量份,其添加量較佳為4質量份以上。含量小於4質量份時,有不充分地得到能抑制紫外線所致的薄片之劣化的效果之虞。另一方面,即使超過8質量份,也不僅抑制紫外線所致的薄片之劣化的效果係到達頂點,而且從成本方面來看亦不宜。
作為滑劑・脫模劑,可使用脂肪族烴系化合物、高級脂肪酸系化合物、高級脂肪族醇系化合物、脂肪酸醯胺系化合物等之烷基系脫模劑、矽系脫模劑、氟系脫模劑等。使用脫模劑時,其添加量係於與樹脂組成物之合計100質量份之中,較佳為0.01~5質量份,更佳為0.05~3質量份,尤佳為0.1~2質量份。添加量小於0.01質量份時,有脫模效果變低之虞,超過5質量份時,有滲出至薄片表面之虞。
又,亦可使用預先將滑劑・脫模劑摻合至熱塑性樹脂中而成的母料等。例如,作為以胺基甲酸酯系熱塑性彈性體為基底之母料的市售品,可舉出「Wax Master V」(BASF公司製),若考慮生產效率,則較佳為使用母料者。母料之添加量係於與樹脂組成物之合計100質量份之中,較佳為1~8質量份,更佳為2~7質量份,尤佳為3~6質量份。
<毛狀體>
所謂毛狀體(1b),就是如圖1所示,指從基底層(1a)之表面伸展成毛狀的部分。毛狀體係規則排列於基底層之表面。此處,所謂規則排列,就是意指毛狀體係非無規的排列狀態,亦即於一方向或二方向中整齊(例如以一定的間隔)排列之狀態。以毛狀體的根部之排列狀態來判斷毛狀體的排列是否為規則。於某一實施形態中,毛狀體係以特定的間隔位於基底層上,且毛狀體之底面的位置係整齊排列於基底層之長邊方向及短邊方向。又,毛狀體之配置形態係沒有特別的限定,可選擇縱橫配置的棋盤格配置或交錯配置等。藉由將毛狀體規則排列於基底層之表面,而均勻且無不一致,容易展現良好觸感性。毛狀體例如係藉由手指描摹等施加荷重而發生倒毛,可形成與周圍的部分看起來光澤、色調不同的指痕。又,藉由毛狀體,可成為如仿麂皮的起毛薄片之觸感。
毛狀體的平均高度(h)較佳為30μm~500μm,更佳為30μm~250μm,尤佳為30μm~200μm。藉由將平均高度設為30μm以上,可充分確保良好觸感性,藉由將平均高度設為500μm以下,可得到濕潤感、柔軟感、蓬鬆感等之良好觸感性。
毛狀體對於基底層幾乎直立時,從毛狀體的根部到前端為止的長度表示毛狀體的高度。另一方面,毛狀體對於基底層呈傾斜時或毛狀體具有捲繞部分時,將毛狀體最遠離基底層的表面之地方到基底層的表面之距離當作毛狀體的高度h。又,藉由多點間計測從毛狀體之前端到根部的中央部為止,將經細分化的間隔之合計值當作毛狀體的長度L。
毛狀體的平均高度及毛狀體的平均長度係可使用電子顯微鏡及顯像處理軟體,於樹脂薄片的任意之數處,測定毛狀體的高度及毛狀體的長度,使用其測定值的算術平均值。
毛狀體的平均直徑(d)較佳為1μm~50μm,更佳為5μm~30μm。由於將毛狀體的平均直徑設為1μm以上,可確保良好觸感性,由於將毛狀體的平均直徑設為50μm以下,可得到濕潤感、柔軟感、蓬鬆感等之良好觸感性。毛狀體的平均直徑係使用電子顯微鏡及顯像處理軟體,從樹脂薄片之數處,測定毛狀體的中間高度(h/2)的直徑,使用其測定值的算術平均值之值。
又,毛狀體的縱橫比係可以(毛狀體的平均高度/毛狀體的平均直徑)表示。毛狀體的縱橫比較佳為2~20,更佳為2~10,尤佳為2~5。由於將縱橫比設為2以上,可確保良好觸感性,由於將縱橫比設為20以下,不僅得到濕潤感、柔軟感、蓬鬆感等之良好觸感性,而且可減少毛狀體的高度對長度之比成為一定以下之虞。
另一方面,縱橫比亦可以毛狀體的平均底面直徑為基準。毛狀體的平均底面直徑較佳為10μm~150μm。毛狀體的平均底面直徑係於樹脂薄片的數處中,測定鄰接的毛狀體之間隔,使用其測定值的算術平均值之值。以毛狀體的底面直徑為基準時之縱橫比,較佳為1.0~10,更佳為1.0~5,尤佳為1.0~2.5。由於將縱橫比設為1.0以上,可確保良好觸感性,由於將縱橫比設為10以下,不僅得到濕潤感、柔軟感、蓬鬆感等之良好觸感性,而且可減少毛狀體的高度對長度之比變成一定以下之虞。
毛狀體的平均間隔(t)較佳為20μm~200μm,更佳為40μm~150μm。所謂毛狀體的間隔,就是意指毛狀體的根部之中心與鄰接的毛狀體的根部之中心的距離。由於將平均間隔設為20μm以上,可確保良好觸感性,由於設為200μm以下,可得到濕潤感、柔軟感、蓬鬆感等之良好觸感性。毛狀體的平均間隔係在樹脂薄片之數處中,測定鄰接之毛狀體的間隔,使用其測定值的算術平均值之值。
毛狀體之形狀係沒有特別的限定,但可為在離開基底層的方向中伸展成毛狀,隨著接近前端而逐漸變細之形狀,或於其前端形成有鼓起之構成。即,可隨著離開基底層,剖面積逐漸變小後,一旦變大後終結之形狀。又,毛狀體的前端部之形狀可為花蕾狀或蘑菇形狀。另外,毛狀體可具有:位於在離開基底層的方向中延伸出的基端之部分,與從位於該基端部分延伸出而以一定的曲率或使曲率逐漸變化而彎曲之部分,還可進一步具有被捲為螺旋狀或漩渦狀的部分。於此情況下,亦可為毛狀體之前端部被折入內側之形狀。藉由為這樣的形狀,展現良好的觸感。又,藉由花蕾狀或蘑菇形狀的部分為中空,展現更良好的觸感。將花蕾狀或蘑菇形狀形成在毛狀前端時,花蕾狀或蘑菇形狀之寬度的平均直徑相對於毛狀體的平均直徑之比較佳為1.1倍以上。花蕾狀或蘑菇形狀的高度較佳為7μm以上。毛狀體的平均直徑、花蕾狀或蘑菇形狀之寬度的平均直徑、高度係由電子掃描型顯微鏡照相來測定,為使用算術平均值之值。毛狀體包含熱塑性樹脂。作為熱塑性樹脂,可使用與在上述基底層所可用的樹脂同樣之樹脂。
