201130655 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種於表面形成透明導電膜之透明樹脂 層合板。 【先前技術】 於汽車導航系統、行動資訊終端、產業機械之操作面 板、個人電腦之畫面、攜帶遊戲機等係可利用觸控面板。 觸控面板係具備互相對向之板狀的一對透明導電體、用以 於該透明導電體間設有空間之點狀間隔物,與押住一者之 透明導電體(上部電極)時,藉由該透明導電體與另一者 之透明導電體(下部電極)接觸而進行通電所構成(例如 ,參照專利文獻1 )。 前述透明導電體一般係於由聚對酞酸乙二酯、聚碳酸 酯等所構成之透明基板的表面上,形成含有參雜錫之氧化 銦(IT 0 )等的導電性物質之透明導電膜(例如,參照專 利文獻1〜3)。 在前述透明基板中,於與形成前述透明導電膜之側的 表面相反側的背面,係要求優異之表面硬度。亦即,使用 前述透明導電體作爲下部電極時,係前述透明基板的背面 係配置於加工時與加工桌台對向之下側,故從加工桌台受 到物理性衝擊。又,使用前述透明導電體作爲上部電極時 係前述透明基板之背面成爲以指、觸控筆等碰觸的觸控面 ,故從觸控筆等受到物理性衝擊。因此,即使下部電極及 -5- 201130655 上部電極之任一者的情形,於前述透明基板之背面係要求 優異之表面硬度。但對於此表面硬度之要求,在如專利文 獻1〜3記載的習知之透明基板中,係未能充分對應乃爲現 狀。 [先前技術文獻] [專利文獻] [專利文獻1]特開2008 - 3 02601號公報 [專利文獻2]特開平7 - 2053 85號公報 [專利文獻3]特開2001 - 322197號公報 【發明內容】 [發明之槪要] [發明欲解決之課題] 本發明之課題係提供一種適宜於與形成透明導電膜側 的表面相反側之背面具有優異的表面硬度之觸控面板的透 明基板之透明樹脂層合板。 [用以解決課題之手段] 本發明人等係爲解決上述課題,累積專心硏究之結果 ’發現由以下之構成所構成的解決方法,終完成本發明。 (1 ) 一種透明樹脂層合板,其係於表面形成透明導 電膜之透明樹脂層合板,其係具備:聚碳酸酯樹脂層、及 層合於該聚碳酸酯樹脂層之形成前述透明導電膜側的單面 -6 - 201130655 與相反側之另一面的丙烯酸樹脂層。 (2) 如前述(1 )項之透明樹脂層合板,其中前述聚 碳酸酯樹脂層之厚度爲全體之厚度的50 %以上。 (3) 如前述(1)或(2)項之透明樹脂層合板,其 中前述丙烯酸樹脂層爲由甲基丙烯酸樹脂及橡膠狀聚合物 所構成之層。 (4) 如前述(1)〜(3)項之透明樹脂層合板,其中 於聚碳酸酯樹脂層之前述單面層合丙烯酸樹脂層。 (5 )如前述(1 )〜(4 )項中任一項之透明樹脂層合 板,其係可使用來作爲觸控面板之透明導電體的透明基板 〇 (6 )如前述(1 )〜(4 )項中任一項之透明樹脂層合 板,其係可使用來作爲觸控面板之下部電極的透明基板。 [發明之效果] 若依本發明之透明樹脂層合板,與形成透明導電膜之 側的表面相反側之背面,爲由表面硬度優異之丙烯酸樹脂 層,故可得到優於由聚對苯二甲酸乙二酯、聚碳酸酯等所 構成之習知背面的表面硬度。又,使前述丙烯酸樹脂層層 合於具有耐衝擊性之聚碳酸酯樹脂層,故可確保透明樹脂 層合板全體的耐衝擊性。而且,丙烯酸樹脂之折射率係近 似空氣之折射率,故若層合丙烯酸樹脂層,很難反射光, 可得到高於聚碳酸酯樹脂單層之光透過性。 若於前述透明樹脂層合板之表面形成透明導電膜,可 201130655 得到透明導電體。因此,本發明之透明樹脂層合板係如前 述(5)般,可適宜使用來作爲觸控面板之透明導電體的 透明基板。 尤其,如前述(6)般,就在加工時受到物理性衝擊 之下部電極的透明基板爲適宜。 [用以實施發明之形態] 以下,有關本發明之透明樹脂層合板的一實施形態, 參照圖1而詳細說明。如圖1所示般,於本實施形態之透明 樹脂層合板10的表面10a形成透明導電膜21。該透明樹脂 層合板10係具備聚碳酸酯樹脂層1與丙烯酸樹脂層2。 構成聚碳酸酯樹脂層1之聚碳酸酯樹脂係可舉例如: 使1種以上之二價酚與1種以上之羰化劑以界面聚縮合法、 熔融酯交換法等反應所得到的樹脂、使碳酸酯預聚物以固 相酯交換法等聚合所得到之樹脂、使環狀碳酸酯化合物以 開環聚合法聚合所得到的樹脂等。 前述二價酚可舉例如氫醌、間苯二酚、4,4’ -二羥基 二苯基、雙(4 -羥基苯基)甲烷、雙{(4 -羥基-3,5-二甲基)苯基}甲烷、1,1-雙(4 -羥基苯基)乙烷、 1,1_雙(4-羥基苯基)-1-苯基乙烷、2,2-雙(4-羥 基苯基)丙烷(通稱雙酚A) 、2,2 -雙{ (4 -羥基-3-甲基)苯基}丙烷、2,2 -雙{(4 -羥基-3,5 -二甲基)苯 基}丙烷、2,2 -雙{(4 -羥基-3,5 -二溴)苯基}丙烷、 2,2-雙{(3-異丙基-4-羥基)苯基}丙烷、2,2-雙{( 201130655 4 -羥基-3-苯基)苯基}丙烷、2,2 -雙{(4 -羥基苯基 )丁烷、2,2 -雙{(4 -羥基苯基)-3 -甲基丁烷、2,2-雙(4 -羥基苯基)-3,3 -二甲基丁烷、2,4 -雙{(4 -羥 基苯基)-2-甲基丁烷、2,2-雙(4 -羥基苯基)戊烷 、2,2 -雙(4 -羥基苯基)-4-甲基戊烷、1,1-雙(4 -羥基苯基)環己烷、1,1-雙(4 -羥基苯基)-4-異丙 基環己烷、1,1-雙(4 -羥基苯基)-3,3,5 -三甲基環己 烷、9,9_雙(4 -羥基苯基)芴、9,9 -雙{ (4 -羥基- 3-甲基)苯基}芴、α,α’ -雙(4 -羥基苯基)-鄰-二異 丙基苯、α,α’ -雙(4 -羥基苯基)-間-二異丙基苯、 α,α’ -雙(4 -羥基苯基)-對-二異丙基苯、1,3-雙 (4 -羥基苯基)-5,7二甲基金剛烷基、4,4’-二羥基二 苯基楓、4,4’ -二羥基二苯基亞楓、4,4’ -二羥基二苯基 硫醚、4,4’-二羥基二苯基酮、4,4’-二羥基二苯基醚、 4,4’ -二羥基二苯基酯等。 其中,宜使用由雙酚A、2,2-雙{(4 -羥基-3-甲 基)苯基}丙烷、2,2 -雙(4 -羥基苯基)丁烷、2,2 -雙 (4 -羥基苯基)-3 -甲基丁烷、2,2 -雙(4 -羥基苯基 )-3,3 -二甲基丁烷、2,2 -雙(4 -羥基苯基)-4 -甲 基戊烷、1,1-雙(4 -羥基苯基)-3,3,5 -三甲基環己烷 及α,α’_雙(4 -羥基苯基)-間-二異丙基苯所構成之 群中選出的1種以上之二價酚,更宜爲雙酚Α之單獨使用、 雙酚A及1,1-雙(4 -羥基苯基)-3,3,5 -三甲基環己烷的 使用、由雙酚A、2,2 -雙{(4 -羥基-3 -甲基)苯基}丙 -9 - 201130655 烷及α,α’ -雙(4-羥基苯基)-間-二異丙基苯所構成 之群中選出的1種以上之二價酚的並用。 前述羰化劑可舉例如光氣等之鹵化羰基、二苯基碳酸 酯等之碳酸酯、二價酚之二鹵甲酸酯等之鹵化甲酸酯等。 構成丙烯酸樹脂層2之丙烯酸樹脂,一般係可使用甲 基丙烯酸樹脂。前述甲基丙烯酸樹脂可爲甲基丙烯酸甲酯 單元1〇〇重量%之甲基丙烯酸甲酯單體聚合物,可爲甲基丙 烯酸甲酯、與可與該甲基丙烯酸甲酯共聚合之1種以上的 其他單體之共聚物。其中,宜爲以甲基丙烯酸甲酯單元爲 主成分之樹脂,具體上,宜爲含有甲基丙烯酸甲酯單元50 重量%以上之甲基丙烯酸甲酯,更宜爲含有甲基丙烯酸甲 酯單元70重量%以上之甲基丙烯酸甲酯。 可與前述甲基丙烯酸甲酯共聚合之其他單體可舉例如 甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸環己酯、 甲基丙烯酸苯酯、甲基丙烯酸苯甲酯、甲基丙烯酸2-乙基 己酯、甲基丙烯酸2-羥基乙酯等之甲基丙烯酸甲酯以外之 甲基丙烯酸酯類、或丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁 酯、丙烯酸環己酯、丙烯酸苯酯、丙烯酸苯甲酯、丙烯酸 2-乙基己酯、丙烯酸2-羥基乙酯等之丙烯酸甲酯類。又, 苯乙烯或取代苯乙烯類,例如氯苯乙烯、溴苯乙烯等之鹵 化苯乙烯類、或乙烯基甲苯、α -甲基苯乙烯等之烷基苯 乙烯類等。進一步,可舉例如甲基丙烯酸、丙烯酸等之不 飽和酸類、丙烯腈、甲基丙烯腈、馬來酸酐、苯基馬來醯 亞胺、環己基馬來醯亞胺等。 -10- 201130655 丙烯酸樹脂層宜爲含有橡膠狀聚合物。藉 明樹脂層合板1 0很難龜裂。尤其,藉由混合甲 脂與橡膠狀聚合物’而宜使丙烯酸樹脂層2形 烯酸樹脂及橡膠狀聚合物所構成之層。 前述橡膠狀聚合物係可舉例如丙烯酸系多 物、或於5〜80重量份之橡膠狀聚合物與丙烯酸 體等之乙烯性不飽和單體20〜95重量份接枝聚 枝共聚物等。 前述丙烯酸系多層構造聚合物宜爲含有橡 20~60重量%左右,宜爲具有硬質層作爲最外層 含有硬質層作爲最內層。 前述橡膠彈性之層係玻璃轉移點(Tg )爲 丙烯酸系聚合物之層,具體上宜爲使從低級烷 、低級烷基甲基丙烯酸酯、低級烷氧基丙烯酸 丙稀酸醋、丙嫌醯胺、經基低級院基丙烧酸醋 烷基甲基丙烯酸酯、甲基丙烯酸及甲基丙烯鹿 以上之單官能單體,以烯丙基甲基丙烯酸酯等 體交聯而成之聚合物的層。低級烷基可舉例$丨 左右的直鏈或分枝的烷基,低級烷氧基烷基可 1〜8個左右的直鏈或分枝的烷氧基烷基。 前述硬質層宜Tg爲25 °C以上之丙烯酸系聚 具體上宜爲具有碳數1~4個的烷基之烷基甲基 獨或作爲主成分而聚合之單獨聚合物或共聚物 基丙烯酸酯作爲主成分而形成共聚物時,共聚 此,可使透 基丙烯酸樹 成由甲基丙 層構造聚合 系不飽和單 合而成之接 膠彈性之層 ,進一步宜 未達2 5 °C之 基丙烯酸酯 酯、氰乙基 、羥基低級 芝選出的1種 之多官能單 ]碳數1〜8個 舉例如碳數 合物的層, 丙烯酸酯單 。以烷基甲 合成分係可 -11 - 201130655 使用其他之烷基甲基丙烯酸酯或烷基丙烯酸酯、苯乙烯、 取代苯乙烯、丙烯腈、甲基丙烯腈等之單官能單體,進一 步可加入多官能單體而形成交聯聚合物。 丙烯酸系多層構造聚合物已記載於例如特公昭55-27576號公報、特開平6 - 8 073 9號公報、特開昭49 - 23292 號公報。 於前述5~80重量份之橡膠狀聚合物與乙烯性不飽和單 體20~95重量份接枝聚合而成之接枝共聚物中,前述橡膠 狀聚合物係可使用例如聚丁二烯橡膠、丙烯腈/丁二烯共 聚物橡膠、苯乙烯/ 丁二烯共聚物橡膠等之二烯系橡膠、 聚丁基丙烯酸酯、聚丙基丙烯酸酯、聚-2-乙基己基丙 烯酸酯等之丙烯系橡膠、乙烯/丙烯/非共軛二系橡膠等。 又,於此橡膠狀聚合物接枝共聚合所使用之乙烯性單體, 係可舉例如苯乙烯、丙烯腈、烷基(甲基)丙嫌酸醋等。 此等之接枝共聚物已記載於例如特開昭5 5 - 1 4 7 5 1 4號公報 、特公昭47 - 9740號公報等。 於丙烯酸樹脂分散橡膠狀聚合物時係宜相對於丙稀酸 樹脂100重量份,使橡膠狀聚合物一般以3〜150重量份,較 佳係5〜50重量份之比率分散。若橡膠狀聚合物之量太多, 有時表面硬度會降低。又,若橡膠狀聚合物之量太少,很 難得到使透明樹脂層合板10不易龜裂之效果。 又,於聚碳酸酯樹脂層1、丙烯酸樹脂層2中係分別需 要而亦可添加例如光擴散劑、消光劑、染料、光安定劑、 紫外線吸收劑、抗氧化劑、離型劑、耐燃劑、抗靜電劑等 -12- 201130655 之1種以上的添加劑。 此處’前述之聚碳酸酯樹脂層1、丙烯酸樹脂層2係任 一者均具有透明性(光透明性)。前述「透明」意指透過 可見光。以下,「透明」之記載,係與此同樣地規定。透 明樹脂層合板1 0係層合聚碳酸酯樹脂層1、丙烯酸樹脂層2 而成,故具有透明性。 前述丙烯酸樹脂層2係具有優異之表面硬度。該丙烯 酸樹脂層2係層合於聚碳酸酯樹脂層1之形成透明導電膜21 側之單面1 a與相反側之另一面1 b。因此,透明樹脂層合板 10之形成透明導電膜21側之表面10a與相反側之背面l〇b, 係由表面硬度優異之丙烯酸樹脂層2所構成,故該背面l〇b 具有優異之表面硬度。 又,前述之聚碳酸酯樹脂層1係具有耐衝擊性,故可 確保透明樹脂層合板〗〇全體之耐衝擊性。進一步,丙烯酸 樹脂之折射率係近似空氣之折射率,故若層合丙烯酸樹脂 層2,很難反射光。因此,透明樹脂層合板1 〇係可顯示高 的光透過性。 透明樹脂層合板1〇—般爲片狀’其厚度宜爲0.1〜2mm 〇 又,聚碳酸酯樹脂層1之厚度宜爲全體之厚度的50%以 上,更宜爲70%以上,最宜爲80%以上。藉此,可確保透 明樹脂層合板1 〇之耐衝擊性’該透明樹脂層合板1 〇變成很 難龜裂。 另外,若對於全體厚度之聚碳酸酯樹脂層1的厚度太 -13- 201130655 薄,丙烯酸樹脂層2之厚度變大。丙烯酸樹脂層2—般耐熱 性較聚碳酸酯樹脂層1差。因此,若對於全體厚度之聚碳 酸酯樹脂層1的厚度太薄,不僅透明樹脂層合板10之耐衝 擊性降低,亦恐耐熱性亦降低。 丙烯酸樹脂層2之厚度宜爲10// m以上,更宜爲20〜200 // m。若丙烯酸樹脂層2之厚度太薄,恐無法得到充分的表 面硬度。又,若丙烯酸樹脂層2之厚度太大,恐透明樹脂 層合板10之耐熱性降低。 透明樹脂層合板10係可使聚碳酸酯樹脂層1與丙烯酸 樹脂層2介由例如特定之接著劑層合而貼合,或以共押出 成形層合一體化而製造。 以共押出成形製造透明樹脂層合板10時係首先,使用 2基或3基之單軸或雙軸之押出機,而使構成前述聚碳酸酯 樹脂層1之聚碳酸酯樹脂、與構成丙烯酸樹脂層2之丙烯酸 樹脂分別熔融混練之後,使此等介由分流器模頭(feed block die)或分歧管模頭(multi manifold die)等而層合 。繼而,使被層合一體化之薄片狀的熔融樹脂例如使用輥 輪單元等而冷却固化,俾得到透明樹脂層合板1 〇。以下, 有關以共押出成形製造透明樹脂層合板10之一實施形態, 參照圖2而詳細說明。 如圖2所示般,首先,一邊使聚碳酸酯樹脂及丙烯酸 樹脂分別以個別之押出機3 1、32加熱而熔融混練,一邊從 共押出成形用之模頭33押出,層合一體化。繼而,使從模 頭33所共押出之片狀的熔融樹脂34朝略水平方向對向配置 -14 - 201130655 之2根冷却輥輪35挾住進行冷却。若調整熔融樹脂34之厚 度、或2根冷却輥輪3 5的間隔、周速度等,可調整所得到 之透明樹脂層合板1 〇的厚度。 