TW202028002A - 活性能量射線硬化性樹脂組成物 - Google Patents
活性能量射線硬化性樹脂組成物 Download PDFInfo
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- TW202028002A TW202028002A TW109110232A TW109110232A TW202028002A TW 202028002 A TW202028002 A TW 202028002A TW 109110232 A TW109110232 A TW 109110232A TW 109110232 A TW109110232 A TW 109110232A TW 202028002 A TW202028002 A TW 202028002A
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Abstract
一種防霧防污層積體,其係包含:基材;表面平滑的防霧防污層,其位於該基材上; 該防霧防污層係藉由活性能量射線來將活性能量射線硬化性樹脂組成物硬化後之硬化物;該活性能量射線硬化性樹脂組成物係含有:具有自由基聚合性不飽和基團的親水性單體、及光聚合起始劑;其中,該活性能量射線硬化性樹脂組成物中,該具有自由基聚合性不飽和基團的親水性單體的含有量係60質量%以上;及該防霧防污層的表面之純水接觸角為90°以上。
Description
本發明係關於一種具有防霧性與防污性,可使用於建築用途、產業用途、汽車用途、光學用途、太陽能電池面板等廣泛範圍,且容易成形加工之防霧防污層積體、使用該防霧防污層積體之物品及其製造方法、使用該防霧防污層積體之防污方法、以及可使用於該防霧防污層積體的製造之活性能量射線硬化性樹脂組成物。
一直以來,為了裝飾與保護各種物品的表面,而於物品的表面黏合樹脂薄膜、玻璃等。
然而,因為存在著那些為了裝飾與保護物品的表面之樹脂薄膜、玻璃等產生霧化及被污染的情形,而使物品的可辨認性與美觀性下降。
因此,為了防止如此所造成之物品的可辨認性與美觀性下降,於該樹脂薄膜、玻璃施以防霧處理。
舉例來說,有人提出了一種防霧性披膜形成基材,於該基材表面,按照順序層積了作為基底層之矽烷系耦合劑層、作為吸水層之有機無機複合覆膜、作為保護層之疏水加工層(例如,參照專利文獻1)。
然而,因為此提案的技術係於基材表面層積了基底層、吸水層、及保護層3層,故存在製造效率低的問題。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特許公開第2001-233638號公報
[發明所欲解決的課題]
本發明係以解決習知的前述多個問題來達成以下目的,以作為課題。意即,本發明之目的係提供一種具有優異的防霧性與防污性,且製造效率亦優異之防霧防污層積體、使用該防霧防污層積體之物品及其製造方法、使用該防霧防污層積體之防污方法、以及可使用於該防霧防污層積體的製造之活性能量射線硬化性樹脂組成物。
[用於解決課題之手段]
作為解決前述課題的手段而言,如以下所述。意即,
<1> 一種防霧防污層積體,其係包含:
基材;
表面平滑的防霧防污層,其位於該基材上;
該防霧防污層係藉由活性能量射線來將活性能量射線硬化性樹脂組成物硬化後之硬化物;
該活性能量射線硬化性樹脂組成物係含有:具有自由基聚合性不飽和基團的親水性單體、及光聚合起始劑;其中,
該活性能量射線硬化性樹脂組成物中,該具有自由基聚合性不飽和基團的親水性單體的含有量係60質量%以上;及
該防霧防污層的表面之純水接觸角為90°以上。
<2> 如<1>所述之防霧防污層積體,其中,該活性能量射線硬化性樹脂組成物還包含:具有自由基聚合性不飽和基團的疏水性單體。
<3> 如<2>所述之防霧防污層積體,其中,該活性能量射線硬化性樹脂組成物中,該具有自由基聚合性不飽和基團的疏水性單體的含有量係超過0.018質量%。
<4> 如<1>~<3>中任一者所述之防霧防污層積體,其中,該基材係樹脂製基材及無機基材中任一者。
<5> 一種物品,其表面係具有<1>~<4>中任一者所述之防霧防污層積體。
<6> 一種物品的製造方法,其係製造<5>所述之物品的製造方法,其係包含:
加熱製程,將該防霧防污層積體加熱;及
防霧防污層積體成形製程,將加熱後之該防霧防污層積體成形為所欲之形狀。
<7> 如<6>所述之物品的製造方法,其中,該加熱製程的加熱係藉由紅外線加熱來進行。
<8> 一種防污方法,其係藉由將<1>~<4>中所述之防霧防污層積體積層於物品的表面,以防止該物品被污染。
<9> 一種活性能量射線硬化性樹脂組成物,其係包含:
具有自由基聚合性不飽和基團的親水性單體;
具有自由基聚合性不飽和基團的疏水性單體;及
光聚合起始劑;其中,
藉由活性能量射線來將該活性能量射線硬化性樹脂組成物硬化後之防霧防污層的表面之純水接觸角為90°以上。
<10> 如<9>所述之活性能量射線硬化性樹脂組成物,其中,該具有自由基聚合性不飽和基團的親水性單體係具有聚氧伸烷鏈(polyoxyalkylene chain)之(甲基)丙烯酸酯,且該具有自由基聚合性不飽和基團的疏水性單體係具有氟與矽中至少任一者之(甲基)丙烯酸酯。
[發明的效果]
根據本發明,能解決習知的前述多個問題,達成前述目的,能提供一種具有優異的防霧性與防污性,且製造效率亦優異之防霧防污層積體、使用該防霧防污層積體之物品及其製造方法、使用該防霧防污層積體之防污方法、以及可使用於該防霧防污層積體的製造之活性能量射線硬化性樹脂組成物。
(防霧防污層積體)
本發明的防霧防污層積體係至少包含基材、防霧防污層,更因應必要,含有其他構件。
<基材>
就該基材而言,並未特別限制,能因應目的適當選擇,舉例來說,例如樹脂製基材、無機基材等。
就該樹脂製基材的材質而言,並未特別限制,能因應目的適當選擇,舉例來說,例如三醋酸纖維素(TAC, triacetyl cellulose)、聚酯(聚酯類彈性體(TPEE, thermoplastic polyester elastomer))、聚對苯二甲酸乙二酯(PET, polyethylene-telephthalate)、聚萘二甲酸乙二酯(PEN, polyethylene naphthalate)、聚醯亞胺(PI, polyimide)、聚醯胺(PA, polyamide)、醯胺、聚乙烯(PE, polyethylene)、聚丙烯酸酯、聚醚碸、聚碸、聚丙烯(PP, poly propylene)、聚苯乙烯、二乙醯基纖維素、聚氯乙烯、丙烯酸樹脂(聚甲基丙烯酸甲酯(PMMA, poly methyl methacrylate))、聚碳酸酯(PC, poly carbonate)、環氧樹脂、尿素樹脂、胺基甲酸乙酯樹脂、三聚氰胺樹脂、酚醛樹脂、丙烯腈-丁二烯-苯乙烯共聚物、環烯烴聚合物(COP, cyclo-olefin polymer)、環烯烴共聚物(COC, cyclo-olefin copolymer)、PC/PMMA層積體、添加橡膠的PMMA等。