基底層及毛狀體所含有的熱塑性樹脂係可至少部分地形成三次元的交聯結構(例如三次元網狀結構)。例如,於某一實施形態中,毛狀體之至少一部分係成為交聯體,於另一實施形態中,毛狀體之表面全體係成為交聯體,於更另一實施形態中,毛狀體之全體(從與基底層的邊界到前端部)係成為交聯體。作為形成交聯體之方法,例如可舉出在形成樹脂薄片後,將電子線照射至具有毛狀體之面的方法,或添加有機過氧化物,在樹脂薄片之成形時或成形後,藉由加熱及加濕而形成的方法。作為已添加有機過氧化物的樹脂,於市售品中,可舉出三菱化學公司製「Linklon」等。於本實施形態中,較佳為藉由電子線的照射而形成交聯體(電子線交聯體)。
<樹脂薄片>
於本發明之一實施形態中,所謂樹脂薄片的厚度,就是指將毛狀體的平均高度與基底層的平均厚度合計之薄片厚度。薄片厚度較佳為50μm~1500μm,更佳為50~1050μm,尤佳為120~500μm。由於將厚度設為50μm以上,可充分確保良好觸感性,由於設為1500μm以下,可降低製造成本。
於本實施形態中,所謂「觸感性」,就是意指樹脂薄片之表面的質感、肌膚觸感。判斷於觸摸了樹脂薄片表面之際是否可感到舒適度,感到時,將濕潤、柔軟、蓬鬆等之具體的肌膚觸感良好者當作良好觸感。又,良好觸感性係除了肌膚觸感等之感官試驗以外,還可藉由樹脂薄片的摩擦係數(MIU)、摩擦係數之變動(MMD)、粗糙度之變動(SMD)或前述縱橫比來規定。
於本實施形態中,摩擦係數(MIU)係依照KES法測定。從兼顧賦予樹脂薄片舒適的觸感與薄膜的生產性之觀點來看,具有毛狀體的表面之摩擦係數較佳為0.5以上1.0以下,更佳為0.6以上0.79以下,尤佳為0.65以上0.78以下。若依照KES法測定的摩擦係數小於0.5,則有時薄膜不具有舒適的觸感,另外若超過1.0,則薄膜的滑動性不足,在製程中將薄膜捲繞成捲筒狀時氣體排除係變差,因此有發生捲繞形狀不良之情況。
再者,上述摩擦係數係可藉由選擇樹脂薄片的原料或變更毛狀體的高度而達成。
於本實施形態中,摩擦係數之變動(MMD)係依照KES法測定。為了賦予薄膜光滑的觸感,薄片具有毛狀體的表面之摩擦係數之變動較佳為0.010以上0.025以下,更佳為0.012以上0.022以下,尤佳為0.013以上0.021以下。若依照KES法測定的摩擦係數之變動小於0.010,則可能無法感受毛狀體之獨特的觸感。又,若超過0.025,則在觸摸時可能手指卡住,可能無法感受光滑度。
再者,上述摩擦係數之變動係可藉由選擇樹脂薄片的原料或變更毛狀體的高度而達成。
於本實施形態中,粗糙度之變動(SMD)係依照KES法測定。可間接地確認薄膜表面之形狀,薄片具有毛狀體的表面之粗糙度之變動較佳為0.2以上1.5以下,更佳為0.22以上1.0以下,尤佳為0.24以上0.7以下。若依照KES法測定的粗糙度之變動小於0.2,則接近平坦的表面形狀,有無法感受毛狀體之獨特的觸感之可能性,又若超過1.5,則有表面形狀粗糙而不光滑之觸感的可能性。
再者,上述粗糙度之變動係可藉由變更毛狀體的高度或形狀而達成。
於本發明之一實施形態中,具有毛狀體的面中之依照KES法測定的摩擦係數與依照KES法測定的摩擦係數之變動之比(MIU/MMD)較佳為40以上且小於55,更佳為42以上且小於55,尤佳為44以上且小於55。具有毛狀體的面之MIU/MMD高時,雖然感受更光滑的肌膚觸感柔軟之毛的觸感性,但是55以上時,觸摸時可能感受到手指被卡住。具有毛狀體的面之MIU/MMD低時,為乾燥的觸感而感覺不到濕潤感。
於本發明之另一實施形態中,使用氙燈式促進耐候性試驗機,於黑色面板溫度63℃、放射照度60W/m2
下照射500小時後之試驗前後的毛狀體及基底層之色差ΔE較佳為10以下,更佳為5以下,尤佳為3以下。若毛狀體及基底層之色差ΔE為10以下,則縱然使用於照射紫外線光等之場所也變色少,因此適用作為汽車內裝材料等。
[第二實施形態]
作為本發明之第二實施形態的樹脂薄片之例,如圖5所示,為在基底層(1)與基材層(3)之間形成有密封樹脂層(2)之樹脂薄片。即,第二實施形態之樹脂薄片的層構成係從上到下為毛狀體及基底層(1)、密封樹脂層(2)、基材層(3)。此處,毛狀體係與第一實施形態中說明者相同,故省略說明。但是,以毛狀體的平均高度及基底層的平均厚度之合計所表示之毛狀體及基底層的厚度,較佳為150μm~1500μm,更佳為150μm~1050μm,尤佳為150μm~500μm。由於設為150μm以上,可確保良好觸感性,由於設為1500μm以下,可降低生產成本。
<基材層>
基材層較佳為苯乙烯系樹脂、烯烴系樹脂、聚酯系樹脂、尼龍系樹脂、丙烯酸系樹脂、熱塑性彈性體等之熱塑性樹脂。又,積層時,有藉由共擠出成形之積層或藉由使用無延伸薄膜、雙軸延伸薄膜的擠出層壓成形、乾層壓成形之積層。
作為聚酯系樹脂,可使用聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚2,6-萘二甲酸乙二酯、聚對苯二甲酸甲二酯,及作為共聚合成分,例如可使用二乙二醇、新戊二醇、聚烷二醇等二醇成分或己二酸、癸二酸、鄰苯二甲酸、間苯二甲酸、2,6-萘二甲酸等二羧酸成分等共聚合成的聚酯樹脂等。