冷却輥輪3 5係以1號輥輪3 6、2號輥輪3 7所構成。1號 輥輪36、2號輥輪37係至少一者連接於馬達等之旋轉驅動 機構,兩輥輪以特定之周速度旋轉所構成。1號輥輪36、2 號輥輪37之中,2號輥輪37係在兩輥輪間挾持之後的片狀 之透明樹脂層合板10被捲覆之捲覆輥輪。 1號輥輪3 6、2號輥輪3 7可舉例如具有剛性之金屬輥輪 、具有彈性之金屬彈性輥輪等。前述金屬輥輪係可舉例如 鑽孔式輥輪或螺旋式輥輪等。前述金屬彈性輥輪係具備例 如軸輥輪、與以被覆此軸輥輪之外周面之方式配置且接觸 於熔融樹脂34之圓筒形的金屬製薄膜,於此等軸輥輪與金 屬製薄膜之間封入水或油等已被溫度控制之液體者、或於 橡膠輥輪之表面捲繞金屬皮帶者等。 1號輥輪36、2號輥輪37係可只以金屬輥輪,或只以金 屬彈性輥輪構成,亦可組合金屬輥輪與金屬彈性輥輪而構 成。 組合金屬輥輪與金屬彈性輥輪時,係可得到強度或熱 收縮之異方性被降低之透明樹脂層合板1 〇。亦即,若使熔 融樹脂34挾持於金屬輥輪與金屬彈性輥輪之間,金屬彈性 輥輪介由熔融樹脂34而沿著金屬輥輪之外周面而呈凹狀彈 性變形,金屬彈性輥輪與金屬輥輪介由熔融樹脂3 4而以特 定之接融長度接融。藉此,金屬輥輪與金屬彈性輥輪對於 -15- 201130655 熔融樹脂34而以面接融壓接,被挾持於此等輥輪間之熔融 樹脂34係一邊被均一加壓成面狀一邊製膜。若如此地進行 製膜,降低製膜時之變形,故可得到強度或熱收縮之異方 性被降低之透明樹脂層合板10。 又,組合金屬輥輪與金屬彈性輥輪時,係宜使金屬彈 性輥輪作爲1號輥輪36,以金屬輥輪作爲2號輥輪37。藉此 ,藉由組合金屬輥輪與金屬彈性輥輪,俾提高所得到之效 果》 於1號輥輪3 6、2號輥輪3 7間所挾持之後的片狀之透明 樹脂層合板10係被捲繞於2號輥輪37之後,一邊藉未圖示 之拉引輥輪於搬送輥輪上冷却一邊拉引,藉此得到透明樹 脂層合板1 0。 另外,於透明樹脂層合板10之表面l〇a所形成的透明 導電膜21係含有導電性物質之透明膜,可採用於觸控面板 所採用之各種公知者》 前述導電性物質並無特別限定,可舉例如氧化銦、摻 雜錫之氧化銦(ITO)、慘雜鎵之氧化銦、摻雜鋅之氧化 銦、氧化錫 '摻雜銻之氧化錫(A Τ Ο )、慘雜氟之氧化錫 CFTO)、氧化鮮、慘雜銘之氧化鋅(AZO)、慘雜鎵之 氧化鋅(GZO )、摻雜氟之氧化鋅、摻雜銦之氧化鋅、摻 雜硼之氧化鋅、氧化鎘等。 透明導電膜2 1係亦可依需要而含有黏結劑樹脂、添加 劑等。則述黏結劑樹脂可舉例如熱塑性樹脂、熱硬化性樹 月曰、紫外線硬化樹脂等。前述添加劑可舉例如耐燃劑、紫 -16- 201130655 外線吸收劑、著色劑、可塑劑等。 透明導電膜21之厚度適宜爲0.05~5"m左右。透明導 電膜2 1係使例如於溶劑中加入前述導電性物質之塗佈液, 直接塗佈於表面1 〇a而乾燥,或,預先於支撐體上可剝離 地支撐之透明導電膜21,介由特定之接著劑層而從前述支 撐體轉印至表面l〇a而形成。 若於表面1 〇a形成透明導電膜2 1,可得到透明導電體 2 0。因此,透明樹脂層合板1 〇係可適宜使用來作爲例如於 汽車導航系統、行動資訊終端、產業機械之操作面板、個 人電腦之畫面、攜帶遊戲機等之觸控面板中的透明導電體 的透明基板。 透明樹脂層合板1〇係從前述之理由,因其背面1〇b具 有優異之表面硬度’故亦可適宜作爲觸控面板中之下部電 極及上部電極之任一者的透明基板’尤其,可適宜使用來 作爲加工時受到物理衝擊之下部電極的透明基板。 其次,有關本發明之透明樹脂層合板的另一實施型態 參照圖3而詳細說明。又’在圖3中,係與前述圖1、圖2相 同之構成部分係賦予相同的符號而省略說明。 如圖3所示般’於本實施形態之透明樹脂層合板1 1的 表面1 1 a形成透明導電膜2 1 °該透明樹脂層合板1 1係具備 聚碳酸酯樹脂層丙嫌酸樹脂層2 ’故與前述一實施形態 之透明樹脂層合板10同樣地’其背面1113具有優異之表面 硬度。 透明樹脂層合板11係進一步具備丙烯酸樹脂層3。該 -17- 201130655 丙烯酸樹脂層3係層合於聚碳酸酯樹脂層1之單面la。若以 此配置層合丙烯酸樹脂層3,可提昇透明樹脂層合板11之 耐衝擊性。 丙烯酸樹脂層2、3之組成及厚度係可互爲同一,亦可 相異。又,3層構造之透明樹脂層合板1 1係依丙烯酸樹脂 層2' 3之組成或厚度而有時耐衝擊性降低而易龜裂。是故 ,於丙烯酸樹脂層2、3係宜使前述之橡膠狀聚合物分散。 藉此,可抑制透明樹脂層合板1 1之耐衝擊性降低而易龜裂 。其他之構成係與前述一實施形態之透明樹脂層合板10同 樣,故省略說明。 【實施方式】 以下,表示本發明之實施例,但本發明係不限定於此 等。又’以下之實施例中,表示含量及使用量之份係只要 未特別記載’爲重量基準。又,在以下之實施例及比較例 使用之押出裝置的構成係如下。 押出機31 :螺桿徑65mm、單軸、附排氣孔(東芝機 械(股)製)。 押出機32:螺桿徑45mm、單軸、附排氣孔(日立造 船(股)製)。 分流器:2種3層及2種2層分配(日立造船(股)製) 〇 模頭33: T模、模唇寬1400mm、模唇間隔lmm (日立 造船(股)製)。 -18- 201130655 冷却輥輪35 :橫模、面長1 400mm、徑300πιηιφ之冷却 車昆輪2根。 如圖2所示般配置押出機3 1、3 2、模頭3 3 ’將分流器 配置於特定位置。然後,使構成冷却輥輪3 5之1號輕輪3 6 、2號輥輪37分別構成如下。 <輥輪構成1 > (1號輥輪3 6 ) 如被覆軸輥輪之外周面配置金屬製薄膜’以於軸輥輪 與金屬製薄膜之間封入流體的金屬彈性輥輪作爲1號輥輪 3 6。軸輥輪、金屬製薄膜及流體係如下。 軸輥輪:不銹鋼製。 金屬製薄膜:厚2mmm之不銹鋼製的鏡面金屬管筒。 流體:爲油,藉由溫度控制此油,而可溫度控制金屬 彈性輥輪。更具體地,係藉溫度調節機之ON - OFF控制, 加熱、冷却前述油而可溫度控制,於軸輥輪與金屬製薄膜 之間循環。 (2戚輕輪37) 使表面狀態形成鏡面之不銹鋼製的螺旋式輥輪(金屬 輥輪)作爲2號輥輪3 7。 又’ 1號輥輪36、2號輥輪37介由熔融樹脂34而接融之 接融長度係形成4mm。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent resin laminate which forms a transparent conductive film on a surface. [Prior Art] A touch panel can be used for a car navigation system, an action information terminal, an operation panel of an industrial machine, a screen of a personal computer, a portable game machine, and the like. The touch panel is provided with a pair of transparent conductors facing each other in a plate shape, a dot spacer for providing a space between the transparent conductors, and a transparent conductor (upper electrode) for holding one of them. The transparent conductor is electrically connected to the other transparent conductor (lower electrode) (for example, see Patent Document 1). The transparent conductor is generally formed on a surface of a transparent substrate made of polyethylene terephthalate or polycarbonate to form a transparent conductive film containing a conductive substance such as indium oxide (IT 0 ) doped with tin. (For example, refer to Patent Documents 1 to 3). In the transparent substrate, an excellent surface hardness is required on the back surface opposite to the surface on the side on which the transparent conductive film is formed. In other words, when the transparent conductor is used as the lower electrode, the back surface of the transparent substrate is placed on the lower side of the processing table during processing, so that it is physically impacted from the processing table. Further, when the transparent conductor is used as the upper electrode, the back surface of the transparent substrate is a touch surface that is touched by a finger, a stylus pen, or the like, so that it is physically impacted from a stylus or the like. Therefore, even in the case of any of the lower electrode and the upper electrode of -5-201130655, excellent surface hardness is required on the back surface of the transparent substrate. However, in the conventional transparent substrate described in Patent Documents 1 to 3, the requirements for the surface hardness are not sufficiently matched. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] [Problem to be Solved by the Invention] An object of the present invention is to provide a transparent resin for a transparent substrate of a touch panel having an excellent surface hardness on the back side opposite to the surface on the side where the transparent conductive film is formed. Laminate. [Means for Solving the Problems] The inventors of the present invention have completed the present invention by solving the above-mentioned problems and accumulating the results of intensive research. (1) A transparent resin laminated board which is a transparent resin laminated board which forms a transparent conductive film on the surface, and is provided with a polycarbonate resin layer and a side of the polycarbonate resin layer formed on the side of the transparent conductive film One side -6 - 201130655 with an acrylic layer on the opposite side of the other side. (2) The transparent resin laminate according to the above (1), wherein the thickness of the polycarbonate resin layer is 50% or more of the total thickness. (3) The transparent resin laminate according to the above (1) or (2), wherein the acrylic resin layer is a layer composed of a methacrylic resin and a rubbery polymer. (4) The transparent resin laminate of the above (1) to (3), wherein the acrylic resin layer is laminated on the one side of the polycarbonate resin layer. (5) The transparent resin laminate according to any one of the above items (1) to (4), which is a transparent substrate (6) which can be used as a transparent conductor of a touch panel, as described above (1) to (1) The transparent resin laminate of any of the items 4 to 4, which can be used as a transparent substrate for the lower electrode of the touch panel. [Effects of the Invention] According to the transparent resin laminate of the present invention, the back surface on the side opposite to the surface on the side on which the transparent conductive film is formed is an acrylic resin layer excellent in surface hardness, so that it is superior to poly(terephthalic acid). The surface hardness of the conventional back surface composed of ethylene glycol, polycarbonate, or the like. Further, since the acrylic resin layer is laminated on the polycarbonate resin layer having impact resistance, the impact resistance of the entire transparent resin laminate can be ensured. Further, since the refractive index of the acrylic resin is similar to the refractive index of air, if the acrylic resin layer is laminated, it is difficult to reflect light, and light transmittance higher than that of the polycarbonate resin single layer can be obtained. When a transparent conductive film is formed on the surface of the transparent resin laminate, a transparent conductor can be obtained in 201130655. Therefore, the transparent resin laminate of the present invention can be suitably used as a transparent substrate of a transparent conductor of a touch panel as in the above (5). In particular, as in the above (6), a transparent substrate which is physically impacted by the lower electrode during processing is suitable. [Embodiment for Carrying Out the Invention] Hereinafter, an embodiment of the transparent resin laminate of the present invention will be described in detail with reference to Fig. 1 . As shown in Fig. 1, a transparent conductive film 21 is formed on the surface 10a of the transparent resin laminate 10 of the present embodiment. The transparent resin laminate 10 is provided with a polycarbonate resin layer 1 and an acrylic resin layer 2. The polycarbonate resin constituting the polycarbonate resin layer 1 is, for example, a resin obtained by reacting one or more kinds of divalent phenols with one or more kinds of carbonylating agents by an interfacial polycondensation method, a melt transesterification method, or the like. A resin obtained by polymerizing a carbonate prepolymer by a solid phase transesterification method or the like, a resin obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method, or the like. The divalent phenol may, for example, be hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane or bis{(4-hydroxy-3,5-dimethyl Phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyl) Phenyl)propane (commonly known as bisphenol A), 2,2-bis((4-hydroxy-3-methyl)phenyl}propane, 2,2-bis((4-hydroxy-3,5-dimethyl) Phenyl}propane, 2,2-bis((4-hydroxy-3,5-dibromo)phenyl}propane, 2,2-bis{(3-isopropyl-4-hydroxy)phenyl}propane , 2,2-double {( 201130655 4 -hydroxy-3-phenyl)phenyl}propane, 2,2-bis((4-hydroxyphenyl)butane, 2,2-di-{(4-hydroxybenzene) 3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-di-{(4-hydroxyphenyl)-2-methyl Butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl) Cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclo Hexane, 9,9_double (4 - Hydroxyphenyl)anthracene, 9,9-bis{(4-hydroxy-3-methyl)phenyl}anthracene, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α , α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-double (4 -hydroxyphenyl)-5,7-dimethyl hydroxyalkyl, 4,4'-dihydroxydiphenyl maple, 4,4'-dihydroxydiphenyl sulfite, 4,4'-dihydroxydiphenyl A thioether, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester or the like. Among them, it is preferred to use bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-di (4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydroxyphenyl) -4 -methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and α,α'_bis(4-hydroxyphenyl)-inter- One or more divalent phenols selected from the group consisting of diisopropylbenzene, more preferably bisphenol oxime alone, bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3 , the use of 5-trimethylcyclohexane, from bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propan-9 - 201130655 alkane and α,α'-double ( A combination of one or more divalent phenols selected from the group consisting of 4-hydroxyphenyl)-m-diisopropylbenzene. The carbonylating agent may, for example, be a halogenated carbonyl group such as phosgene or a carbonate such as diphenyl carbonate or a halogenated formate such as a dihaloformate of divalent phenol. As the acrylic resin constituting the acrylic resin layer 2, a methacrylic resin can be generally used. The methacrylic resin may be a methyl methacrylate monomer having a methyl methacrylate unit of 1% by weight, which may be methyl methacrylate, and may be copolymerized with the methyl methacrylate. A copolymer of the above other monomers. Wherein, it is preferably a resin containing a methyl methacrylate unit as a main component, and specifically, it is preferably a methyl methacrylate containing 50% by weight or more of a methyl methacrylate unit, and more preferably a methyl methacrylate unit. 70% by weight or more of methyl methacrylate. Other monomers copolymerizable with the aforementioned methyl methacrylate may, for example, be ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, or a methacrylate other than methyl methacrylate such as 2-ethylhexyl acrylate or 2-hydroxyethyl methacrylate; or methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, A methyl acrylate such as phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate or 2-hydroxyethyl acrylate. Further, styrene or a substituted styrene, for example, a halogenated styrene such as chlorostyrene or bromostyrene, or an alkylstyrene such as vinyltoluene or ?