就該無機基材的材質而言,並未特別限制,能因應目的適當選擇,舉例來說,例如金屬氧化物(例如石英、藍寶石、玻璃等)、金屬(例如鐵、鉻、鎳、鉬、鈮、銅、鈦、鋁、鋅、矽、鎂、錳等)、合金(例如前述金屬的組合等)。
該基材較佳係具有透明性。
就該基材的形狀而言,雖並未特別限制,能因應目的適當選擇,但舉例來說,例如較佳為薄膜狀。
於該樹脂製基材為薄膜之情況,就該樹脂製基材的平均厚度而言,雖並未特別限制,能因應目的適當選擇,但舉例來說,例如較佳為5μm~1,000μm,更佳為50μm~500μm。
於該無機基材為薄膜之情況,就該樹脂製基材的平均厚度而言,雖並未特別限制,能因應目的適當選擇,但舉例來說,例如0.1mm~100mm。
可於該樹脂製基材的表面印刷文字、圖案、圖形等。
為了提高該防霧防污層積體在成形加工時,該樹脂製基材與成形材料的黏合性,或者,為了保護該文字、該圖案、該圖形於成形加工時不受到來自成形材料之流動壓的損害,可於該樹脂製基材的表面設置黏合層。就該黏合層的材質而言,除了使用丙烯酸系、胺基甲酸乙酯系、聚酯系、聚醯胺系、乙烯-丁醇系、乙烯-醋酸乙烯酯共聚物系等之各種黏合劑以外,亦可使用各種接著劑。再者,該黏合層亦可設置兩層以上。可選擇具有適用於成形材料之感熱性、感壓性的成分作為所用之黏合劑。
<防霧防污層>
該防霧防污層的表面之純水接觸角為90°以上。
該防霧防污層係藉由活性能量射線來將活性能量射線硬化性樹脂組成物硬化後之硬化物。
該防霧防污層配置於該基材上。
該防霧防污層係表面平滑。此處,表面平滑係指表面不具有特意形成的凸部與凹部。舉例來說,就該防霧防污層積體而言,於形成該防霧防污層時(形成該硬化物時),沒有於表面形成經由物理性加工而成的細微的凸部與凹部。
因為沒有於該防霧防污層表面形成細微的凸部與凹部,使得魔術油墨、指紋、汗、及化妝品(粉底、UV保護等)等之水性污漬及/或油性污漬很難附著於表面。同時,舉例來說,即使於此等污漬附著的情況,也能使用面紙等,容易地將其去除,故可得到具有優異的防霧特性持續性之物品。
因為該防霧防污層自身的表面具有疏水性,故與日本特許公開第2001-233638號公報所記載的技術般、層積有吸水層與保護層等2層之情況相比,可得到耐磨耗性優異的防霧防污層積體。
-純水接觸角-
該防霧防污層表面的純水接觸角為90°以上,較佳為100°以上,更佳為110°以上,特佳為115°以上。就該純水接觸角的上限值而言,並未特別限制,能因應目的適當選擇,舉例來說,例如170°等。
舉例來說,該純水接觸角係可使用接觸角計(商品名Drop Master(DM)-701,協和界面化學股份有限公司製))並使用橢圓擬合法(ellipse fitting)以下述條件測定。
將蒸餾水注入塑膠注射器,於塑膠注射器前端安裝不鏽鋼製的針,並將蒸餾水滴下至評價面。
‧水的滴下量:2μL
‧測定溫度:25℃
將滴下水並經過4秒後的接觸角在防霧防污層表面任意的10個地方做測定,並將其平均值作為純水接觸角。
-十六烷接觸角-
該防霧防污層表面的十六烷接觸角為30°以上,較佳為60°以上,更佳為70°以上,特佳為80°以上。就該十六烷接觸角的上限值而言,並未特別限制,能因應目的適當選擇,舉例來說,例如150°等。
一旦該十六烷接觸角在上述較佳範圍內,即使於指紋、皮脂、汗、淚、化妝品等附著於表面之情況,因為能夠簡單的將其等擦拭去除,故對於維持優異的防霧性之觀點來看係有利的。
舉例來說,該十六烷接觸角係可使用接觸角計(商品名Drop Master(DM)-701,協和界面化學股份有限公司製))並使用橢圓擬合法(ellipse fitting)以下述條件測定。
將十六烷注入塑膠注射器,於塑膠注射器前端安裝具有Teflon(聚四氟乙烯)塗層的不鏽鋼製的針,並將十六烷滴下至評價面。
‧十六烷的滴下量:2μL
‧測定溫度:25℃
將滴下十六烷並經過4秒後的接觸角在防霧防污層表面任意的10個地方做測定,並將其平均值作為十六烷接觸角。
一旦純水接觸角與十六烷接觸角皆在上述範圍內,即使於附著有魔術油墨、指紋、汗、及化妝品(粉底、UV保護等)等之水性污漬及/或油性污漬的情況下,亦可防止此等污漬浸透至主體的下層。因此,藉由面紙等的擦拭,使污漬容易地擦拭去除的同時,亦能恢復至污漬附著前的狀態。
-活性能量射線硬化性樹脂組成物-
該活性能量射線硬化性樹脂組成物係至少含有,具有自由基聚合性不飽和基團的親水性單體(以下,稱為「親水性單體」)、光聚合起始劑,較佳係含有,具有自由基聚合性不飽和基團的疏水性單體(以下,稱為「疏水性單體」),更因應必要,含有其他成分。
--疏水性單體--
就該具有自由基聚合性不飽和基團的疏水性單體而言,舉例來說,例如具有自由基聚合性不飽和基團、以及氟與矽中至少任一者之單體。就如此之疏水性單體而言,舉例來說,例如具有氟與矽中至少任一者之(甲基)丙烯酸酯,更可例如氟化(甲基)丙烯酸酯、含矽(甲基)丙烯酸酯等,更具體而言,具有氟烷基的(甲基)丙烯酸酯、具有氟烷醚基的(甲基)丙烯酸酯、具有二甲基矽氧烷基的(甲基)丙烯酸酯等。
該疏水性單體較佳係與該親水性單體相溶。
此處,本發明的(甲基)丙烯酸酯係指丙烯酸酯或甲基丙烯酸酯。此種表示方法對於(甲基)丙烯醯基、(甲基)丙烯酸亦相同。
該疏水性單體可為市售品。
就該氟化(甲基)丙烯酸酯的市售品而言,舉例來說,例如信越化學工業股份有限公司製之KY-1200系列、DIC股份有限公司製之Megafac RS系列、大金工業股份有限公司製之OPTOOL DAC等。
就該含矽(甲基)丙烯酸酯的市售品而言,舉例來說,例如信越化學工業股份有限公司製之X-22-164系列、Evonik股份有限公司製之TEGO Rad系列等。
就該活性能量射線硬化性樹脂組成物中疏水性單體的含有量而言,雖並未特別限制,能因應目的適當選擇,但為超過0.018質量%,較佳為超過0.018質量%且未滿5.0質量%,更佳為0.075質量%~3.0質量%,特佳為0.18質量%~1.5質量%。一旦該含有量超過5質量%,雖然硬化物的疏水性優異,但因為硬化物的玻璃轉移溫度下降而變得過軟,所以耐磨耗性下降。同時,該防霧防污層中疏水單體的反應物過多則會造成呼氣防霧性下降。再者,於該活性能量射線硬化性樹脂組成物含有揮發成分(例如有機溶劑)的情況下,該含有量係相對於該活性能量射線硬化性樹脂組成物中非揮發成分的含有量。
--親水性單體--
就該親水性單體而言,舉例來說,例如含有聚氧伸烷鏈的(甲基)丙烯酸酯、含有四級銨鹽的(甲基)丙烯酸酯、含有三級胺基的(甲基)丙烯酸酯、含有磺酸基的單體、含有羧酸基的單體、含有磷酸基的單體、含有膦酸基的單體等。此等可為單官能基單體,亦可為多官能基單體。
就該聚氧伸烷鏈而言,舉例來說,例如聚氧乙烯鏈、聚氧丙烯鏈等。此等當中,以親水性優異的觀點來看,較佳係聚氧乙烯鏈。
