1247639 ⑴ 玖、發明說明 【發明所屬之技術領域】 本發明係有關，表面改質之樹脂複合薄片者；更詳細 的說，是有關在電機·電子製品、車輛構件、顯示器等之 領域中，受使用環境之影響等亦難以發生翹曲、變形之樹 脂複合薄片者。 【先前技術】 一般而言，透明樹脂比無機玻璃柔軟、表面容易受到 損傷；另一方面，透明樹脂的彎曲強度、耐衝擊強度等之 實用強度，成型加工性，及輕量性優異；因此，在已往使 用無機玻璃之領域中，亦正廣泛的取代而使用。 近年來，在液晶方式之電視、個人電腦監控器、行動 電話顯示窗之保護蓋、及車輛用計測器蓋、電照明附帶招 牌、店面之商品廚櫃等使用透明樹脂之領域，強烈要求畫 像、計測器文字之辨視性不降低，又可長期保持表面光澤 ，耐擦傷性優異，表面不易受損傷的薄片狀透明樹脂成型 加工品；更要求具有防止空氣中之塵埃附著的防帶電功能 、防止外部光線之照入的防表面反射功能等之高功能化。 已往，爲使樹脂材料之表面改質，有施行以塗佈、蒸 鍍等二次加工，形成具有耐擦傷性等之功能的表面層之方 法。 特開昭5 3 - 1 0463 8號公報上有，關於設置比基材樹脂 硬之層，所謂硬塗層的配方；藉由以活性能量線照射具有 -5- (2) 1247639 丙烯醯氧基或（甲基）丙烯醯氧基之多功能聚合性單體、 與光敏化劑之混合物，形成硬化皮膜之方法的揭示；又， 特開昭5 3 - 1 0293 6號公報及特開昭62-2 3 6 8 3 2號公報上有 ，將以具有丙烯醯氧基、或（甲基）丙烯醯氧基之多功能 聚合性單體爲主成份、與有機溶劑、及光敏化劑之混合物 塗佈後，使有機溶劑揮發去除；藉由活性能量線之照射， 形成硬化皮膜之方法的揭示。 另一方面，特開昭 62-45669號公報及特開 200 1 -2 3 2 728號公報上有，形成有機矽氧烷系樹脂之硬化塗膜 層，以提升耐擦傷性之矽系硬塗技術的揭示；但是，此種 情況下，必須以加熱硬化，其硬化之際，需要大量的熱能 ，極不經濟；又，硬化時之加熱，會產生基材樹脂變形等 之問題。 因此，以僅藉由紫外線等之活性能量線的照射，形成 硬化皮膜之前者的活性能量線硬化方式，在獲得製品上較 具優勢。 此等技術，一般而言，必要有樹脂材料之洗淨、乾燥 、頭道處理等之前處理；其結果，步驟複雜、而且產生必 須防止損害外觀、設計性之塵埃的混入之問題；爲能連續 生產，必須投入大量的設備，很難實行。 特開平1 1 - 3 09 8 1 3號公報上有，就樹脂薄片之表面改 質以利連續生產的對應；於熱塑性樹脂之押出薄片成型時 ，預先準備在樹脂薄膜之單面上形成具有耐擦傷性、防帶 電性、防反射性等功能的表面層；於另一面上準備設置有 -6 - (3) 1247639 黏著層之樹脂薄膜，連續層壓的方法，及可使用其之附帶 黏著層的硬塗薄膜，之揭示。 又，亦有不設置黏著層，樹脂薄膜之材質由與押出薄 片同種之樹脂、及親和性高之樹脂中選擇，在熔融溫度以 上之溫度領域直接押出薄片的熱層壓方法之提案；在此等 薄膜之押出薄片層壓面的另一面表面上，形成具有各種功 能之表面層，能獲得具有所期望目標之耐擦傷性等的押出 複合薄片。 不過，在前者之設置黏著層的薄膜之情況下，此黏著 層受溫度變化、溫度變化之所謂環境變化的影響，經長時 間使用，容易引起變色、剝離等之外觀不良；又，在後者 之直接熱層壓的情況下，由於薄膜熔融時之變形的影響， 具有上述各種功能之表面層，發生龜裂損及外觀，不能獲 得所期望之性能；又，所得之製品表面，很難避免發生凹 凸等之變形現象。 