-methylstyrene. Further, examples thereof include unsaturated acids such as methacrylic acid and acrylic acid, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, and cyclohexylmaleimide. -10- 201130655 The acrylic resin layer is preferably a rubbery polymer. It is difficult to crack the resin laminate 10 . In particular, a layer composed of an acrylic resin layer 2 type olefin resin and a rubbery polymer is preferably used by mixing the resin and the rubbery polymer. The rubber-like polymer may, for example, be an acrylic-based compound or a graft-polymerized copolymer of 50 to 80 parts by weight of a rubbery polymer and an ethylenically unsaturated monomer such as an acrylate. The acrylic multilayer structure polymer preferably contains about 20 to 60% by weight of the rubber, and preferably has a hard layer as the outermost layer and a hard layer as the innermost layer. The rubber elastic layer is a layer of an acrylic polymer, and is preferably a layer derived from a lower alkane, a lower alkyl methacrylate, a lower alkoxy acrylate, or a propylene. A polymer obtained by crosslinking an amine, a low-grade base-based acrylic acid acetoacetate alkyl methacrylate, a methacrylic acid or a methacrylic deer or the like, and a propylene acrylate or the like. Layer. The lower alkyl group may, for example, be a linear or branched alkyl group of about 丨, and the lower alkoxyalkyl group may have about 1 to 8 linear or branched alkoxyalkyl groups. The hard layer preferably has an acryl polycondensation having a Tg of 25 ° C or higher, specifically, an alkyl group having an alkyl group having 1 to 4 carbon atoms, or a single polymer or copolymer acrylate polymerized as a main component. When a copolymer is formed as a main component, the copolymerizable acrylic acid tree can be formed into a layer of a rubber-elastic layer which is formed by polymerization of a monomethyl acrylate layer, and further preferably has a base of less than 25 ° C. One type of polyfunctional monomer selected from the group consisting of acrylate ester, cyanoethyl group and hydroxy acetonide has a carbon number of 1 to 8 layers such as a carbon complex, and an acrylate monomer. The alkyl group can be synthesized as a -11 - 201130655 using other alkyl methacrylate or alkyl acrylate, styrene, substituted styrene, acrylonitrile, methacrylonitrile and the like, and further A polyfunctional monomer is added to form a crosslinked polymer. The acryl-type multilayer structure polymer is described in, for example, Japanese Patent Publication No. Sho 55-27576, Japanese Patent Application Laid-Open No. Hei No. Hei. In the graft copolymer obtained by graft-polymerizing 5 to 80 parts by weight of the rubbery polymer and 20 to 95 parts by weight of the ethylenically unsaturated monomer, the rubbery polymer may be, for example, polybutadiene rubber. , acrylonitrile/butadiene copolymer rubber, styrene/butadiene copolymer rubber, etc., diene rubber, polybutyl acrylate, polypropyl acrylate, poly-2-ethylhexyl acrylate, etc. It is a rubber, ethylene/propylene/non-conjugated secondary rubber, and the like. Further, examples of the vinyl monomer used in the graft copolymerization of the rubbery polymer include styrene, acrylonitrile, alkyl (meth) propylene vinegar, and the like. Such a graft copolymer is described in, for example, Japanese Laid-Open Patent Publication No. Hei-5-57-141, and Japanese Patent Publication No. Sho 47-9740. When the rubbery polymer is dispersed in the acrylic resin, the rubbery polymer is preferably dispersed in a ratio of from 3 to 150 parts by weight, preferably from 5 to 50 parts by weight, based on 100 parts by weight of the acrylic resin. If the amount of the rubbery polymer is too large, the surface hardness may be lowered. Further, if the amount of the rubbery polymer is too small, it is difficult to obtain an effect that the transparent resin laminate 10 is less likely to be cracked. Further, in the polycarbonate resin layer 1 and the acrylic resin layer 2, for example, a light diffusing agent, a matting agent, a dye, a light stabilizer, an ultraviolet absorber, an antioxidant, a release agent, a flame retardant, or the like may be added. One or more additives such as antistatic agent -12- 201130655. Here, the polycarbonate resin layer 1 and the acrylic resin layer 2 described above each have transparency (light transparency). The aforementioned "transparent" means that visible light is transmitted. Hereinafter, the description of "transparent" is defined in the same manner as above. Since the transparent resin laminate 10 is formed by laminating a polycarbonate resin layer 1 and an acrylic resin layer 2, it has transparency. The aforementioned acrylic resin layer 2 has excellent surface hardness. The acrylic resin layer 2 is laminated on the single surface 1 a of the polycarbonate resin layer 1 on the side of the transparent conductive film 21 and the other surface 1 b on the opposite side. Therefore, the surface 10a on the side of the transparent conductive film 21 of the transparent resin laminate 10 and the back surface lb on the opposite side are composed of the acrylic resin layer 2 having excellent surface hardness, so that the back surface l〇b has excellent surface hardness. . Further, since the polycarbonate resin layer 1 described above has impact resistance, it is possible to ensure the overall impact resistance of the transparent resin laminate. Further, since the refractive index of the acrylic resin is approximately the refractive index of air, it is difficult to reflect light if the acrylic resin layer 2 is laminated. Therefore, the transparent resin laminate 1 can exhibit high light transmittance. The transparent resin laminate 1 is generally in the form of a sheet, and its thickness is preferably 0.1 to 2 mm. Further, the thickness of the polycarbonate resin layer 1 is preferably 50% or more of the total thickness, more