就該親水性單體而言,舉例來說,例如經由將多元醇(含有聚醇或聚羥基的化合物)與丙烯酸、甲基丙烯酸及此等的衍生物組成之群中所選之化合物反應,而得到之單或聚丙烯酸酯、單或聚甲基丙烯酸酯等。就該多元醇而言,舉例來說,例如二元醇、三元醇、四元醇以上的多元醇等。就該二元醇而言,舉例來說,例如乙二醇、二乙二醇、三乙二醇、四乙二醇、數平均分子量300~1,000的聚乙二醇、丙二醇、二丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、2-乙基-1,3-己二醇、2,2'-硫二乙醇、1,4-環己烷二甲醇等。就該三元醇而言,舉例來說,例如三羥甲基乙烷、三羥甲基丙烷、五丙三醇、丙三醇、1,2,4-丁三醇、1,2,6-己三醇等。就該四元醇而言,舉例來說,例如季戊四醇、二丙三醇、二季戊四醇等。
就該含有聚氧伸烷鏈的(甲基)丙烯酸酯而言,舉例來說,例如聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、乙氧基化丙三醇(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯等。就該聚乙二醇(甲基)丙烯酸酯而言,舉例來說,例如甲氧基聚乙二醇(甲基)丙烯酸酯等。就該聚乙二醇(甲基)丙烯酸酯中聚乙二醇單元的分子量而言,並未特別限制,能因應目的適當選擇,舉例來說,例如300~1,000等。就該甲氧基聚乙二醇(甲基)丙烯酸酯而言,可使用市售品。就該市售品而言,舉例來說,例如MEPM-1000(第一工業製藥股份有限公司製)等。
此等當中,就使防霧防污層同時具有適度的硬度與親水性的觀點來看,較佳為乙氧基化丙三醇(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯。
就該含有四級銨鹽的(甲基)丙烯酸酯而言,舉例來說,例如(甲基)丙烯醯氧乙基三甲基氯化銨((meth) acryloyloxyethyl trimethyl ammonium chloride)、(甲基)丙烯醯氧乙基二甲基芐基氯化銨((meth) acryloyloxyethyl dimethyl benzyl ammonium chloride)、(甲基)丙烯醯氧乙基二甲基環氧丙基氯化銨((meth) acryloyloxyethyl dimethyl glycidyl ammonium chloride)、(甲基)丙烯醯氧乙基三甲基甲基硫酸銨((meth) acryloyloxyethyl trimethyl ammonium methyl sulfate)、(甲基)丙烯醯氧基二甲基乙基乙基硫酸銨((meth) acryloyloxy dimethylethyl ammonium ethyl sulfate)、(甲基)丙烯醯氧乙基三甲基銨-p-甲苯磺酸酯((meth) acryloyloxyethyl trimethyl ammonium-p-toluenesulfonate)、(甲基)丙烯醯胺丙基三甲基氯化銨((meth) acrylamide propyl trimethyl ammonium chloride)、(甲基)丙烯醯胺二甲基芐基氯化銨((meth) acrylamide propyl dimethyl benzyl ammonium chloride)、(甲基)丙烯醯胺丙基二甲基環氧丙基氯化銨((meth) acrylamide propyl dimethyl glycidyl chloride)、(甲基)丙烯醯胺丙基三甲基甲基硫酸銨((meth) acrylamide propyl trimethyl ammonium methyl sulfate)、(甲基)丙烯醯胺丙基二甲基乙基乙基硫酸銨((meth) acrylamide propyl dimethyl ethyl ammonium ethyl sulfate)、(甲基)丙烯醯胺丙基三甲基銨-p-甲苯磺酸酯((meth) acrylamide propyl trimethyl ammonium-p-toluenesulfonate)等。
就該含有三級胺基的(甲基)丙烯酸酯而言,舉例來說,例如(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基丙酯、(甲基)丙烯酸二乙基胺基丙酯、(甲基)丙烯酸1,2,2,6,6-五甲基哌啶酯、(甲基)丙烯酸2,2,6,6-四甲基哌啶酯等。
就該含有磺酸基的單體而言,舉例來說,例如乙烯基磺酸、丙烯基磺酸、乙烯基甲苯磺酸、苯乙烯磺酸、含磺酸基的(甲基)丙烯酸酯等。就該含磺酸基的(甲基)丙烯酸酯而言,舉例來說,例如(甲基)丙烯酸磺乙酯、(甲基)丙烯酸磺丙酯、2-丙烯醯胺基-2-甲基丙磺酸、末端磺酸改質的聚乙二醇單(甲基)丙烯酸酯等。此等當中,亦可形成鹽類。就該鹽類而言,舉例來說,例如鈉鹽、鉀鹽、銨鹽等。
就該含有羧酸基的單體而言,舉例來說,例如丙烯酸、甲基丙烯酸等。
就該含有磷酸基的單體而言,舉例來說,例如含有磷酸酯的(甲基)丙烯酸酯等。
就該親水性單體而言,較佳為多官能基的親水性單體。
就該親水性單體的分子量而言,雖並未特別限制,能因應目的適當選擇,但較佳為200以上。
就該活性能量射線硬化性樹脂組成物中親水性單體的含有量而言,雖並未特別限制,能因應目的適當選擇,但為60質量%以上,較佳為60質量%~99.9質量%,更佳為63質量%~95質量%,特佳為65質量%~90質量%。再者,於該活性能量射線硬化性樹脂組成物含有揮發成分(例如有機溶劑)的情況下,該含有量係相對於該活性能量射線硬化性樹脂組成物中非揮發成分的含有量。
--光聚合起始劑--
就該光聚合起始劑而言,舉例來說,例如光自由基聚合起始劑、光酸產生劑、雙疊氮化合物、六甲氧基甲基三聚氰胺(hexamethoxy methyl melamine)、四甲氧基乙炔脲(tetramethoxy glycoluril)等。
就該光自由基聚合起始劑而言,雖並未特別限制,能因應目的適當選擇,但舉例來說,例如乙氧苯基(2,4,6-三甲基苯甲醯)膦氧化物、雙(2,6-二甲基苯甲醯)-2,4,4-三甲基戊基膦氧化物、雙(2,4,6-三甲基苯甲醯)-2,4,4-三甲基戊基膦氧化物、雙(2,6-二氯苯甲醯)-2,4,4-三甲基戊基膦氧化物、1-苯基2-羥基-2甲基丙烷-1-酮、1-羥基環己基苯基甲酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1,2-二苯基乙烷二酮、甲基苯基乙醛酸酯等。
就該活性能量射線硬化性樹脂組成物中光聚合起始劑的含有量而言,雖並未特別限制,能因應目的適當選擇,但較佳為0.1質量%~10質量%,更佳為0.5質量%~8質量%,特佳為1質量%~5質量%。再者,於該活性能量射線硬化性樹脂組成物含有揮發成分(例如有機溶劑)的情況下,該含有量係相對於該活性能量射線硬化性樹脂組成物中非揮發成分的含有量。