作為尼龍系樹脂,可使用己內醯胺、月桂內醯胺等之內醯胺聚合物、6-胺基己酸、11-胺基十一酸、12-胺基十二酸等之胺基羧酸的聚合物、六亞甲基二胺、十亞甲基二胺、十二亞甲基二胺、2,2,4-或2,4,4-三甲基六亞甲基二胺等之脂肪族二胺、1,3-或1,4-雙(胺基甲基)環己烷、雙(對胺基環己基甲烷)等之脂環式二胺、m-或p-苯二甲基二胺等之芳香族二胺等的二胺單元、與己二酸、辛二酸、癸二酸等之脂肪族二羧酸、環己烷二羧酸等之脂環式二羧酸、對苯二甲酸、間苯二甲酸等之芳香族二羧酸等之二羧酸單元的聚縮合物、及此等之共聚物等。例如有尼龍6、尼龍9、尼龍11、尼龍12、尼龍66、尼龍610、尼龍611、尼龍612、尼龍6T、尼龍6I、尼龍MXD6、尼龍6/66、尼龍6/610、尼龍6/6T、尼龍6I/6T等,其中較佳為尼龍6、尼龍MXD6。
只要是以甲基丙烯酸酯單體為基礎的乙烯基聚合物,則可作為丙烯酸系樹脂使用,其結構等係沒有特別的限定。作為甲基丙烯酸酯單體,例如可舉出甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸戊酯及甲基丙烯酸己酯等。又,甲基丙烯酸酯單體中的丙基、丁基、戊基及己基等烷基係可為直鏈,也可為分支。甲基丙烯酸酯樹脂可為甲基丙烯酸酯單體之均聚物、或複數的甲基丙烯酸酯單體之共聚物,也可具有來自甲基丙烯酸酯以外之眾所周知的乙烯基化合物之乙烯、丙烯、丁二烯、苯乙烯、α-甲基苯乙烯、丙烯腈及丙烯酸等的單體單元。
於基材層中,視需要在不妨礙本發明的效果之範圍內,亦可與上述各熱塑性樹脂以任意之比例摻合。再者,也可含有其它的添加物。作為其它的添加物,在不妨礙本發明的效果之範圍內,可添加如撥水・撥油劑、顏料、染料等之著色劑、矽油或烷酯系等之脫模劑、玻璃纖維等之纖維狀強化劑、滑石、黏土、矽石等之粒狀滑劑、磺酸與鹼金屬等之鹽化合物或抗靜電劑、紫外線吸收劑、難燃劑、抗菌劑之添加劑等。又,亦可混合使用樹脂薄片製程中所產生的廢料樹脂。
又,於實施形態中,在不妨礙本發明的效果之範圍內,基材層亦可部分地具有交聯結構。
於本實施形態中,基材層的平均厚度較佳為50μm~1500μm,更佳為100μm~1000μm,尤佳為150μm~500μm。由於設為50μm以上,製膜步驟變容易,由於設為1500μm以下,可降低生產成本。
<密封樹脂層>
密封樹脂層係用於展現基底層與基材層之接著性者,作為樹脂成分,可使用改質烯烴系樹脂、氫化苯乙烯系熱塑性彈性體等。
作為改質烯烴系樹脂,可使用乙烯、丙烯、丁烯-1等碳數2~8左右的烯烴、彼等的烯烴與乙烯、丙烯、丁烯-1、3-甲基丁烯-1、戊烯-1、4-甲基戊烯-1、己烯-1、辛烯-1、癸烯-1等碳數2~20左右的其它烯烴之共聚物,或與乙酸乙烯酯、氯乙烯、丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯、苯乙烯等乙烯基化合物之共聚物等烯烴系樹脂,或將乙烯-丙烯共聚物、乙烯-丙烯-二烯共聚物、乙烯-丁烯-1共聚物、丙烯-丁烯-1共聚物等之烯烴系橡膠,以丙烯酸、甲基丙烯酸、巴豆酸、異巴豆酸、馬來酸、富馬酸、伊康酸、檸康酸、四氫鄰苯二甲酸等不飽和羧酸、或其醯鹵、醯胺、醯亞胺、酐、酯等之衍生物,具體而言以馬來醯氯、馬來醯亞胺、馬來酸酐、檸康酸酐、馬來酸單甲酯、馬來酸二甲酯、馬來酸環氧丙酯等,在接枝反應條件下改質者。
其中,經不飽和二羧酸或其酐,尤其馬來酸或其酐所改質的「乙烯-丙烯-二烯共聚物」或乙烯-丙烯或丁烯-1共聚物橡膠係較宜。
作為氫化苯乙烯系熱塑性彈性體,可舉出苯乙烯系單體與丁二烯或異戊二烯的共聚物之氫化物、苯乙烯-丁二烯-苯乙烯嵌段共聚物之氫化物(苯乙烯-乙烯・丁烯-苯乙烯嵌段共聚物)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物之氫化物(苯乙烯-乙烯・丙烯-苯乙烯嵌段共聚物)等,特佳為苯乙烯-乙烯・丁烯-苯乙烯嵌段共聚物。
密封樹脂層的平均厚度較佳為20~90μm,更佳為40~80μm。由於設為20μm以上,可抑制在基底層與基材層間發生層間剝離,由於設為90μm以下,可降低生產成本。
於密封樹脂層中,視需要在不妨礙本發明的效果之範圍內,可將上述各熱塑性樹脂以任意之比例摻合。再者,亦可含有其它的添加物。作為其它的添加物,在不妨礙本發明的效果之範圍內,可添加如撥水劑、撥油劑、顏料、染料等之著色劑、矽油或烷酯系等之滑材・脫模劑、玻璃纖維等之纖維狀強化劑、作為填充劑的滑石、黏土、矽石等之粒狀微粒子或雲母等之鱗片狀微粒子、磺酸與鹼金屬等之鹽化合物等之低分子型抗靜電劑或聚醚酯醯胺等之高分子型抗靜電劑、紫外線吸收劑、難燃劑、抗菌劑、抗病毒劑、熱安定劑之添加劑等。又,於本實施形態中,在不妨礙本發明的效果之範圍內,密封樹脂層亦可部分地具有交聯結構。
[第三實施形態]
本發明之第三實施形態的樹脂薄片係如圖6所示,不使用第二實施形態所示的密封樹脂層(2),而是將毛狀體及基底層(1)與基材層(3)直接積層者。即,第三實施形態的樹脂薄片之層構成係從上到下為毛狀體及基底層(1)/基材層(3),具有從第二實施形態的熱塑性樹脂薄片去除密封樹脂層後的層構成。此處,毛狀體及基底層係與第一實施形態及第二實施形態中的層相同,故省略說明。另一方面,本實施形態中的基材層(3)較佳為具備與基底層的充分接著性者。
又,於第三實施形態之樹脂薄片中,作為基材層,較佳為使用與基底層的接著性優異之熱塑性樹脂。例如,基底層為氟系樹脂時,可使用丙烯酸系樹脂,基底層為烯烴系樹脂時,亦可使用加有氫化苯乙烯系熱塑性彈性體之苯乙烯系樹脂組成物。併用耐衝擊性聚苯乙烯樹脂與氫化苯乙烯系熱塑性彈性體時,相對於耐衝擊性聚苯乙烯樹脂為90~95質量份,較佳為添加5~10質量份的氫化苯乙烯系熱塑性彈性體。此時,由於氫化苯乙烯系熱塑性彈性體之添加量為5質量份以上,而與基底層的接著性變充分,可抑制層間剝離之發生,由於為10質量份以下,可降低生產成本。