preferably 70% or more, and most preferably More than 80%. Thereby, the impact resistance of the transparent resin laminate 1 can be ensured. The transparent resin laminate 1 becomes very difficult to crack. Further, when the thickness of the polycarbonate resin layer 1 of the entire thickness is too thin from -13 to 201130655, the thickness of the acrylic resin layer 2 becomes large. The acrylic resin layer 2 is generally inferior in heat resistance to the polycarbonate resin layer 1. Therefore, if the thickness of the polycarbonate resin layer 1 of the entire thickness is too thin, not only the impact resistance of the transparent resin laminate 10 but also the heat resistance is lowered. The thickness of the acrylic resin layer 2 is preferably 10/m or more, more preferably 20 to 200 // m. If the thickness of the acrylic resin layer 2 is too thin, sufficient surface hardness may not be obtained. Further, if the thickness of the acrylic resin layer 2 is too large, the heat resistance of the transparent resin laminate 10 may be lowered. In the transparent resin laminate 10, the polycarbonate resin layer 1 and the acrylic resin layer 2 can be laminated by, for example, laminating a specific adhesive, or can be produced by co-extrusion molding lamination. When the transparent resin laminate 10 is formed by co-extrusion molding, first, a 2- or 3-base uniaxial or biaxial extruder is used to form the polycarbonate resin constituting the polycarbonate resin layer 1 and constitute an acrylic resin. After the acrylic resin of the layer 2 is separately melt-kneaded, the layers are laminated by a feed block die or a multi-manifold die or the like. Then, the sheet-like molten resin which is laminated and integrated is cooled and solidified, for example, using a roller unit or the like, and a transparent resin laminate 1 is obtained. Hereinafter, an embodiment in which the transparent resin laminate 10 is produced by co-extrusion molding will be described in detail with reference to Fig. 2 . As shown in Fig. 2, the polycarbonate resin and the acrylic resin are respectively melted and kneaded by heating by the individual extruders 31 and 32, and are extruded from the die 33 for co-extrusion molding, and laminated and integrated. Then, the sheet-like molten resin 34 which is co-extruded from the die 33 is cooled in a direction slightly horizontally facing the two cooling rolls 35 of the arrangement -14 - 201130655. The thickness of the obtained transparent resin laminate 1 〇 can be adjusted by adjusting the thickness of the molten resin 34, the interval between the two cooling rolls 35, the peripheral speed, and the like. The cooling roller 35 is composed of a No. 1 roller 36 and a No. 2 roller 37. At least one of the No. 1 roller 36 and the No. 2 roller 37 is connected to a rotary drive mechanism such as a motor, and the two rollers are rotated at a specific peripheral speed. Among the No. 1 roller 36 and No. 2 roller 37, the No. 2 roller 37 is a winding roller which is wound by the sheet-shaped transparent resin laminate 10 after being held between the two rollers. The No. 1 roller 3 and the No. 2 roller 3 7 may be, for example, a metal roller having rigidity, a metal elastic roller having elasticity, or the like. The metal roller system may be, for example, a drilled roller or a spiral roller. The metal elastic roller train includes, for example, a shaft roller and a cylindrical metal film disposed so as to be in contact with the outer circumferential surface of the shaft roller and in contact with the molten resin 34, and the isometric roller and the metal film. The temperature-controlled liquid such as water or oil is sealed between them, or the metal belt is wound around the surface of the rubber roller. The No. 1 roller 36 and the No. 2 roller 37 may be formed only by a metal roller or only a metal elastic roller, or may be formed by combining a metal roller and a metal elastic roller. When the metal roller and the metal elastic roller are combined, the transparent resin laminate 1 which is reduced in the anisotropy of strength or heat shrinkage can be obtained. That is, if the molten resin 34 is held between the metal roller and the metal elastic roller, the metal elastic roller is elastically deformed in a concave shape along the outer peripheral surface of the metal roller via the molten resin 34, and the metal elastic roller It is blended with the metal roller by a specific melt length through the molten resin 34. As a result, the metal roller and the metal elastic roller are surface-bonded to the -15-201130655 molten resin 34, and the molten resin 34 held between the rollers is uniformly pressed into a planar shape. . When the film formation is carried out in this manner, the deformation at the time of film formation is lowered, so that the transparent resin laminate 10 having reduced strength or heat shrinkage is obtained. Further, when the metal roller and the metal elastic roller are combined, it is preferable to use the metal elastic roller as the No. 1 roller 36 and the metal roller as the No. 2 roller 37. By combining the metal roller and the metal elastic roller, the effect obtained by the combination of the metal roller and the metal elastic roller is the sheet-like transparent resin laminate 10 after being held between the No. 1 roller 3 and the No. 2 roller 37. After being wound around the No. 2 roller 37, the drawing roller is pulled by cooling on the conveying roller by a drawing roller (not shown), whereby the transparent resin laminated plate 10 is obtained. In addition, the transparent conductive film 21 formed on the surface 10a of the transparent resin laminate 10 contains a transparent film of a conductive material, and can be used in various known persons used in a touch panel. The conductive material is not particularly limited. For example, indium oxide, tin-doped indium oxide (ITO), indium gallium indium oxide, zinc-doped indium oxide, tin oxide-doped tin oxide (A Τ Ο ), miscellaneous fluorine Tin oxide CFTO), oxidized fresh, miscellaneous zinc oxide (AZO), gallium-doped zinc oxide (GZO), fluorine-doped zinc oxide, indium-doped zinc oxide, boron-doped zinc oxide, oxidation Cadmium and so on. The transparent conductive film 21 may contain a binder resin, an additive, or the like as needed. The binder resin may, for example, be a thermoplastic resin, a thermosetting tree, or an ultraviolet curable resin. The aforementioned additives may, for example, be a flame retardant, a violet-16-201130655 external absorbent, a colorant, a plasticizer or the like. The thickness of the transparent conductive film 21 is suitably about 0.05 to 5 " m. The transparent conductive film 21 is applied, for example, by adding a coating liquid of the above-mentioned conductive material to a solvent, and directly applying it to the surface 1 〇a to be dried, or a transparent conductive film 21 which is previously detachably supported on a support. It is formed by transferring a specific adhesive layer from the aforementioned support to the surface 10a. If the transparent conductive film 2 1 is formed on the surface 1 〇a, the transparent conductor 20 can be obtained. Therefore, the transparent resin laminate 1 can be suitably used as, for example, a transparent conductor in a car navigation system, a mobile information system, an operation panel of an industrial machine, a screen of a personal computer, a touch panel of a portable game machine, or the like. Substrate. The transparent resin laminate 1 is a transparent substrate which is suitable as any of the lower electrode and the upper electrode in the touch panel because of the excellent surface hardness of the back surface 1 〇 b. It is suitably used as a transparent substrate that is subjected to a physical impact lower electrode during processing. Next, another embodiment of the transparent resin laminate of the present invention will be described in detail with reference to Fig. 3 . In FIG. 3, the same components as those in FIGS. 1 and 2 are denoted by the same reference numerals, and description thereof will be omitted. As shown in FIG. 3, a transparent conductive film 2 is formed on the surface 1 1 a of the transparent resin laminate 1 1 of the present embodiment. The transparent resin laminated plate 11 is provided with a polycarbonate resin layer acrylic acid resin layer 2 In the same manner as the transparent resin laminate 10 of the above-described embodiment, the back surface 1113 has excellent surface hardness. The transparent resin laminate 11 is further provided with an acrylic resin layer 3. The -17-201130655 acrylic resin layer 3 is laminated on one side la of the polycarbonate resin layer 1. When the acrylic resin layer 3 is laminated in this manner, the impact resistance of the transparent resin laminate 11 can be improved. The composition and thickness of the acrylic resin layers 2, 3 may be the same or different. Further, the transparent resin laminate 1 1 having a three-layer structure is likely to be cracked due to a decrease in impact resistance due to the composition or thickness of the acrylic resin layer 2' 3 . Therefore, it is preferable to disperse the rubbery polymer described above in the acrylic resin layers 2 and 3. Thereby, it is possible to suppress the impact resistance of the transparent resin laminate 1 1 from being lowered and to be easily cracked. The other components are the same as those of the transparent resin laminate 10 of the above-described embodiment, and thus the description thereof is omitted. [Embodiment] Hereinafter, embodiments of the present invention are shown, but the present invention is not limited thereto. Further, in the following examples, the parts indicating the content and the amount used are based on weight unless otherwise specified. Further, the configuration of the extruding device used in the following examples and comparative examples is as follows. Extruder 31: screw diameter 65 mm, single shaft, and vent hole (made by Toshiba Machine Co., Ltd.). Extruder 32: screw diameter 45 mm, single shaft, and vent hole (made by Hitachi Shipbuilding Co., Ltd.). Diverter: 2 types of 3 layers and 2 types of 2 layers (Hitachi Shipbuilding Co., Ltd.) 模 Die 33: T die, lip width 1400mm, lip spacing lmm (Hitachi Shipbuilding Co., Ltd.). -18- 201130655 Cooling roller 35: Two cooling cylinders with a length of 1 400mm and a diameter of 300πιηιφ. The extruders 3 1 and 3 2 and the die 3 3 ' are disposed as shown in Fig. 2 to arrange the flow dividers at specific positions. Then, the No. 1 light wheel 3 6 and the No. 2 roller 37 which constitute the cooling roller 35 are respectively configured as follows. <Roller Configuration 1 > (No. 1 Roller 3 6 ) A metal elastic film is disposed on the circumferential surface of the coated shaft roller to seal the fluid between the shaft roller and the metal film as No. 1 Roller 36. The shaft roller, the metal film and the flow system are as follows. Shaft roller: stainless steel. Metal film: Mirror metal tube made of stainless steel with a thickness of 2 mm. Fluid: is oil, which is controlled by temperature to control the metal elastic roller. More specifically, the ON-OFF control of the temperature controller is used to heat and cool the oil to control the temperature, and to circulate between the shaft roller and the metal film. (2 戚 light wheel 37) A stainless steel spiral roller (metal roller) which is mirror-finished on the surface is used as the No. 2 roller 37. Further, the first and second rolls 36 and 2 are formed by the molten resin 34 to form a joint length of 4 mm.