特開平5-5 723 5號公報上有，除在物品上塗佈硬化性 樹脂組成物以爲塗膜之外，將其使用於薄膜以另一面加上 之黏著層，在物品上添附、或做爲轉印層之最外層使用的 揭示；但是，其中並無有關轉印方法之具體條件的揭示。 又，特開平5 - 1 6 2 2 3 0號公報上有，將設置有防帶電 層之轉印薄膜在加熱狀態下壓黏，以獲得具有防帶電功能 之化粧材料的方法之揭示，以押出機之狀況標示此化粧材 料之製造方法的工程圖；不過，其中亦無有關轉印薄膜之 加熱壓黏的具體條件之任何說明。 (4) 1247639 此等樹脂材料，基本上經過成型加工後，供應實際使 用；成型品內部之應力（成型應變）大時，成爲在製品階 段之翹曲、變形的原因。 尤其是，在上述液晶顯示窗之用途中，爲減輕重量’ 要求厚度爲〇·8〜1.5mm之較薄薄片成型品，藉此與厚度 較厚之成型品相比較，其強度相對的降低，有易使成型時 之應變增大的困難。 【發明內容】 〔發明之揭示〕 本發明的目的之一爲提供，透明、具有良好光學特性 ，耐擦傷性、防帶電性、防反射性等之表面功能優異，而 且很難由於使用環境等之影響而發生翹曲、變形等現象的 樹脂複合薄片；本發明之另一目的爲，提供能安定而連續 的生產如此之樹脂複合薄片的製造方法。 本發明之工作同仁，首先著眼於樹脂材料之複折射値 ;一般而言，構成樹脂之結構單位（聚合物分子）爲各向 異性者，此結構單位無規則的存在時，各向異性互相抵消 ，不會產生內部應力；但是，樹脂材料，基本上經過成型 加工後，供應實際使用之故’其成型品產生內部應力；內 部應力爲，透明樹脂材料產生光學相位差（Retardation ) 之原因；所謂內部應力大，係指由光學相位差換算的複折 射値大之意；即，複折射値爲，樹脂成型加工品之內部應 力的一種指標；複折射，有定向複折射與應力複折射之兩 (5) 1247639 種。 定向複折射爲’例如以射出成型獲得成型品時，以射 出成型之際的強勁剪切力’爲使構成樹脂之聚合物分子定 向的起因。 應力複折射爲’以金屬模具內的樹脂冷卻•硬化之際 所引起收縮速度的差’而發生殘餘應力（剪切應力等）等 之起因者；一般而言’將樹脂成型之際，成型體依由表皮 層向內部層之方向冷卻而固化；此時表皮層與內部層之溫 度差太大與體積收縮不均勻有關係，又，表皮層與內部層 之間有發生剪切應力的傾向。 此寺複折射之顯現’以最適化之成型條件可有某一程 度之抑制，但是’射出成型時’基本上產生很大的剪切力 之故，聚合物分子之定向的操縱有限；尤其在閘門附近， 與其他部份比較，內部應力增大，呈現極大之複折射値。 爲使樹脂複合薄片在製品階段實際上不產生翹曲、變 形，儘可能使內部應力減小，以不普遍存在爲重要者；即 ，使樹脂複合薄片之複折射値在適當値以下，而且面方向 之複折射値的偏差在適當範圍內，可以防止在實際使用階 段中整體的翹曲、或局部的收縮變形等等。 本發明之工作同仁，由上述之觀點深入探討，不斷硏 究；結果發現（i )在熱塑性樹脂之押出成型薄片上，連 續供應於基底薄膜上形成薄膜層及黏著層而成之轉印薄膜 、（U)將此轉印薄膜在押出成型薄片表面，於所定之溫 度條件下轉印成爲複合薄片、接著（iii )將基底薄膜剝離 •9- (6) 1247639 ，確定能連續生產樹脂複合薄片；又，本發明之工作同仁 ，發現藉由抑制樹脂之成型加工品的內部應力（即，其做 爲尺度之複折射値）在一定値以內，能形成實際上不會發 生之起因於使用環境等的翹曲、變形之樹脂複合薄片；因 而發現’爲保持所得樹脂複合薄片之良好外觀及設計性（ 透明、良好之光學特性）、簡便且安定的進行生產，必要 有特定之製造條件；進而發現，此樹脂複合薄片以特定之 層構成時，可以製造耐擦傷性、防帶電性、防反射性等之 表面功能優異的樹脂複合薄片，至此完成本發明。 