於基材層中,如與第二實施形態相同,在不妨礙本發明的效果之範圍內,可將上述各熱塑性樹脂以任意之比例摻合。再者,亦可含有其它的添加物。作為其它的添加物,在不妨礙本發明的效果之範圍內,可添加如撥水劑、撥油劑、顏料、染料等之著色劑、矽油或烷酯系等之滑材・脫模劑、玻璃纖維等之纖維狀強化劑、作為填充劑的滑石、黏土、矽石等之粒狀微粒子或雲母等的鱗片狀微粒子、磺酸與鹼金屬等的鹽化合物等之低分子型抗靜電劑或聚醚酯醯胺等之高分子型抗靜電劑、紫外線吸收劑、難燃劑、抗菌劑、抗病毒劑、熱安定劑之添加劑等。又,於本實施形態中,在不妨礙本發明的效果之範圍內,基材層亦可部分地具有交聯結構。
[樹脂薄片之製造]
本發明之樹脂薄片之製造方法係沒有限定,可藉由任何的方法,但典型上包含將原料樹脂熔融擠出,賦予在所得之擠出樹脂薄片的至少一面上規則排列的毛狀體之步驟。
製作單層薄片或多層樹脂薄片時,可使用任意的樹脂薄片成形方法。例如可舉出:單層時係使用1台的單軸擠壓機,複層時係使用複數台的單軸擠壓機,將各個原料樹脂熔融擠出,藉由T字模得到樹脂薄片之方法。多層時可使用供料頭(feed block)或多歧管模頭。還有,本發明之樹脂薄片之各實施形態的層構成係基本上如前述,但此外例如只要未見到物性等之劣化,則可將本發明之樹脂薄片或成形容器之製程中所產生的廢料原料添加至基材層,也可積層作為另一層。
賦予毛狀體之方法係沒有特別的限制,可使用本業者所已知的任意之方法。例如,使用擠出成形方式進行製造之方法,使用輥對輥方式進行製造之方法,使用光微影方式進行製造之方法,使用熱壓方式進行製造之方法,使用圖案輥與UV硬化樹脂進行製造之方法,使用3D列印機進行製造之方法,將毛狀體埋入樹脂層中後,藉由聚合反應使其共價鍵結之方法等。
例如,使用擠出成形方式時,可藉由T字模法,擠出樹脂薄片,以將毛狀體形狀賦予至該樹脂薄片之表面的方式,藉由完成凹凸加工的轉印輥與接觸輥進行鑄造,而製造本發明之樹脂薄片。
作為完成凹凸加工的轉印輥,可使用藉由雷射雕刻法或電鑄法、蝕刻法、鋼蕊雕刻法(mill engraving method)等,於輥之表面規則地施予數μm~數百μm大小的微細凹凸者。此處,所謂規則地,就是凹凸為非無規的排列狀態,亦即於一方向或二方向中整齊排列之狀態。作為某一實施形態中的凹凸之配置,可選擇縱橫配置的棋盤格配置或交錯配置等。作為凹凸部之形狀,例如若為凹部的形狀,則可舉出錐形(圓錐、四角錐、三角錐、六角錐等)、半圓形、矩形(四角柱)等。尺寸係凹部的開口徑、凹部深度、凹部形狀的間隔為數μm至數百μm。作為轉印輥之材質,例如可使用金屬、陶瓷等。可藉由調節轉印輥之凹部的間隔而調節毛狀體的間隔,可藉由調節轉印輥之凹部深度而調節毛狀體高度,亦可藉此而調節觸感。
又,較佳為對轉印輥表面進行高縱橫比的凹凸加工。例如,對轉印輥表面加工凹部形狀時的縱橫比(凹部深度/凹部開口徑)較佳為1.0~9.0。為了對轉印輥表面進行高縱橫比的凹凸加工,相較於蝕刻法或噴砂法、鋼蕊雕刻法等,雷射雕刻法或電鑄法由於較適合於在深度方向中進行精密加工之情況,故特宜使用。
作為轉印輥之材質,例如可使用金屬、陶瓷等。另一方面,作為接觸輥,可使用各式各樣的材質,例如可使用矽系橡膠、NBR系橡膠、EPT系橡膠、丁基橡膠、氯平橡膠、氟橡膠製之輥。於某一實施形態中,可使用橡膠硬度(JIS K 6253)40~100的接觸輥。又,亦可於接觸輥之表面上形成鐵氟龍(註冊商標)層。
又,作為接觸輥,可使用各式各樣的材質,例如可使用矽系橡膠、NBR系橡膠、EPT系橡膠、丁基橡膠、氯平橡膠、氟橡膠製之輥。於某一實施形態中,可使用橡膠硬度(JIS K 6253)40~100的接觸輥。又,亦可於接觸輥之表面上形成鐵氟龍(註冊商標)層。
藉由使用上述轉印輥及接觸輥之輥組,可製造本實施形態之樹脂薄片。
於某一實施形態中,藉由將轉印輥的溫度調節至熱塑性樹脂的結晶熔解溫度、玻璃轉移點或熔點附近的溫度(例如,使用無規聚丙烯時為100~150℃),將轉印輥與接觸輥之夾壓設為30~120Kg/cm2
而進行鑄造,可製造本實施形態之樹脂薄片。經鑄造的樹脂薄片係使用夾送輥等,以0.5~30m/分鐘之線速度牽引。
又,雖然已具體地顯示上述實施形態,但不受該等所限定。
[成形品]
本發明之成形品係使用本發明之樹脂薄片之成形品。本發明之樹脂薄片係可對應於一般的成形,作為成形方法,除了插入成形、模內成形之外,還有一般的真空成形、加壓成形,或作為此等之應用,可舉出使樹脂薄片在真空狀態化下加熱軟化,在大氣壓下開放而覆蓋(成形)至既有的成形品表面之方法等,但不受此等所限定。又,作為在成形前使薄片加熱軟化之方法,可採用非接觸加熱的紅外線加熱器等之輻射加熱等眾所周知之薄片加熱方法。於某一實施形態的真空加壓成形中,例如樹脂薄片係在表面溫度為60℃~220℃,加熱20秒~480秒後,成形到既有的成形品表面,依照表面的形狀,可被延伸至1.05~2.50倍。
[物品]
本發明之在表面上賦予有毛狀體之樹脂薄片,係可適用於需要前述所示的良好觸感性之用途。例如,本發明之樹脂薄片係可適用作為汽車內裝材料、電子機器、電子機器外裝材料、化妝品容器或容器構件、文具構件、照明器具構件、生活用品構件。