S -19- 201130655 (輥輪構成2 ) 使1號輥輪36、2號輥輪37形成任一者均使表面狀態形 成鏡面之不銹鋼製的螺旋式輥輪。 在以下之實施例及比較例所使用的樹脂如下。 樹脂1:僅芳香族聚碳酸酯之聚合物(住友Dow (股 )製之「Calibre 301 - 10」)。 樹脂2:甲基丙烯酸甲酯/丙烯酸甲酯=98/2 (重量比 )之共聚物。 樹脂3:於甲基丙烯酸甲酯/丙烯酸甲酯=96/4(重量 比)之共聚物9 1重量%含有於下述參考例得到之丙烯酸系 多層構造聚合物9重量%之丙烯酸樹脂系組成物。 樹脂4:於甲基丙烯酸甲酯/丙烯酸甲酯=96/4 (重量 比)之共聚物79重量%含有於下述參考例得到之丙烯酸系 多層構造聚合物21重量%之丙烯酸樹脂系組成物。 [參考例] (橡膠狀聚合物之製造) 依據特公昭5 5 - 275 76號之實施例記載的方法,製造 由3層構造所構成之丙烯酸系多層構造聚合物。具體上, 首先,於內容積5升之玻璃製反應容器中,饋入離子交換 水I 700g、碳酸鈉〇.7g、過硫酸鈉0.3g,在氮氣流下攪拌後 ,饋入Pelex OT-P ((股)花王製)4.46g、離子交換水 I50g、甲基丙烯酸甲酯150g、烯丙基甲基丙烯酸酯〇.3g後 ’昇溫至75°C,持續攪拌150分鐘。 -20- 201130655 繼而,從另一入口花90分鐘添加丁基丙烯酸酯689g、 苯乙烯162g、烯丙基甲基丙烯酸酯I7g之混合物、與過硫 酸鈉0.85g,pelex 〇τ — p 7,4g、離子交換水50g之混合物 ,進一步持續聚合90分鐘。 終止聚合後,進一步從各別之口花3 0分鐘添加甲基丙 烯酸甲酯326g、乙基丙烯酸酯14g之混合物與溶·解有過硫 酸鈉0.34g之離子交換水3〇g。 添加終了後,進一步保持60分鐘,結束聚合。使所得 到之乳膠投入於0.5 %氯化鋁水溶液而使聚合物凝集。再以 溫水洗淨5次後,乾燥而得到丙烯酸系多層構造聚合物。 [實施例1〜1 1 ] <透明樹脂層合板之製作> 就樹脂層A而言,以押出機3 1熔融混練表1所示之種類 的樹脂,供給至分流器。另外,就樹脂層B而言,以押出 機32熔融混練表1所示之種類的樹脂,供給至分流器。從 押出機3 1供給至分流器之樹脂層A成爲主層,從押出機3 2 供給至分流器之樹脂層B成爲表層(2號輥輪37側),進行 共押出成形。 繼而,使從模頭3 3所押出之熔融樹脂3 4,一邊以表1 所示之輥輪構成的1號輥輪3 6及2號輥輪3 7挾持,一邊製膜 ’得到由表1所示之厚度的2層構造所構成之透明樹脂層合 板。又,1號輥輪36之表面溫度爲120 °C,2號輥輪37之表 面溫度爲130C。此寺之溫度爲貫測各輕輪之表面溫度的 -21 - 201130655 値。又,在表1中之押出機31、32中的「厚度」表示樹脂 層A、B之各厚度。表1中之「總厚度」表示所得到之透明 樹脂層合板的總厚度。 [實施例12~22及比較例1] 就樹脂層A而言,以押出機31熔融混練表1所示之種類 的樹脂,供給至分流器。另外,就樹脂層B而言,以押出 機3 2熔融混練表1所示之種類的樹脂,供給至分流器。從 押出機3 1供給至分流器之樹脂層A成爲中間層,從押出機 32供給至分流器之樹脂層B成爲兩表層,進行共押出成形 〇 繼而,使從模頭33所押出之熔融樹脂34,一邊以表1 所示之輥輪構成的1號輥輪36及2號輥輪37挾持,一邊製膜 ,得到由表1所示之厚度的3層構造所構成之透明樹脂層合 板。又,1號輥輪36之表面溫度爲110 °c,2號輥輪37之表 面溫度爲1 2 5 °C。 [比較例2~4] 以押出機3 1熔融混練表1所示之種類的樹脂,依順序 供給至分流器及模頭33。繼而,使從模頭33所押出之熔融 樹脂34,一邊以表1所示之輥輪構成的〗號輥輪36及2號輥 輪37挾持,一邊製膜,得到由表1所示之厚度的單層構造 所構成之透明樹脂板。 -22- 201130655 <評估> 有關所得到之各透明樹脂層合板及透明樹脂板(實施 例1〜2 2及比較例1〜4 ),進行鉛筆硬度及全光線透過率之 評估。各評估方法表示於以下,同時其結果一倂表示於表 (鉛筆硬度) 依據J I S K 5 6 0 0而測定。又,在實施例1〜1 1之透明樹 脂層合板中的測定面爲樹脂層B。 (全光線透過率) 依據JIS K 7361- 1 : 1997,使用霧度計HM - 150(股 )村上色彩技術硏究所製)而測定。又,實施例1 ~ 1 1係使 樹脂層B對向於光源而測定。 -23- 201130655 【一撇】 骧褂 mm CM CO ύ CO CM ή σ> σ> CO r· σ> csi a> ca σ> 寸 C4 〇> CO C>i σ> CO csi σ> csi σ» csi 〇> CO csi σ> CM oi a> csi 〇> csi σ> CO g CO g s CO § η to# ts m m m at X X X X X X 工 X X X X 工 I 工 ffl X X X ω X X X m CO CD CO CD CO CQ CO m ΆΑ m r— OJ CsJ CVJ CM CM CM T~ it m E E 5 〇 5 CO ο IO o in o 00 1〇 i〇 τ· CM 00 o s o in ο 00 r™ in o IT) 00 CSI tr> ▼·· in tr> o CSI o % m m 尝 S a. o a. I o < 1 ο ·< i o 1 o. Μ ο <C i 〇 S 〇 ζ ο s ο I < Ϊ 論 I 1 1 a. <c I 0 1 < i a. 0 1 < 〇 ·< i a. 晏 0 1 Q. s M a. I & O- i Q_ 1 a. i 〇_ 1 M M 0 1 〇 s CL· o o CO m B S; ft E E s o 呂 o ο o g d d o g 〇 g ο 5 o s o s o 〇 〇 g o g o g o o o s o s o 〇 5 O o o g d o d g o g o g O > o d g d o o g o g d 1 1 1 m D33 m m 承F\ «Iwnl m Csl CM CM Csl CM CM CSI CM Csl CM CO CM CNI CM CM CO CO 兮 CO CO CO CO 1 1 1 m B S; it E E 5 O CO 5 CO eg ο o o o d CO CO <x> o ▼»· σ> 00 CO o 卜 5 CO CO ο CO (O o iO 00 〇 % o iO CO d CO CO o (D (O o g <〇 CO <〇 CO T~ 对 o 对 o Y·— Csl < ss m m 卿 一 - 一 — t— T* CM i 闺 CM 握 1¾ CO m 1¾ 寸 提 in in m 堤 K (0 m 闺 1¾ 闺 00 闺 σ> 辑 ο i 揭 u i 揭 K CM i 捶 舾 CO i 握 K 对 i 翠 In IO i 闺 (O i 捶 u 卜 i 辑 sm 00 i 握 u σ> i 闺 UK s m 辑 u 握 u CM CM 莩 堤 u i 鑑 CM 鎰 CO 鑑 寸 m £. 鬆嵌铱·Ν®ώ趙/避ώ趙^Esfr: νϊά , f嵌N避趙磐嵌搂軸淞n(:uda 從表1明顯可知,實施例1〜22較比較例1〜4在鉛筆硬度 及全光線透過率顯示良好的結果。 另外,有關實施例1 ~ 1 1之2層構造所構成之透明樹脂 層合板,評估是否可以手彎曲該層合板(彎曲性)。其結 果,該層合板即使彎曲亦顯示很難龜裂之結果。又,由3 -24- 201130655 層構造所構成之實施例1 2〜22的透明樹脂層合板中,有關 丙烯酸樹脂層由甲基丙烯酸樹脂及橡膠狀聚合物所構成之 層的實施例16〜22之層合板,與上述同樣做法而評估彎曲 性。其結果’該層合板即使彎曲亦顯示很難龜裂之結果。 【圖式簡單說明】 圖1係表示本發明之一實施形態的透明樹脂層合板之 槪略截面說明圖。 圖2係表示本發明之一實施形態的透明樹脂層合板之 製造方法的槪略說明圖。 圖3係表示本發明之另一實施形態的透明樹脂層合板 之槪略截面說明圖。 【主要元件符號說明】 1 =聚碳酸酯樹脂層 I a : 單面 lb :另一面 2,3 :丙烯酸樹脂層 1 〇、1 1 :透明樹脂層合板 1 0a、1 1 a :表面 1 Ob、1 lb :背面 20 :透明導電體 2 1 :透明導電膜 31、32 :押出機 -25- 201130655 3 3 :模頭 3 4 :熔融樹脂 3 5 :冷却輥輪 3 6 : 1號輥輪 37 : 2號輥輪 -26S -19- 201130655 (Roll wheel configuration 2) The No. 1 roller 36 and the No. 2 roller 37 are formed into a stainless steel spiral roller in which the surface state is formed into a mirror surface. The resins used in the following examples and comparative examples are as follows. Resin 1: Polymer of only aromatic polycarbonate ("Calibre 301 - 10" manufactured by Sumitomo Dow Co., Ltd.). Resin 2: a copolymer of methyl methacrylate/methyl acrylate = 98/2 (weight ratio). Resin 3: a copolymer of 9% by weight of methyl methacrylate/methyl acrylate = 96/4 (weight ratio), and an acrylic resin composition of 9% by weight of the acrylic multilayer structural polymer obtained in the following Reference Example Things. Resin 4: 79% by weight of a copolymer of methyl methacrylate/methyl acrylate = 96/4 (weight ratio), an acrylic resin-based composition containing 21% by weight of the acrylic multilayer structure polymer obtained in the following Reference Example . [Reference Example] (Production of a rubbery polymer) An acrylic multilayer structure polymer composed of a three-layer structure was produced by the method described in the examples of JP-A-5-27576. Specifically, first, in a glass reaction vessel having an internal volume of 5 liters, 700 g of ion-exchanged water I, 7 g of sodium carbonate, and 0.3 g of sodium persulfate were fed, and the mixture was stirred under a nitrogen stream, and then fed to Pelex OT-P ( (Fly) Kao) 4.46 g, ion-exchanged water I50g, methyl methacrylate 150g, allyl methacrylate 〇.3g, 'warmed to 75 ° C, stirring for 150 minutes. -20- 201130655 Then, 689 g of butyl acrylate, 162 g of styrene, I7g of allyl methacrylate, and 0.85 g of sodium persulfate were added from another inlet for 90 minutes, pelex 〇τ - p 7,4g A mixture of 50 g of ion-exchanged water was further polymerized for 90 minutes. After the polymerization was terminated, a mixture of 326 g of methyl methacrylate and 14 g of ethyl acrylate and 3 g of ion-exchanged water having 0.34 g of sodium persulfate dissolved therein were further added from the respective mouths for 30 minutes. After the addition was completed, the polymerization was further continued for 60 minutes. The obtained latex was poured into a 0.5% aqueous solution of aluminum chloride to agglomerate the polymer. After washing with warm water for 5 times, it was dried to obtain an acrylic multilayer structure polymer. [Examples 1 to 1 1] <Production of Transparent Resin Laminate> In the resin layer A, the resin of the type shown in Table 1 was melt-kneaded by the extruder 31 and supplied to the flow divider. Further, in the resin layer B, the resin of the type shown in Table 1 was melt-kneaded by the extruder 32 and supplied to the flow divider. The resin