--其他成分--
就該其他成分而言,並未特別限制,能因應目的適當選擇,舉例來說,例如胺基甲酸乙酯(甲基)丙烯酸酯、含有異三聚氰酸基的(甲基)丙烯酸酯、填充物等。
此等係用作於該防霧防污層的延伸率、硬度等之調整。
就該胺基甲酸乙酯(甲基)丙烯酸酯而言,並未特別限制,能因應目的適當選擇,舉例來說,例如脂肪族胺基甲酸乙酯(甲基)丙烯酸酯、芳香族胺基甲酸乙酯(甲基)丙烯酸酯等。此等當中,較佳為脂肪族胺基甲酸乙酯(甲基)丙烯酸酯。
就該活性能量射線硬化性樹脂組成物中胺基甲酸乙酯(甲基)丙烯酸酯的含有量而言,雖並未特別限制,能因應目的適當選擇,但較佳為10質量%~45質量%,更佳為15質量%~40質量%,特佳為20質量%~35質量%。再者,於該活性能量射線硬化性樹脂組成物含有揮發成分(例如有機溶劑)的情況下,該含有量係相對於該活性能量射線硬化性樹脂組成物中非揮發成分的含有量。
就該填充物而言,並未特別限制,能因應目的適當選擇,舉例來說,例如氧化矽、氧化鋯、氧化鈦、氧化錫、氧化銦錫、摻雜銻之氧化錫、五氧化銻等。就該氧化矽而言,舉例來說,例如實心氧化矽、中空氧化矽。
使用時,能夠利用有機溶劑將該活性能量射線硬化性樹脂組成物稀釋。就該有機溶劑而言,舉例來說,例如芳香族系溶劑、醇系溶劑、酯系溶劑、酮系溶劑、乙二醇醚系溶劑、乙二醇醚酯系溶劑、氯系溶劑、醚系溶劑、N-甲基吡咯烷酮、二甲基甲醯胺、二甲基亞碸、二甲基乙醯胺等。
該活性能量射線硬化性樹脂組成物係藉由照射活性能量射線來硬化。就該活性能量射線而言,並未特別限制,能因應目的適當選擇,舉例來說,例如電子束、紫外線、紅外線、雷射光、可見光、電離輻射(X射線、α射線、β射線、γ射線等)、微波、高頻波等。
就該防霧防污層的馬氏硬度而言,雖並未特別限制,能因應目的適當選擇,但較佳為5N/mm2
~300N/mm2
,更佳為10N/mm2
~290N/mm2
,特佳為15N/mm2
~280N/mm2
。舉例來說,於將該防霧防污層積體成形加工時,例如,於使用聚碳酸酯的射出成型時,以290℃、200Mpa的條件將該防霧防污層積體加熱加壓。一旦該馬氏硬度未滿5N/mm2
,該防霧防污層積體於製造或成形加工時的處理與表面清潔等步驟,會較平常使用時還容易使該防霧防污層受損。一旦該馬氏硬度超過300N/mm2
,於成形加工時,該防霧防污層產生裂痕而使該防霧防污層剝離。就容易將該防霧防污層積體成形加工成各種立體形狀的觀點來看,一旦該馬氏硬度在上述的特佳範圍,該防霧防污層的防霧性能不會劣化且不會產生受損、裂痕、剝離等不佳的情形。
再者,因為於該防霧防污層積體的成形加工後,還在射出成型製程中對該防霧防污層的施加高溫高壓,因此該防霧防污層的馬氏硬度會比成形加工前還提高。
舉例來說,該馬氏硬度係可使用PICODENTOR HM500(商品名;Fisher Instruments公司製)來測定。將負載設為1mN/20s且使用金剛石錐體作為針,以面角136°來測定。
就該防霧防污層的鉛筆硬度而言,雖並未特別限制,能因應目的適當選擇,但較佳為B~4H,更佳為HB~4H,特佳為F~4H。一旦該鉛筆硬度未滿B(比B還軟),則該防霧防污層積體於製造或成形加工時的處理與表面清潔等步驟,會較平常使用時還容易使該防霧防污層受損。一旦該鉛筆硬度超過4H(比4H還硬),則於成形加工時,該防霧防污層產生裂痕而使該防霧防污層剝離。就容易將該防霧防污層積體成形加工成各種立體形狀的觀點來看,一旦該鉛筆硬度在上述的特佳範圍,該防霧防污層的防霧性能不會劣化且不會產生受損、裂痕、剝離等不佳的情形。
再者,因為於該防霧防污層積體的成形加工後,還在射出成型製程中對該防霧防污層的施加高溫高壓,因此該防霧防污層的鉛筆硬度會比成形加工前還提高。
該鉛筆硬度係依據JIS K 5600-5-4來測定。
就該防霧防污層的平均厚度而言,雖並未特別限制,能因應目的適當選擇,但較佳為1μm~100μm,更佳為4μm~50μm,特佳為10μm~30μm。一旦該平均厚度在上述較佳範圍,則就防霧性優異、降低干涉不均勻、及生產性優異的觀點來看,係有利的。一旦該平均厚度在上述特佳範圍,則可更進一步降低干涉不均勻。
<其他部材>
就該其他部材而言,舉例來說,例如定向層、保護層等。
-定向層-
該定向層係設置於該基材與該防霧防污層之間的層。
藉由設置該定向層,可使該基材與該防霧防污層的接著性提升。
為了防止干渉不均勻,該定向層的折射率較佳係接近防霧防污層的折射率。因此,該定向層的折射率較佳為該防霧防污層的折射率之±0.10以內,更佳為±0.05以內。同時,該定向層的折射率較佳係在該防霧防污層的折射率及該樹脂製基材的折射率之間。
舉例來說,該定向層係可藉由塗佈活性能量射線硬化性樹脂組成物來形成。意即,舉例來說,該定向層係藉由活性能量射線來將活性能量射線硬化性樹脂組成物硬化後之硬化物。就該活性能量射線硬化性樹脂組成物而言,舉例來說,其係至少含有胺基甲酸乙酯(甲基)丙烯酸酯及光聚合起始劑,更因應必要,含有其他成分之活性能量射線硬化性樹脂組成物等。就該胺基甲酸乙酯(甲基)丙烯酸酯、該光聚合起始劑而言,舉例來說,例如於該防霧防污層的說明中分別所示例的胺基甲酸乙酯(甲基)丙烯酸酯、光聚合起始劑。就該塗佈的方法而言,並未特別限制,能因應目的適當選擇,舉例來說,例如線棒塗佈、刮刀塗佈、旋轉塗佈、逆轉滾筒塗佈、模塗佈、噴霧塗佈、滾筒塗佈、凹版塗佈(gravure coating)、微凹版塗佈、唇塗佈(lip coating)、氣刀塗佈、簾塗佈、缺角輪塗佈法、浸泡法等。
於該基材係無機基材的情況下,就該定向層的材料而言,舉例來說,例如矽烷耦合劑、鈦酸鹽耦合劑、鋁酸鹽耦合劑等。此等係較佳具有自由基聚合性不飽和基團。
於該基材係無機基材的情況下,就該定向層的形成方法而言,舉例來說,將溶有該材料的溶液塗佈於該無機基材上,並將溶劑乾燥後,以給定時間進行加熱處理的方法等。
就使用於該溶液的溶劑而言,係選擇溶解該材料之物。舉例來說,例如使用選自水、醇(例如甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、仲丁醇、叔丁醇等)、酮(例如環己酮、環戊酮)、醯胺(例如N,N-二甲基甲醯胺:DMF)、硫化物(例如二甲基亞碸:DMSO)等所組成之群中至少1種以上。
就塗佈的方法而言,並未特別限定,可使用公知的塗佈法。就公知的塗佈法而言,舉例來說,例如微凹版塗佈法、線棒塗佈法、直接凹版塗佈法、模塗佈法、浸漬法、噴霧塗佈法、逆轉滾筒塗佈法、簾塗佈法、缺角輪塗佈法、刮刀塗佈法、旋轉塗佈法、凸版印刷、平版印刷、捲筒紙凹版印刷(rotogravure)、凹版印刷、膠版印刷、網版印刷、噴墨印刷等。
就該加熱溫度而言,例如80℃以上且200以下。加熱時間例如為1分鐘以上12小時以內。
就該定向層的平均厚度而言,雖並未特別限制,能因應目的適當選擇,但較佳為1nm~100μm,更佳為0.01μm~10μm,特佳為0.1μm~5μm,最佳為0.3μm~3μm。