作為汽車內裝材料,於汽車車內手觸摸的部分,可舉出方向盤、儀表板、操縱桿、開關等。例如,可舉出在眾所周知的儀表板、支柱(例如日本特開2009-184421號公報)的表面上,例如進行真空加壓成形而貼合有上述樹脂薄片之內裝材料。藉由貼合樹脂薄片,可成為賦予有良好觸感性的內裝材料。作為貼合的樹脂薄片之材質,考慮耐候性、耐化學性,較佳為烯烴系樹脂、氯乙烯系樹脂、胺基甲酸酯系彈性體。貼合樹脂薄片與內裝材料之方法係沒有特別的限定。
作為電子機器外裝材料,可舉出免鑰匙登錄系統(keyless entry system)的發訊機殼體、智慧型手機殼體、智慧型手機外殼、音樂播放器盒、遊戲機殼體、數位相機殼體、電子筆記本殼體、電子計算機殼體、平板電腦殼體、攜帶型個人電腦殼體、鍵盤、滑鼠等。例如,可舉出在眾所周知的免鑰匙登錄系統的攜帶用發訊機殼體(例如日本特開2005-228911號公報)的表面上,例如進行真空加壓成形而貼合有本發明樹脂薄片之攜帶用發訊機。藉由貼合樹脂薄片,可成為賦予有良好觸感性的攜帶用發訊機。作為貼合的樹脂薄片之材質,較佳為烯烴系樹脂、胺基甲酸酯系彈性體。貼合樹脂薄片與殼體之方法係沒有特別的限定。
作為化妝品容器構件,可舉出面霜、敷料乳霜、粉底、眼影的容器,例如可舉出於眾所周知的粉底用容器(日本特開2017-29608號公報)之蓋構件的表面上,例如進行真空加壓成形而貼合有本發明樹脂薄片之化妝品容器。藉由貼合樹脂薄片,可成為賦予有良好觸感性的化妝品容器。作為貼合的樹脂薄片之材質,較佳為烯烴系樹脂、胺基甲酸酯系彈性體。與樹脂薄片貼合之方法係沒有特別的限定。
作為文具構件,可舉出書套、筆記本套、筆盒套等,例如可使用本發明樹脂薄片製作眾所周知的書套(例如日本特開2007-246122號公報),而成為賦予有良好觸感性、防水性之書套。又,書套形態係沒有特別的限定。作為薄片之材質,較佳為烯烴系樹脂、胺基甲酸酯系彈性體。使用樹脂薄片製作之方法係沒有特別的限定。
作為照明機器構件,可舉出室內用、車內用的照明機器,例如可舉出於眾所周知的LED照明裝置之蓋構件的表面上,例如進行真空加壓成形而貼合有本發明樹脂薄片之照明裝置。藉由貼合樹脂薄片,可成為賦予有良好觸感性、光的擴散性之LED照明裝置。作為貼合的樹脂薄片之材質,較佳為烯烴系樹脂、氟系樹脂。與樹脂薄片貼合之方法係沒有特別的限定。
作為生活用品構件,可舉出廁所用品、室內用墊、桌子用薄片等,例如可舉出於廁所裝置的馬桶座構件之表面上,例如進行真空加壓成形而貼合有本發明樹脂薄片之廁所裝置。藉由貼合樹脂薄片,可成為賦予有良好觸感性的馬桶座之廁所裝置。作為貼合的樹脂薄片之材質,較佳為烯烴系樹脂、氯乙烯系樹脂、氟系樹脂。與樹脂薄片貼合之方法係沒有特別的限定。
再者,製作以一般的印刷方法(平版印刷法、凹版印刷法、柔版印刷法、網版印刷法、燙金等)在毛狀體之表面上印刷有文字、圖樣之毛狀體薄片,可適用於上述之用途。作為印刷的樹脂薄片之材質,並沒有特別的限定,但較佳為考慮與印刷所使用的油墨劑之印刷性。
又,本發明樹脂薄片係可製作與印刷有文字、圖樣等的印刷物(紙、金屬薄膜等)、不織布等進行層壓成形(乾層壓成形、擠出層壓成形)而成的積層體,例如,可在名片的印刷面上層壓成形,製作具有觸感性的名片。層壓的樹脂薄片之材質係沒有特別的限定。
[實施例]
以下,舉出實施例及比較例來更具體地說明本發明,但本發明完全不受實施例等之內容所限定。
實施例等所用之各種原料係如以下。
(1)毛狀體及基底層
・(A-1)TPU(胺基甲酸酯系彈性體)「XN2001:聚碳酸酯系」(東曹公司製)
・(A-2)TPU(胺基甲酸酯系彈性體)「HD1085A:聚碳酸酯系」(BASF公司製)
・(A-3)TPU(胺基甲酸酯系彈性體)「ET880:聚醚系」(BASF公司製)
・(B)直鏈狀低密度PE「NEO-ZEX 45200」(Prime Polymer公司製)
・(C)脫模劑母料「Wax Master V」(BASF公司製)
(2)密封樹脂層
・(D-1)氫化苯乙烯系熱塑性彈性體「Tuftec M1943」(旭化成化學公司製)
・(D-2)氫化苯乙烯系熱塑性彈性體「Tuftec P2000」(旭化成化學公司製)
(3)基材層
・(E-1)ABS「Denka ABS GT-R-61A」(DENKA公司製)
・(E-2)PC/ABS「IM 6011」(住化聚碳酸酯公司製)
・(E-3)直鏈狀低密度PE「NEO-ZEX 45200」(Prime Polymer公司製)
・(E-4)HIPS「Toyo Styrol H850N」(東洋苯乙烯公司製,丁二烯含量9.0質量%)
(4)市售品薄片
・(F-1)人工皮革「Ultrasuede」(東麗公司製)
・(F-2)毛氈「Feltence」(AMBIC公司製,羊毛60%嫘縈40%)
・(F-3)PVC合成皮革「Hi Largo」(SINCOL公司製)
對於實施例及比較例所製作的樹脂薄片與將該樹脂薄片真空加壓成形的成形品之各種特性之評價方法係如以下。
(1)耐候性試驗
對於毛狀體及基底層之熱塑性樹脂原料,藉由熱壓機製作厚度約0.3mm的薄片,以氙燈式促進耐候性試驗機(氙燈耐候計,SUGA試驗機製),於黑色面板溫度63±3℃、照射強度60W/m2
下照射500小時,使用色差計Color meter ZE6000(日本電色工業製),測定薄片的試驗前後之色差(透過法)ΔE。
(2)毛狀體的平均高度、毛狀體的平均長度、毛狀體的平均直徑、毛狀體的平均間隔、基底層的平均厚度