layer A supplied from the extruder 31 to the flow divider becomes the main layer, and the resin layer B supplied from the extruder 3 2 to the flow divider becomes the surface layer (on the side of the No. 2 roller 37), and co-extrusion molding is performed. Then, the molten resin 3 4 pushed out from the die 3 3 was held while the No. 1 roller 3 6 and the No. 2 roller 3 constituted by the rollers shown in Table 1 were formed, and the film was obtained. A transparent resin laminate composed of a two-layer structure having a thickness shown. Further, the surface temperature of the No. 1 roller 36 was 120 °C, and the surface temperature of the No. 2 roller 37 was 130C. The temperature of this temple is -21 - 201130655 贯 for measuring the surface temperature of each light wheel. Further, "thickness" in the extruders 31, 32 in Table 1 indicates the respective thicknesses of the resin layers A, B. The "total thickness" in Table 1 indicates the total thickness of the obtained transparent resin laminate. [Examples 12 to 22 and Comparative Example 1] In the resin layer A, the resin of the type shown in Table 1 was melt-kneaded by the extruder 31 and supplied to the flow divider. Further, in the resin layer B, the resin of the type shown in Table 1 was melt-kneaded by the extruder 32 and supplied to the flow divider. The resin layer A supplied from the extruder 31 to the flow divider becomes an intermediate layer, and the resin layer B supplied from the extruder 32 to the flow divider becomes a two-layer layer, and a co-extrusion molding is carried out, and the molten resin extruded from the die 33 is then carried out. 34. The film was formed while holding the No. 1 roller 36 and the No. 2 roller 37 which are formed by the rollers shown in Table 1, and a transparent resin laminated plate having a three-layer structure having the thickness shown in Table 1 was obtained. Further, the surface temperature of the No. 1 roller 36 was 110 °C, and the surface temperature of the No. 2 roller 37 was 1 2 5 °C. [Comparative Examples 2 to 4] The resin of the type shown in Table 1 was melt-kneaded by the extruder 3 1 and supplied to the flow divider and the die 33 in this order. Then, the molten resin 34 extruded from the die 33 was held while being held by the No. 3 roller 36 and the No. 2 roller 37 constituted by the rollers shown in Table 1, and the thickness shown in Table 1 was obtained. A transparent resin plate composed of a single layer structure. -22-201130655 <Evaluation> Each of the obtained transparent resin laminates and transparent resin sheets (Examples 1 to 2 2 and Comparative Examples 1 to 4) was evaluated for pencil hardness and total light transmittance. Each evaluation method is shown below, and the results are shown in the table (pencil hardness) according to J I S K 5 600. Further, the measurement surface in the transparent resin laminate of Examples 1 to 1 was the resin layer B. (Total light transmittance) Measured according to JIS K 7361-1: 1997, using a haze meter HM-150 (manufactured by Murakami Color Technology Research Institute). Further, in Examples 1 to 1 1, the resin layer B was measured against the light source. -23- 201130655 [撇 撇] 骧褂mm CM CO ύ CO CM ή σ>σ> CO r· σ> csi a> ca σ> inch C4 〇> CO C>i σ> CO csi σ> csi σ» Csi 〇> CO csi σ> CM oi a> csi 〇> csi σ> CO g CO gs CO § η to# ts mmm at XXXXXX work XXXX work I work ffl XXX ω XXX m CO CD CO CD CO CQ CO m ΆΑ mr— OJ CsJ CVJ CM CM CM T~ it m EE 5 〇5 CO ο IO o in o 00 1〇i〇τ· CM 00 oso in ο 00 rTM in o IT) 00 CSI tr> ▼·· in Tr> o CSI o % mm taste S a. o a. I o < 1 ο · < io 1 o. Μ ο <C i 〇S 〇ζ ο s ο I < Ϊ I 1 1 a. <c I 0 1 < i a. 0 1 <〇·< i a. 晏0 1 Q. s M a. I & O- i Q_ 1 a. i 〇_ 1 MM 0 1 〇s CL· oo CO m BS; ft EE so üo ο ogddog 〇g ο 5 ososo 〇〇gogogooososo 〇5 O oogdodgogog O > odgdoogogd 1 1 1 m D33 mm F\ «Iwnl m Csl CM CM Csl CM CM CSI CM Csl CM CO CM CNI CM CM CO CO 兮CO CO CO CO 1 1 1 m BS; it EE 5 O CO 5 CO eg ο oood CO CO <x> o ▼»· σ> 00 CO o Bu 5 CO CO ο CO (O o iO 00 〇% o iO CO d CO CO o (D (O og < 〇CO < 〇CO T~ to o vs o Y·- Csl < ss mm 卿一一一 t- T* CM i 闺CM grip 13⁄4 CO m 13⁄4寸提in in in m 堤 K (0 m 闺13⁄4 闺00 闺σ> ο ui ui 揭 K CM i 捶舾CO i grip K on i 翠 In IO i 闺 (O i 捶u 卜 i sm 00 i握u σ> i 闺UK sm series u grip u CM CM 莩 ui CM CM 镒CO 鉴 inch m £. 松铱铱·Ν®ώ赵/避ώ赵^Esfr: νϊά , f embedded N 磐 磐 磐搂 axis 淞n (: uda It is apparent from Table 1 that Examples 1 to 22 show better results in pencil hardness and total light transmittance than Comparative Examples 1 to 4. Further, regarding the transparent resin laminate composed of the two-layer structure of Examples 1 to 1, it was evaluated whether or not the laminate (bending property) can be bent by hand. As a result, even if the laminate is bent, it shows that it is difficult to crack. Further, in the transparent resin laminated plates of Examples 1 to 22 which are composed of a layer structure of 3 - 24 - 201130655, examples 16 to 22 in which the acrylic resin layer is composed of a layer composed of a methacrylic resin and a rubber-like polymer The laminate was evaluated for the same bending as described above. As a result, the laminate showed a result of being difficult to crack even if it was bent. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a transparent resin laminate according to an embodiment of the present invention. Fig. 2 is a schematic explanatory view showing a method of producing a transparent resin laminate according to an embodiment of the present invention. Fig. 3 is a schematic cross-sectional view showing a transparent resin laminate according to another embodiment of the present invention. [Description of main component symbols] 1 = Polycarbonate resin layer I a : Single lb : Other surface 2, 3 : Acrylic resin layer 1 〇, 1 1 : Transparent resin laminate 1 0a, 1 1 a : Surface 1 Ob, 1 lb : Back surface 20 : Transparent conductor 2 1 : Transparent conductive film 31 , 32 : Extruder - 25 - 201130655 3 3 : Die 3 4 : Molten resin 3 5 : Cooling roller 3 6 : No. 1 roller 37 : No. 2 roller -26