再者,亦可賦予該定向層減低反射率或防止帶電的功能。
-保護層-
該保護層係保護該防霧防污層的表面(純水接觸角90°以上的表面)。
該保護層係於製造使用該防霧防污層積體之後述物品時,保護該表面。
該保護層係配置於該防霧防污樹脂層的表面上。
就該保護層的材質而言,舉例來說,例如與該定向層相同的材質。
就該防霧防污層積體的延伸率而言,雖並未特別限制,能因應目的適當選擇,但較佳為10%以上,更佳為10%~200%,特佳為40%~150%。一旦該延伸率未滿10%,則成形加工變得困難。就成形加工性優異的觀點來看,一旦該延伸率在特佳範圍內,係有利的。
該延伸率例如可藉由以下的方法來求得。
使用長度10.5cm*寬度2.5cm的長條狀之防霧防污層積體來作為測定試料。將所得到的測定試料之拉伸延伸率使用拉伸實驗機(Autograph AG-5kNXplus、島津製作所股份有限公司製)進行測定(測定條件:拉伸速度=100mm/min;夾具間距離=8cm)。於該延伸率的測定中,測定溫度係依據該樹脂製基材的品種而不同,該延伸率係以該樹脂製基材的軟化點附近或軟化點以上的溫度進行測定。具體而言,測定溫度係在10℃~250℃之間。舉例來說,於該樹脂製基材為聚碳酸酯或PC/PMMA層積體的情況下,較佳係以150℃進行測定。
該防霧防污層積體中,該防霧防污層積體的面內之X方向與Y方向的加熱收縮率差較佳為小者。所謂該防霧防污層積體的X方向與Y方向,舉例來說,在防霧防污層積體為滾筒形狀的情況下,相當於滾筒的長邊方向與寬邊方向。以成形時之加熱製程所使用的加熱溫度進行加熱時,防霧防污層積體中X方向的加熱收縮率與Y方向的加熱收縮率之差值較佳係5%以內。一旦在此範圍外,於成形加工時,該防霧防污層產生剝離或裂痕,且印刷於樹脂製基材的表面的文字、圖案、圖形等產生變形或位置偏移,使得成形加工變得困難。
該防霧防污層積體係特別適用於熱彎曲用薄膜、模內成形用薄膜(film for in-mold molding)、嵌入成形用薄膜(film for insert molding)、覆蓋成形用薄膜(film for overlay molding)。
就該防霧防污層積體的製造方法而言,雖並未特別限制,能因應目的適當選擇,但較佳係後述之本發明防霧防污層積體的製造方法。
<防霧防污層積體的製造方法>
該防霧防污層積體的製造方法係至少包含未硬化樹脂層形成製程與防霧防污層形成製程,更因應必要,包含其他製程。
該防霧防污層積體的製造方法係為製造本發明防霧防污層積體的方法。
<<未硬化樹脂層形成製程>>
就該未硬化樹脂層形成製程而言,只要是將活性能量射線硬化性樹脂組成物塗佈於樹脂製基材上,來形成未硬化樹脂層的製程,並未特別限制,能因應目的適當選擇。
就該基材而言,並未特別限制,能因應目的適當選擇,舉例來說,例如於本發明防霧防污層積體的說明中所示例之基材等。
就該活性能量射線硬化性樹脂組成物而言,並未特別限制,能因應目的適當選擇,舉例來說,例如於本發明該防霧防污層積體的防霧防污層之說明中所示例的活性能量射線硬化性樹脂組成物等。
該未硬化樹脂層係藉由將該活性能量射線硬化性樹脂組成物塗佈於該基材上,且因應必要進行乾燥來形成。該未硬化樹脂層可為固體的膜,亦可為藉由被包含在該活性能量射線硬化性樹脂組成物內的低分子量硬化性成分而具有流動性的膜。
就該塗佈的方法而言,並未特別限制,能因應目的適當選擇,舉例來說,例如線棒塗佈、刮刀塗佈、旋轉塗佈、逆轉滾筒塗佈、模塗佈、噴霧塗佈、滾筒塗佈、凹版塗佈(gravure coating)、微凹版塗佈、唇塗佈(lip coating)、氣刀塗佈、簾塗佈、缺角輪塗佈法、浸泡法等。
因為該未硬化樹脂層未被活性能量射線照射,所以不會硬化。
該未硬化樹脂層形成製程中,較佳係將該活性能量射線硬化性樹脂組成物塗佈於形成有定向層的該樹脂製基材之定向層上,來形成該未硬化樹脂層。
就該定向層而言,並未特別限制,能因應目的適當選擇,舉例來說,例如於本發明防霧防污層積體的說明中所示例之定向層等。
<<防霧防污層形成製程>>
就該防霧防污層形成製程而言,只要是照射活性能量射線於該未硬化樹脂層且使該未硬化樹脂層硬化,來形成防霧防污層的製程,並未特別限制,能因應目的適當選擇。
於形成該防霧防污層時,不進行於表面形成細微的凸部與凹部之物理性加工。
該活性能量射線硬化性樹脂組成物藉由具有該疏水性單體與該親水性單體,使低表面能量成分一直局部化於得到之防霧防污層的表面,並於該防霧防污層中存在親水性成分(吸水性成分)。藉此,使得水滴於該防霧防污層的表面被疏水化,亦使得水蒸氣變得容易被捕捉至該防霧防污層中。最終,可得到更優異的防霧性。
-活性能量射線-
就該活性能量射線而言,只要是使該未硬化樹脂層硬化的活性能量射線,並未特別限制,能因應目的適宜選擇,舉例來說,例如於本發明防霧防污層積體的說明中所示例之活性能量射線等。
(活性能量射線硬化性樹脂組成物)
本發明的活性能量射線硬化性樹脂組成物係至少含有:具有自由基聚合性不飽和基團的親水性單體、具有自由基聚合性不飽和基團的疏水性單體、及光聚合起始劑,更因應必要,含有其他成分。
藉由活性能量射線來將該活性能量射線硬化性樹脂組成物硬化後之防霧防污層的表面之純水接觸角為90°以上。舉例來說,該防霧防污層的表面之純水接觸角係於製作平均厚度4μm的該防霧防污層後,藉由前述測定方法來測定的。就該防霧防污層的特性而言,舉例來說,例如於該防霧防污層積體的說明中所示例之特性,且較佳之態樣亦例如於該防霧防污層積體的說明中所示例之態樣。
就該活性能量射線硬化性樹脂組成物的成分而言,舉例來說,例如於該防霧防污層積體的說明中所示例之活性能量射線硬化性樹脂組成物的各成分等,且較佳之態樣亦例如於該防霧防污層積體的說明中所示例之態樣。
意即,就該具有自由基聚合性不飽和基團的親水性單體而言,舉例來說,例如於該防霧防污層積體的說明中所示例之具有自由基聚合性不飽和基團的親水性單體等。含有量等之較佳態樣亦例如於該防霧防污層積體的說明中所示例之態樣。
就該具有自由基聚合性不飽和基團的疏水性單體而言,舉例來說,例如於該防霧防污層積體的說明中所示例之具有自由基聚合性不飽和基團的疏水性單體等。含有量等之較佳態樣亦例如於該防霧防污層積體的說明中所示例之態樣。
(物品)
本發明物品的表面具有本發明該防霧防污層積體,且更因應必要,具有其他部材。
就該物品而言,並未特別限制,能因應目的適宜選擇,舉例來說,例如玻璃窗、冷藏/冷凍展示櫃、汽車的窗戶等窗材、浴室內的鏡、汽車側鏡等鏡子、浴室的地板與牆壁、太陽能電池面板、防盜監視攝影機等。
同時,該物品亦可為眼鏡、護目鏡、頭盔、透鏡、微透鏡陣列、汽車的車前燈罩、前面板、側板、後板等。此等物品較佳係藉由模內成形、嵌入成形、覆蓋成形來形成。
該防霧防污層積體可以形成於該物品的表面之一部分,也可以形成於表面之全部。
就該物品的製造方法而言,雖並未特別限制,能因應目的適宜選擇,但較佳係後述之本發明物品的製造方法。