使用雷射顯微鏡(VK-X100,KEYENCE公司製),測定樹脂薄片之毛狀體的高度(h)、毛狀體的直徑(d)、毛狀體的間隔(t)、基底層的厚度。還有,所測定之試料係使用切片機,從樹脂薄片的任意3處切出剖面切片而使用。毛狀體的平均高度係對於各自的試料,測定毛狀體10個的高度,使用其30測定值的算術平均值。關於毛狀體的平均直徑,對於各自的試料,測定10個毛狀體的中間高度(h/2)之直徑,使用其30測定值的算術平均值。關於毛狀體的平均間隔,對於各自的試料,測定10處的毛狀體的根部之中心與鄰接之毛狀體的根部之中心的距離,使用其30測定值的算術平均值。關於基底層的平均厚度,對於各自的試料,測定10處的從毛狀體的根部到另一方的層界面為止之厚度,使用其30測定值的算術平均值。
(3)摩擦係數(MIU)
使用質感試驗機「KES-FB4-A表面試驗機(Kato Tech製)」,將20cm×20cm之大小的樹脂薄片,以賦予有毛狀體形狀之面朝上,安裝於試驗台,以荷重25gf、1mm/sec之速度,使測定頭在樣品之表面上移動,於室溫23℃、相對濕度50%的環境之條件下測定薄片的摩擦係數(MIU)。機械方向、寬度方向皆進行3次(合計6次)的測定,將其全部數據的平均值之小數第3位予以四捨五入後之值當作該薄片的摩擦係數。再者,作為接觸頭,使用標準摩擦件(指紋型)。
(4)摩擦係數之變動(MMD)
使用質感試驗機「KES-FB4-A表面試驗機(Kato Tech製)」,將20cm×20cm之大小的樹脂薄片,以賦予有毛狀體形狀之面朝上,安裝於試驗台,以荷重25gf、1mm/sec之速度,使測定頭在樣品之表面上移動,於室溫23℃、相對濕度50%的環境之條件下,測定薄片的摩擦係數之變動(MMD)。機械方向、寬度方向皆進行3次(合計6次)的測定,將其全部數據的平均值之小數第4位予以四捨五入後之值當作該薄片的摩擦係數之變動。再者,作為接觸頭,使用標準摩擦件(指紋型)。
(5)表面粗糙度之變動(SMD)
使用質感試驗機「KES-FB4-A表面試驗機(Kato Tech製)」,將20cm×20cm之大小的樹脂薄片,以賦予有毛狀體形狀之面朝上,安裝於試驗台,以荷重10gf、1mm/sec之速度,使測定頭在樣品之表面上移動,於室溫23℃、相對濕度50%的環境之條件下,測定薄片的表面粗糙度之變動(SMD)。機械方向、寬度方向皆進行3次(合計6次)的測定,將其全部數據的平均值之小數第4位予以四捨五入後之值當作該薄片的表面粗糙度之變動。再者,作為接觸頭,使用1條的直徑0.5mm之鋼琴線。
(6)良好觸感性感官評價
良好觸感性係實施請男性5人、女性5人之合計10人觸摸樹脂薄片之感官評價。以觸摸樹脂薄片表面時之具體的觸感(光滑度或濕潤感等)進行評價,將最多人數所感受到的觸感當作該樹脂薄片表面之觸感。
(7)真空加壓成形
以雙面真空成形機(NGF-0709-S型:布施真空公司製),將樹脂薄片在真空環境下加熱,然後,對在大氣壓環境下所準備之智慧型手機外罩的表面進行真空加壓成形,藉此而製作成形品。以80℃加熱120秒鐘,在最被延伸的部位係延伸至1.5倍。
[實施例1、2、4~8]
從1台的40mm單軸擠壓機流出作為毛狀體及基底層的(A)熱塑性樹脂與(C)脫模劑之乾摻合品,從1台的65mm單軸擠壓機流出作為基材層的(E)熱塑性樹脂,將經由T字模法所擠出的樹脂薄片,使用以氧化鉻噴鍍且雷射雕刻法完成凹凸加工,且經調節至60~150℃的完成凹凸加工之轉印輥,與經調節至10~90℃的橡膠硬度70的矽系橡膠製接觸輥進行鑄造,使用夾送輥以線速度1m/分鐘~15m/分鐘來牽引。藉此,得到表1所示的組成、厚度及表面形狀之樹脂薄片。
[實施例3]
從1台的40mm單軸擠壓機流出作為毛狀體及基底層的(A)熱塑性樹脂與(C)脫模劑之乾摻合品,從1台的40mm單軸擠壓機流出作為密封樹脂層的(D)熱塑性樹脂,從1台的65mm單軸擠壓機流出作為基材層的(E)熱塑性樹脂,使用供料頭,將經由T字模法所擠出的樹脂薄片,使用以氧化鉻噴鍍且雷射雕刻法完成凹凸加工,且經調節至60~150℃的完成凹凸加工之轉印輥,與經調節至10~90℃的橡膠硬度70的矽系橡膠製接觸輥進行鑄造,使用夾送輥以線速度1m/分鐘~15m/分鐘來牽引。藉此,可得到表1所示的組成、厚度及表面形狀之樹脂薄片。
[實施例9]
從1台的40mm單軸擠壓機流出(A)熱塑性樹脂與(C)脫模劑之乾摻合品,將經由T字模法所擠出的樹脂薄片,使用以氧化鉻噴鍍且雷射雕刻法完成凹凸加工,且經調節至60~150℃的完成凹凸加工之轉印輥,與經調節至10~90℃的橡膠硬度70的矽系橡膠製接觸輥進行鑄造,使用夾送輥以線速度1m/分鐘~15m/分鐘來牽引。藉此,得到表1所示的組成、厚度及表面形狀之樹脂薄片。
[比較例1]
以熱壓機,作成(A)熱塑性樹脂與(C)脫模劑之乾摻合品的樹脂薄片。藉此,得到表1所示的組成、厚度及表面形狀之樹脂薄片。
[比較例2~4]
使用市售品薄片。
使用各實施例、比較例所得之樹脂薄片,對於各種特性實施評價試驗,表1中顯示結果。
[表1]
毛狀體及基底層 | 毛狀體 | 密封層 | 基材層 | 物性 | |||||||||||||||||
TPU (A-1) | TPU (A-2) | TPU (A-3) | LLDPE (B) | 脫模劑 (C) | 耐候性 (色差ΔE) | 平均高度,h (μm) | 平均直徑,d (μm) | 平均間隔,t (μm) | 熱塑性 彈性體 (D) | 熱塑性 彈性體 (D) | ABS (E-1) | PC /ABS (E-2) | LLDPE (E-3) | PS (E-4) | MIU | MMD | SMD | MIU/ MMD | 良好觸感性 | ||