(物品的製造方法)
關於本發明物品的製造方法,其係至少包含加熱製程、防霧防污層積體成形製程,更因應必要,包含射出成型製程與流延(cast)成形製程等其他製程。
該物品的製造方法係為本發明物品的製造方法。
<加熱製程>
就該加熱製程而言,只要是加熱防霧防污層積體的製程,並未特別限制,能因應目的適宜選擇。
該防霧防污層積體係為本發明防霧防污層積體。
就該加熱而言,雖並未特別限制,能因應目的適宜選擇,但較佳係使用紅外線加熱或暴露於高溫氛圍中。
就該加熱的溫度而言,雖並未特別限制,能因應目的適宜選擇,但較佳係使用該樹脂製基材的玻璃轉移溫度附近或玻璃轉移溫度以上。
就該加熱的時間而言,並未特別限制,能因應目的適宜選擇。
<防霧防污層積體成形製程>
就該防霧防污層積體成形製程而言,只要是能將所加熱的防霧防污層積體成形為所欲形狀之製程,並未特別限制,能因應目的適宜選擇,舉例來說,例如藉由將其黏合於特定的模具,並藉由空氣加壓,來成形為所欲之形狀的製程等。
<射出成型製程>
於該防霧防污層積體成形製程後,可因應必要,進行射出成型製程。
就該射出成型製程而言,只要是於形成有所欲形狀的防霧防污層積體之樹脂製基材側射出成形材料,而將該成形材料成形的製程,並未特別限制,能因應目的適宜選擇。
就該成形材料而言,舉例來說,例如樹脂等。就該樹脂而言,舉例來說,例如烯烴系樹脂、苯乙烯系樹脂、ABS樹脂(丙烯腈-丁二烯-苯乙烯共聚物)、AS樹脂(丙烯腈-苯乙烯共聚物)、丙烯酸系樹脂、胺基甲酸乙酯系樹脂、不飽和聚酯樹脂、環氧樹脂、聚苯醚-聚苯乙烯系樹脂、聚碳酸酯、聚碳酸酯改質聚苯醚、聚對苯二甲酸乙二酯、聚碸、聚苯硫化物、聚苯醚、聚醚醯亞胺、聚醯亞胺、聚醯胺、液晶聚酯、聚丙烯系耐熱樹脂、各種複合樹脂、各種改質樹脂等。
就該射出的方法而言,並未特別限制,能因應目的適宜選擇,舉例來說,例如於黏合在特定模具之該防霧防污層積體的樹脂製基材側,將熔融的該成形材料注入之方法等。
<流延成形製程>
於該防霧防污層積體成形製程後,可因應必要,進行流延成形製程。
就該流延成形製程而言,只要是將溶解於溶液之樹脂材料注入於形成有所欲形狀的防霧防污層積體之樹脂製基材側,並將該樹脂材料固化成形的製程,並未特別限制,能因應目的適宜選擇。
該物品的製造方法較佳係使用模內成形裝置、嵌入成形裝置、覆蓋成形裝置來進行。
此處,使用圖來說明本發明物品的製造方法之一例。此製造方法係為使用模內成形裝置的製造方法。
首先,加熱防霧防污層積體500。加熱較佳係使用紅外線加熱,或者暴露於高溫氛圍中。
接著,如圖1A所示,將加熱後的防霧防污層積體500配置於第一模具501與第二模具502間的特定位置。此時,防霧防污層積體500的樹脂製基材朝第一模具501配置,防霧防污層朝第二模具502配置。圖1A中,第一模具501係為固定模具,第二模具502係為可動模具。
於第一模具501與第二模具502間配置防霧防污層積體500後,將第一模具501與第二模具502進行合模。接著,於第二模具502的凹面開口,以吸引孔504吸引防霧防污層積體500,並於第二模具502的凹面裝載防霧防污層積體500。藉此,凹面讓防霧防污層積體500賦形。而且,此時,較佳係使用圖未示的薄膜加壓機構將防霧防污層積體500的外周圍固定並定位。之後,將防霧防污層積體500不要的部位裁切(圖1B)。
再者,因為第二模具502不具有吸引孔504,而於第一模具501具有壓縮空氣孔(圖未示)的情況下,藉由從第一模具501的壓縮空氣孔將壓縮空氣送入至防霧防污層積體500,進而將防霧防污層積體500裝載於第二模具502的凹面。
接著,從第一模具501的進模口505,朝向防霧防污層積體500的樹脂製基材射出熔融的成形材料506,並將成形材料506注入藉由第一模具501與第二模具502合模而形成的凹槽內部(圖1C)。藉此,熔融的成形材料506填充於凹槽內部(圖1D)。再者,填充完熔融的成形材料506後,將熔融的成形材料506冷卻至給定的溫度來固化。
之後,移動第二模具502,並將第一模具501與第二模具502開模(圖1E)。藉此,將防霧防污層積體500形成於成形材料506的表面,且得到具有所欲形狀之模內成形後的物品507。
最後,從第一模具501推出頂針508,來取出所得到之物品507。
於使用該覆蓋成形裝置時的製造方法,係如以下所述。該製造方法係將防霧防污層積體直接裝飾於成形材料表面的製程,且就此方法的一例而言,例如三次元表面裝飾(TOM, Three dimension Overlay Method)的施工方法。以下,說明使用該TOM施工方法的本發明物品之製造方法的一例。
首先,就藉由固定於固定框架的防霧防污層積體來分離的裝置內之兩空間而言,係使用真空幫浦等來吸引空氣,並將該兩空間內抽至真空。
此時,事先將射出成型的成形材料設置於空間的一側。同時,使用紅外線加熱器將防霧防污層積體加熱至使其軟化的給定溫度。於防霧防污層積體被加熱軟化的時間中,藉由將大氣壓力送入裝置內空間之沒有成形材料的一側,並在真空環境下,使成形材料的立體形狀緊緊地黏合防霧防污層積體。且因應必要,較佳係進一步併用來自送入大氣壓力側的壓縮空氣加壓。在防霧防污層積體黏合於成形體後,將所得到之裝飾成形品從固定框架移除。真空成形通常在80℃~200℃左右進行,較佳係在110℃~160℃左右進行。
於覆蓋成形時,為了將該防霧防污層積體與該成形材料接著,較佳係將黏著層設置於該防霧防污層積體的防霧防污面之相反側的面。就該黏著層而言,並未特別限制,能因應目的適宜選擇,舉例來說,例如丙烯酸系黏合劑、熱熔接著劑等。就該黏著層的形成方法而言,並未特別限制,能因應目的適宜選擇,舉例來說,例如於該樹脂製基材上形成該防霧防污層後,於該樹脂製基材的防霧防污層側之相反側塗佈黏著層用塗佈液,進而形成該黏著層的方法等。同時,於剝離薄片上塗佈黏著層用塗佈液來形成該黏合層後,將該樹脂製基材與該剝離薄片上的黏著層進行層積,較佳係於該樹脂製基材上層積該黏著層。
此處,使用圖來說明本發明物品的一例。
圖2~5係為本發明物品的一例之概略剖面圖。
圖2的物品係具有成形材料506、樹脂製基材211、及防霧防污層212,且樹脂製基材211與防霧防污層212以此順序層積於成形材料506上。
舉例來說,此物品係可藉由嵌入成形來製造。
圖3的物品係具有成形材料506、樹脂製基材211、防霧防污層212、及硬塗層600,且樹脂製基材211與防霧防污層212以此順序層積於成形材料506上。同時,硬塗層600形成於成形材料506之樹脂製基材211側的相反側。
舉例來說,此物品係可於製造圖2的物品並於該物品的防霧防污層212上形成保護層後,藉由將成形材料506浸漬於硬塗液,並於其後乾燥、硬化而將硬塗層600形成於成形材料506的表面,接著將保護層剝離來製造該物品。
再者,於防霧防污層係平滑面、純水接觸角係在前述的範圍內、及十六烷接觸角亦在前述的範圍內之情況下,因為防霧防污層將硬塗液彈開,故於不形成保護層的同時亦不形成硬塗層於防霧防污層上,且因為只有於成形材料506之樹脂製基材211側的相反側形成硬塗層600,故生產性優異。
圖4的物品係具有成形材料506、樹脂製基材211、及防霧防污層212,且樹脂製基材211與防霧防污層212以此順序層積於成形材料506的兩側。
圖5的物品係具有成形材料506、樹脂製基材211、防霧防污層212、及光學薄膜601,且樹脂製基材211與防霧防污層212以此順序層積於成形材料506上。光學薄膜601形成於成形材料506之樹脂製基材211側的相反側。就該光學薄膜601而言,舉例來說,例如硬塗薄膜、防反射薄膜、防眩薄膜、偏光薄膜等。
舉例來說,圖4或圖5所示的物品可藉由雙重嵌入成形來製造。雙重嵌入成形係一種使雙面層積膜一體成形的成形方法,例如可使用日本專利特開平03-114718號公報所載的方法等來進行。
(防污方法)
本發明的防污方法係藉由將本發明的防霧防污層積體層積於物體表面而防止該物品污染的方法。
就該物品而言,並未特別限制,能因應目的適宜選擇,舉例來說,例如玻璃窗、冷藏/冷凍展示櫃、汽車的窗戶等窗材、浴室內的鏡、汽車側鏡等鏡子、浴室的地板與牆壁、太陽能電池面板、防盜監視攝影機等。
同時,該物品亦可為眼鏡、護目鏡、頭盔、透鏡、微透鏡陣列、汽車的車前燈罩、前面板、側板、後板等。此等物品較佳係藉由模內成形、嵌入成形來形成。
就將該防霧防污層積體層積於物體表面的方法而言,並未特別限制,能因應目的適當選擇,舉例來說,例如將該防霧防污層積體貼附於該物體表面的方法等。同時,亦可藉由本發明該物品的製造方法將該防霧防污層積體層積於物體表面。
[實施例]
以下,雖然說明了本發明的實施例,但本發明並不受此等實施例限定。
<純水接觸角>
純水接觸角係使用作為接觸角計的DM-701(協和界面化學股份有限公司製) 並使用橢圓擬合法(ellipse fitting)以下述條件測定。
將蒸餾水注入塑膠注射器,於塑膠注射器前端安裝不鏽鋼製的針,並將蒸餾水滴下至評價面。
‧水的滴下量:2μL
‧測定溫度:25℃
將滴下水並經過4秒後的接觸角在防霧防污層表面任意的10個地方做測定,並將其平均值作為純水接觸角。
<十六烷接觸角>
十六烷接觸角係使用作為接觸角計的DM-701(協和界面化學股份有限公司製) 並使用橢圓擬合法(ellipse fitting)以下述條件測定。
將十六烷注入塑膠注射器,於塑膠注射器前端安裝具有Teflon(聚四氟乙烯)塗層的不鏽鋼製的針,並將十六烷滴下至評價面。
‧十六烷的滴下量:2μL
‧測定溫度:25℃
將滴下十六烷並經過4秒後的接觸角在防霧防污層表面任意的10個地方做測定,並將其平均值作為十六烷接觸角。
<呼氣防霧性>
在25℃37%RH的環境下,自離防霧防污層表面的法線方向5cm的距離,吐一口大氣於該表面後,立即以目視觀察表面,並使用下述評價基準進行評價。
[評價基準]
○:防霧防污層表面的外觀完全沒有變化。
╳:防霧防污層表面確認到外觀的變化,表面形成白色混濁、水膜等。
<防污試驗>
使用市售的油性筆(油性筆:Mckee,ZEBRA公司製)接觸防霧防污層的表面。接著,藉由目視確認防霧防污層表面的油墨狀態(彈開),並使用下述評價基準進行評價。
[評價基準]
○:油墨被彈開。
╳:油墨附著。
<擦拭試驗>
使用市售的油性筆(油性筆:Mckee,ZEBRA公司製)接觸防霧防污層的表面。接著,使用面紙(大王製紙股份有限公司製,elleair)以畫圓的方式擦拭3次後,以目視確認擦拭後的狀態,並於其後進行呼氣防霧性試驗。使用下述評價基準進行評價。
[評價基準]
○:油墨被擦拭去除,且呼氣試驗後,防霧防污層表面的外觀完全沒有變化。
╳:油墨沒有被擦拭去除,及/或防霧防污層表面確認到外觀的變化,表面形成白色混濁、水膜等。
(實施例1)
<防霧防污層積體的製作>
就樹脂製基材而言,使用三菱瓦斯化學股份有限公司製的FE-2000(聚碳酸酯(PC, Polycarbonate)基材,平均厚度180μm)。
接著,將下述組成的活性能量射線硬化性樹脂組成物塗佈於該樹脂製基材上,使其塗佈厚度為4μm。於氮氛圍下,使用金屬鹵化物燈,以照射量1,800mJ/cm2
照射紫外線,使防霧防污層硬化,並得到防霧防污層積體。
-活性能量射線硬化性樹脂組成物(合計100質量%)-
‧NK酯 A-GLY-20E (新中村化學工業股份有限公司製) 67.307質量%
‧PETIA(DAICEL-ALLNEX股份有限公司製) 28.846質量%
‧KY-1203(信越化學工業股份有限公司製) 0.962質量%
‧Irgacure 184D(BASF公司製) 2.885質量%
將得到之防霧防污層積體進行上述的評價。將結果顯示於表1-1。
(實施例2~8、及比較例1~4)
除了將實施例1中的塗佈厚度、及活性能量射線硬化性樹脂組成物的組成變更為表1-1與表1-2所記載的塗佈厚度、及活性能量射線硬化性樹脂組成物的組成以外,與實施例1相同地,得到(防霧防污)層積體。
將得到之(防霧防污)層積體進行上述的評價。將結果顯示於表1-1與表1-2。
(比較例5)
使用樹脂製基材、及表1-2所記載的活性能量射線硬化性樹脂組成物之組成,並使用如日本特許公開第2014-159154號公報中實施例1所記載的使用玻璃滾筒基板來製造精細凹凸構造之製造方法,得到具有精細凹凸構造的層積體。
再者,得到之層積體的精細凹凸構造係與日本特許公開第2014-159154號公報中段落[0177][表2]的實施例1所記載的樹脂層之凹凸構造相同。
將得到之層積體進行上述的評價。將結果顯示於表1-2。
表1-1與表1-2中的各種材料係如下所述。
[親水性單體]
‧NK酯 A-GLY-20E:新中村化學工業股份有限公司製
乙氧基化丙三醇三丙烯酸酯
(構造中所含聚環氧乙烷鏈重複單元的合計數:20)
‧NK酯 A-TM-35E:新中村化學工業股份有限公司製
乙氧基化季戊四醇四丙烯酸酯
(構造中所含聚環氧乙烷鏈重複單元的合計數:35)
‧NK酯 A-600:新中村化學工業股份有限公司製
聚乙二醇二丙烯酸酯
(構造中所含聚環氧乙烷鏈重複單元的合計數:14)
[其他單體]
‧PETIA:DAICEL-ALLNEX股份有限公司製
季戊四醇三丙烯酸酯與季戊四醇四丙烯酸酯的混合物
(構造中所含聚環氧乙烷鏈重複單元的合計數:無)
‧EBECRYL 40:DAICEL-ALLNEX股份有限公司製
季戊四醇乙氧基四丙烯酸酯
(構造中所含聚環氧乙烷鏈重複單元的合計數:無)
‧ARONIX M313:東亞合成工業股份有限公司製
含有異三聚氰酸基的丙烯酸酯
[疏水性單體]
‧KY-1203:信越化學工業股份有限公司製
末端(甲基)丙烯酸改質的全氟聚醚系添加劑
‧OPTOOL DAC-HP:大金工業股份有限公司製
末端(甲基)丙烯酸改質的全氟聚醚系添加劑
[起始劑]
‧Irgacure 184D:BASF公司製