實施例1 | 組成 (質量%) | 95 | - | - | - | 5 | 3 | 150 | 26 | 62 | - | - | 100 | - | - | - | 0.78 | 0.018 | 0.459 | 43.3 | 光滑、濕潤 |
厚度(μm) | 200(基底50+毛狀150) | - | 350 | ||||||||||||||||||
實施例2 | 組成 (質量%) | 95 | - | - | - | 5 | 3 | 102 | 32 | 64 | - | - | 100 | - | - | - | 0.75 | 0.015 | 0.490 | 50.0 | 光滑、濕潤 |
厚度(μm) | 130(基底50+毛狀100) | - | 350 | ||||||||||||||||||
實施例3 | 組成 (質量%) | 95 | - | - | - | 5 | 3 | 150 | 30 | 62 | 50 | 50 | - | - | - | 100 | 0.88 | 0.020 | 0.250 | 44.0 | 光滑、濕潤 |
厚度(μm) | 200(基底50+毛狀150) | 50 | 300 | ||||||||||||||||||
實施例4 | 組成 (質量%) | - | 95 | - | - | 5 | 3 | 200 | 25 | 63 | - | - | 100 | - | - | - | 0.90 | 0.021 | 0.413 | 42.9 | 光滑、濕潤 |
厚度(μm) | 250(基底50+毛狀200) | - | 350 | ||||||||||||||||||
實施例5 | 組成 (質量%) | - | 95 | - | - | 5 | 3 | 80 | 35 | 61 | - | - | 100 | - | - | - | 0.75 | 0.015 | 0.490 | 50.0 | 光滑、濕潤 |
厚度(μm) | 130(基底50+毛狀80) | - | 350 | ||||||||||||||||||
實施例6 | 組成 (質量%) | - | 95 | - | - | 5 | 3 | 150 | 28 | 62 | - | - | - | 100 | - | - | 0.76 | 0.018 | 0.570 | 42.2 | 光滑、濕潤 |
厚度(μm) | 200(基底50+毛狀150) | - | 350 | ||||||||||||||||||
實施例7 | 組成 (質量%) | - | 95 | - | - | 5 | 3 | 80 | 38 | 63 | - | - | - | - | 100 | - | 0.68 | 0.015 | 0.338 | 45.3 | 光滑、濕潤 |
厚度(μm) | 130(基底50+毛狀80) | - | 350 | ||||||||||||||||||
實施例8 | 組成 (質量%) | - | - | 95 | - | 5 | 30 | 150 | 32 | 63 | - | - | 100 | - | - | - | 0.85 | 0.022 | 0.450 | 38.6 | 光滑、濕潤 |
厚度(μm) | 200(基底50+毛狀150) | - | 350 | ||||||||||||||||||
實施例9 | 組成 (質量%) | - | - | - | 100 | - | 3 | 250 | 18 | 62 | - | - | - | - | - | - | 0.80 | 0.022 | 0.202 | 36.4 | 濕潤 |
厚度(μm) | 400(基底150+毛狀250) | - | - | ||||||||||||||||||
比較例1 | 組成 (質量%) | - | - | 95 | - | 5 | 30 | - | - | - | - | - | - | - | - | - | 2.70 | 0.041 | 0.212 | 65.9 | 黏稠 |
厚度(μm) | 300(沒形成毛狀體) | - | - | ||||||||||||||||||
比較例2 | 種類 | (F-1)人工皮革 | - | - | - | - | - | - | - | - | - | - | 1.45 | 0.030 | 2.610 | 48.3 | 粗糙、乾燥的 | ||||
厚度(μm) | 900 | - | - | ||||||||||||||||||
比較例3 | 種類 | (F-2)毛氈 | - | - | - | - | - | - | - | - | - | - | 1.18 | 0.020 | 2.920 | 59.0 | 粗糙、乾燥的 | ||||
厚度(μm) | 900 | - | - | ||||||||||||||||||
比較例4 | 種類 | (F-3)PVC合成皮革 | - | - | - | - | - | - | - | - | - | - | 1.12 | 0.021 | 2.020 | 53.3 | 粗糙 | ||||
厚度(μm) | 900 | - | - |
由表1中所示的結果可明顯得知以下者。
於實施例1~9之全部的樹脂薄片中,得到能滿足關於良好觸感性的評價物性之依照KES法測定的摩擦係數、摩擦係數之變動、粗糙度之變動的結果。相對於其,比較例1~4之樹脂薄片及市售品薄片係在依照KES法測定的摩擦係數、摩擦係數之變動、粗糙度之變動的任一者中,得不到能滿足的結果。