實施例1~8中,防霧防污層係含有親水性分子構造且該防霧防污層表面的純水接觸角為90°以上,且藉由使防霧防污層含有親水性分子構造,可得到呼氣防霧性與防污性皆優異的防霧防污層積體。
比較例1中,因為未含有疏水性單體,純水接觸角未滿90°,變成防污性與擦拭性皆劣化的層積體。
因為比較例2~3中親水性單體的含有量過少,變成呼氣防霧性劣化的層積體。
因為比較例4中表面的純水接觸角未滿90°,變成防污性與擦拭性皆劣化的層積體。
比較例5雖然含有給定量的親水性單體,且表面的純水接觸角為90°以上,但因為具有凹凸構造,故變成防污性與擦拭性皆劣化的層積體。
(實施例9)
除了將實施例5的塗佈厚度變更為10μm以外,與實施例5相同地,得到防霧防污層積體。
將得到之層積體進行與實施例5相同的評價。再者,進行干涉不均勻的評價。將結果顯示於表2。實施例5干涉不均勻的評價為△,相對地,實施例9的評價為○。
<干涉不均勻的評價方法>
使用雙面黏著薄片(日東電工股份有限公司製,商品名:LUCIACS CS9621T)將防霧防污層積體與黑色丙烯酸板(三菱麗陽股份有限公司製,商品名:ACRYLITE)貼合,使防霧防污層積體的評價面(防霧防污層表面)朝上。接著,在白色螢光燈下觀察評價面,並使用下述評價基準進行評價。
[評價基準]
○:評價面係黑色,干涉不均勻沒有被確認到。
△:評價面稍微染上顏色,確認到些微地干涉不均勻。
╳:評價面染上綠色或紅色等顏色,確認到干涉不均勻。
(實施例10)
將實施例9製作之防霧防污層積體曝露於400℃的氛圍中13秒,並藉由真空成型,使凹面成為防霧防污層般,成型了具有φ80mm的「8」曲線透鏡狀的防霧防污層積體。防霧防污層沒有產生受損、裂痕、剝離等外觀不佳的情形。之後,使用湯姆森刀片(Thomson blade)重擊該具有φ80mm的「8」曲線透鏡狀的防霧防污層積體。將其設置於嵌入成形用模具,並填充溶融的聚碳酸酯後,進行冷卻直到聚碳酸酯固化。之後,打開模具得到凹面係防霧防污層的「8」曲線透鏡。將得到之「8」曲線透鏡直接用於硬塗層形成製程(洗淨透鏡→浸漬於硬塗液→乾燥→硬化)後,可得到於防霧防污層表面不形成硬塗層,只於凸面側形成硬塗層的結果。之後,針對防霧防污層側進行呼氣防霧性評價、防污試驗、及擦拭試驗,得到皆為○之結果。
(實施例11)
將實施例9製作之防霧防污層積體曝露於500℃的氛圍中7秒,並藉由真空成型,使凹面成為防霧防污層般,成型了具有φ80mm的「8」曲線透鏡狀的防霧防污層積體。防霧防污層沒有產生受損、裂痕、剝離等外觀不佳的情形。之後,使用湯姆森刀片(Thomson blade)重擊該具有φ80mm的「8」曲線透鏡狀的防霧防污層積體。
接著,再同樣地製作一個具有φ80mm的「8」曲線透鏡狀的防霧防污層積體。
將此兩個「8」曲線透鏡狀的防霧防污層積體(φ80mm)設置於雙重嵌入成形用模具,並填充溶融的聚碳酸酯後,進行冷卻直到聚碳酸酯固化。之後,打開模具得到凹面與凸面的兩側皆係防霧防污層的「8」曲線透鏡。之後,針對此兩側進行呼氣防霧性評價、防污試驗、及擦拭試驗,得到皆為○之結果。
[表3]
實施例10 | 實施例11 | |
呼氣防霧性 | ○ | ○ |
防污試驗 | ○ | ○ |
擦拭試驗 | ○ | ○ |
(實施例12)
<防霧防污層積體的製作>
使用松浪硝子工業股份有限公司製之S9213(玻璃基材,厚度1.2mm~1.5mm)作為無機基材。
將下述組成的溶液塗佈於無機基材上,使其塗佈厚度為100nm。進行110℃、30分鐘的加熱處理並形成定向層。
-溶液(合計100質量%)-
‧KBM-503(信越化學工業股份有限公司製) 1質量%
‧異丙醇 49.5質量%
‧純水 49.5質量%
接著,以實施例1使用之活性能量射線硬化性樹脂組成物塗佈於定向層上,使其塗佈厚度為30μm。於氮氛圍下,使用金屬鹵化物燈,以照射量1,800mJ/cm2
照射紫外線,使防霧防污層硬化,並得到防霧防污層積體。
將得到之防霧防污層積體進行上述的評價。將結果顯示於表4。
[表4]
實施例12 | ||
塗佈厚度(μm) | 30 | |
接觸角(。) | 純水 | 113 |
十六烷 | 67 | |
呼氣防霧性 | ○ | |
防污試驗 | ○ | |
擦拭試驗 | ○ |
同時,依據JIS K 5400,且藉由交叉切割(1mm間隔x100塊)透明膠帶(NICHIBAN股份有限公司製,CT24)剝離試驗,評價防霧防污層的黏合性,其結果為黏合性良好之100/100(0個地方剝離)。
再者,藉由設置定向層,使得防霧防污層的黏合性顯著地提升。
[產業上的可利用性]
本發明的防霧防污層積體能用在貼合於玻璃窗、冷藏/冷凍展示櫃、汽車的窗戶等窗材、浴室內的鏡、汽車側鏡等鏡子、浴室的地板與牆壁、太陽能電池面板表面、防盜監視攝影機等。同時,因為本發明的防霧防污層積體的一態樣係容易成形加工的,故可利用模內成形、嵌入成形,而將其使用於眼鏡、護目鏡、頭盔、透鏡、微透鏡陣列、汽車的車前燈罩、前面板、側板、後板等。
211:樹脂製基材
212:防霧防污層
500:防霧防污層積體
501:第一模具
502:第二模具
504:吸引孔
505:進模口
506:成形材料
507:物品
508:頂針
600:硬塗層
601:光學薄膜
[圖1A] 圖1A係為藉由模內成形來製造本發明物品的一例的說明用製程圖。
[圖1B] 圖1B係為藉由模內成形來製造本發明物品的一例的說明用製程圖。
[圖1C] 圖1C係為藉由模內成形來製造本發明物品的一例的說明用製程圖。
[圖1D] 圖1D係為藉由模內成形來製造本發明物品的一例的說明用製程圖。
[圖1E] 圖1E係為藉由模內成形來製造本發明物品的一例的說明用製程圖。
[圖1F] 圖1F係為藉由模內成形來製造本發明物品的一例的說明用製程圖。
[圖2] 圖2係為本發明物品的一例的概略剖面圖(其之1)。
[圖3] 圖3係為本發明物品的一例的概略剖面圖(其之2)。
[圖4] 圖4係為本發明物品的一例的概略剖面圖(其之3)。
[圖5] 圖5係為本發明物品的一例的概略剖面圖(其之4)。
211:樹脂製基材
212:防霧防污層
506:成形材料
Claims (2)
- 一種活性能量射線硬化性樹脂組成物,其係包含: 具有自由基聚合性不飽和基團的親水性單體; 具有自由基聚合性不飽和基團的疏水性單體;及 光聚合起始劑;其中, 前述活性能量射線硬化性樹脂組成物係用於形成平滑的最表面層,且防止具有該最表面層的物品被污染; 藉由活性能量射線來將該活性能量射線硬化性樹脂組成物硬化後之作為前述最表面層之防霧防污層的表面之純水接觸角為90°以上。
- 如請求項1所述之活性能量射線硬化性樹脂組成物,其中,該具有自由基聚合性不飽和基團的親水性單體係具有聚氧伸烷鏈之(甲基)丙烯酸酯,且該具有自由基聚合性不飽和基團的疏水性單體係具有氟與矽中至少任一者之(甲基)丙烯酸酯。
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