又,關於實施例1~9所得之樹脂薄片的形狀,使用電場發射型掃描電子顯微鏡(FE-SEM,日本電子股份有限公司JSM-7001F型)進行觀察。
由掃描電子顯微鏡影像,觀察到毛狀體彼此係不纏結,在一定方向中伸長。又,毛狀體之形狀係隨著離開基底層,剖面積逐漸變小之形狀,或於剖面積逐漸變小後,一旦變大後終結之形狀。另外,觀察到:隨著離開基底層,剖面積逐漸變小後,一旦變大後終結之形狀的毛狀體之前端部,係花蕾狀或蘑菇形狀,花蕾狀或蘑菇形狀的部分為一部分中空。藉由具有如此的形狀,推測能展現更良好的觸感。
以上,用各式各樣的實施形態說明了本發明,惟當然本發明之技術範圍係不受上述實施形態中記載的範圍所限定。所屬技術領域中具通常知識者明瞭可對於上述實施形態加以多樣的變更或改良。又,由專利申請範圍之記載可明知:那樣加以變更或改良之形態亦可包含於本發明之技術範圍中。
1:毛狀體及基底層
1a:基底層
1b:毛狀體
d:毛狀體直徑
h:毛狀體的高度
t:毛狀體的間隔
2:密封樹脂層
3:基材層
圖1係顯示本發明之第一實施形態的樹脂薄片之示意縱側剖面圖。
圖2係顯示本發明之第一實施形態的樹脂薄片之變形例之示意縱側剖面圖。
圖3係顯示本發明之第一實施形態的樹脂薄片之再一變形例之示意縱側剖面圖。
圖4係圖1的樹脂薄片之示意平面圖。
圖5係顯示本發明之第二實施形態的樹脂薄片之積層結構之示意縱側剖面圖。
圖6係顯示本發明之第三實施形態的樹脂薄片之積層結構之示意縱側剖面圖。
1:毛狀體及基底層
1a:基底層
1b:毛狀體
d:毛狀體直徑
h:毛狀體的高度
t:毛狀體的間隔
Claims (9)
- 一種樹脂薄片,其特徵為:具有在含有熱塑性樹脂的基底層之至少一面上規則排列的毛狀體,於具有毛狀體的面中,依照KES法測定的摩擦係數為0.5以上1.0以下,且依照KES法測定的摩擦係數之變動為0.010以上0.025以下,而且依照KES法測定的粗糙度之變動為0.2以上1.5以下。
- 如請求項1之樹脂薄片,其中毛狀體的平均高度為30μm以上500μm以下,毛狀體的平均直徑為1μm以上50μm以下,毛狀體的平均間隔為20μm以上200μm以下。
- 如請求項1或2之樹脂薄片,其中該依照KES法測定的粗糙度之變動為0.22以上1.0以下。
- 如請求項1至3中任一項之樹脂薄片,其中於具有毛狀體的面中,依照KES法測定的摩擦係數與依照KES法測定的摩擦係數之變動之比(MIU/MMD)為40以上且小於55。
- 如請求項1至4中任一項之樹脂薄片,其中使用氙燈式促進耐候性試驗機,於黑色面板溫度63℃、放射照度60W/m2 下照射500小時後之試驗前後的毛狀體及基底層之色差ΔE為10以下。
- 如請求項1至5中任一項之樹脂薄片,其中熱塑性樹脂含有聚碳酸酯系的胺基甲酸酯系彈性體。
- 一種如請求項1至6中任一項之樹脂薄片的成形品。
- 如請求項7之成形品,其係文具構件。
- 如請求項7之成形品,其係被真空加壓成形於汽車內裝材料、電子機器、電子機器外裝材料、化妝品容器或容器構件之表面。
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2020
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- 2020-03-25 KR KR1020217028745A patent/KR20210143179A/ko unknown
- 2020-03-25 JP JP2021509516A patent/JP7446284B2/ja active Active
- 2020-03-25 EP EP20777016.5A patent/EP3928955B1/en active Active
- 2020-03-25 WO PCT/JP2020/013374 patent/WO2020196638A1/ja unknown
- 2020-03-25 CN CN202080022696.1A patent/CN113631351B/zh active Active
- 2020-03-26 TW TW109110233A patent/TW202041356A/zh unknown
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EP3928955A4 (en) | 2022-04-06 |
EP3928955B1 (en) | 2023-03-22 |
JP7446284B2 (ja) | 2024-03-08 |
JPWO2020196638A1 (zh) | 2020-10-01 |
CN113631351A (zh) | 2021-11-09 |
CN113631351B (zh) | 2023-07-04 |
WO2020196638A1 (ja) | 2020-10-01 |
KR20210143179A (ko) | 2021-11-26 |
US20220184917A1 (en) | 2022-06-16 |
EP3928955A1 (en) | 2021-12-29 |
US11987032B2 (en) | 2024-05-21 |
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