即是說，本發明之構成如以下之說明。 (1) 一種透明之熱塑性樹脂複合薄片，其特徵爲， 將於具有脫模性之基底薄膜面上依順序形成含有硬化樹脂 之薄膜層（A)及黏著層（B)所成的轉印薄膜，在由熱 塑性樹脂所成之押出成型薄片表面的至少單面上，使用加 熱壓黏滾筒連續轉印，以黏著層（B )介入其間，將基底 薄膜與薄膜層（A)層合於押出成型薄片表面上，其後將 基底薄膜剝離，押出成型薄片表面以薄膜層（A)被覆而 成。 (2 )如（1 )項記載之透明的熱塑性樹脂複合薄片， 其中在上述透明之熱塑性樹脂複合薄片的面方向之複數處 所中，複折射値之平均値爲5 X 1(Γ5以下者；而且，在 複數處所中複折射値之任一種對該平均値之偏差爲隨時都 在± 5 0 %以內者。 (3 ) —種製造方法，係透明的熱塑性樹脂複合薄片 -10· 1247639 (7) 之製造方法者；其特徵爲，包含有， 以押出成型形成由熱塑性樹脂所成之押出成 步驟； 使押出成型薄片之表面溫度，冷卻至四周溫 性樹脂之Tg+ 10°c (但，Tg係依據J1S-K7121 的範圍之步驟； 將在具有脫模性之基底薄膜面上，依順序形 化樹脂之薄膜層（A )及黏著層（B )而成的轉 以薄膜供給滾筒連續供應之步驟； 以黏著層（B)介入其間，使基底薄膜與薄 )層合於押出成型薄片表面；將轉印薄膜，使用 滾筒連續轉印於表面溫度爲四周溫度〜熱塑性捐 + l〇t的押出成型薄片之至少單面上，形成複合 驟；該複合薄片表面之溫度，以加熱壓黏滾筒加 性樹脂之Tg + 1 (TC〜Tg + 70°C之範圍；以及 藉由自複合薄片將基底薄膜剝離，形成押出 表面以薄膜層（A )被覆之透明的熱塑性樹脂複 步驟。 (4 )如上述（3 )項記載之製造方法，其中 明之熱塑性樹脂複合薄片的面方向之複數處所中 値之平均値爲5 X 1 0_5以下者；而且，在複數 折射値之任一種，對該平均値之偏差，爲隨時都 內者。 (5 )如上述（3 )項記載之製造方法，其中 型薄片的 度〜熱塑 之標準） 成含有硬 印薄膜， 膜層（A 加熱壓黏 ί脂之Tg 薄片的步 熱至熱塑 成型薄片 合薄片之 在上述透 ，複折射 處所中複 在±5%以 在連續供 -11 - 1247639 (8) 應轉印薄膜之步驟中，轉印薄膜以相當於薄膜供給滾筒之 寬度方向的單位長度0·01〜0.1 kg / cm之拉伸下供應； 而且在使用加熱壓黏滾筒，將轉印薄膜連續轉印於押 出成型薄片表面之至少單面的步驟中’加熱壓黏滾筒以相 當於該滾筒之寬度方向的單位長度1〜kg/ cm之線壓 加壓。 (6 )如上述（3 )項記載之製造方法，其中薄膜層（ A)爲，含有分子中至少具有2個以上之丙儲醒氧基、或 (甲基）丙烯醯氧基之多功能聚合性單體的聚合硬化物者 ;而且薄膜層（A)之表面硬度爲3H以上者；表面硬度 係依據JIS-K5400之基準測定者。 (7) 如上述（3)項記載之製造方法，其中薄膜層（ A)之表面電阻値爲1012Ω以下者；表面電阻値係依據 JIS-K691 1之基準測定者。 (8) 如上述（3)項記載之製造方法，其中薄膜層（ Α)之表面反射率爲3 %以下者；表面反射率係在可視光 波長區域之最低反射率者。 (9 )如上述（3 )項記載之製造方法，其中熱塑性樹 脂爲’一種或數種選自丙烯酸系樹脂、MS系樹脂、及PC 系樹脂所成群之樹脂的層合物者。 (1 〇 ) —種透明之熱塑性樹脂複合薄片，其特徵爲， 以上述（3 )〜（9 )項中任一項記載之方法製造而得者。 還有，本說明書中所謂Tg’係以jIS_K7121之差示 掃描熱量測定試驗（D S C )測定之値者，爲樹脂加熱時， -12- (9) 1247639 由玻璃狀之固體轉移至橡膠狀之彈性體的溫度。 〔用以實施發明之最佳形態〕 就本發明，具體的說明如下。 首先，就本發明之透明的熱塑性樹脂複合薄片之製造 方法，詳述如下。 將在轉印薄膜之表面上形成的薄膜層，轉印於熱塑性 樹脂薄片表面，製成樹脂複合薄片的方法，有分別準備上 述兩者，於適當的條件下加壓，以分批式轉印壓縮的方法 ;另外有，對熱塑性樹脂之押出成型薄片，在其押出成型 薄片所定之溫度範圔內的某時點，連續將滾筒捲之轉印薄 膜，以供給滾筒外加壓力同時轉印之方法。 後者之以滾筒外加壓力同時轉印的方法、與前者之以 壓縮整體化的方法相比較，容易連續生產之故，具有優越 之量產性；又，能安定的獲得實際上沒有氣泡等混入之缺 點、外觀品質優異的樹脂複合薄片，更適合於工業上使用 ;而且’爲基材之熱塑性樹脂薄片（押出成型薄片）不需 洗淨步驟，步驟大幅度的簡化，容易連續生產；因而，可 安定的獲得實際上沒有由於氣泡及空氣中塵埃之混入所引 起的凹凸缺陷等、外觀品質優異的樹脂複合薄片，更適合 於工業上使用；因此，本發明中採用如上所述後者之以滾 筒外加壓力同時轉印的方法。 參照圖1同時就本發明之樹脂複合薄片的製造裝置加 以說明；在押出機（圖上未標示）、薄片擠壓模1、磨光 -13- (10) 1247639 滾筒2、取出滾筒7所成之通常的樹脂薄片押出設備中， 形成施行押出成型之熱塑性樹脂薄片3 ;在磨光滾筒2與 取出滾筒7之間，設置加熱壓黏滾筒5 ;對熱塑性樹脂薄 片3，藉由滾筒動力源9，使轉印薄膜4拉出；此轉印薄 膜4，經由薄膜供給滾筒1 G，在拉伸下供應至加熱壓黏滾 筒5 ’轉印於熱塑性樹脂薄片3 (因情況之不同，有於此 將基底薄膜自轉印薄膜剝離者），形成樹脂複合薄片8。 在磨光滾筒2與取出滾筒7之間，以在熱塑性樹脂薄 片之表面溫度爲，其熱塑性樹脂之Tg+lOt：以下〔四周 溫度（例如 2 0 °C )〜T g + 1 〇 °C ;以 T g — 4 0 °C 〜T g + 1 0 °C 較爲適合〕的以下位置，設置加熱壓黏滾筒5爲佳；在熱 塑性樹脂薄片之表面溫度爲熱塑性樹脂之Tg + 1 (TC以上 的位置設置加熱壓黏滾筒5時，於製品階段中，爲基材之 熱塑性樹脂薄片容易產生變形、彎曲或外觀不良，極不適 合。 還有，爲控制熱塑性樹脂薄片之表面溫度，設置能放 射遠紅外線之盤式加熱器（圖中未標示），可容易而有效 的進行步驟管理；加熱壓黏滾筒5之外，倂設具有同樣功 能的加熱壓黏滾筒6爲多段結構，有利於後述之加熱等。 加熱壓黏滾筒5及6之溫度，設定在通過加熱壓黏滾 筒時之複合薄片〔基底薄膜與薄膜層（A)，以黏著層（ B )介入其間，層合於熱塑性樹脂之押出成型薄片表面的 複合薄片〕的表面溫度，可達其熱塑性樹脂之Tg + 1 〇 °C 〜Tg+70°C的範圍。 -14- 1247639 (11) 一般而言，本方式所用轉印薄膜之黏著層（B)的Tg ，比爲基材之熱塑性樹脂薄片的Tg低；因而’使轉印薄 膜及熱塑性樹脂薄片加熱至熱塑性樹脂薄片之T g以上’ 進行加熱壓黏，能獲得充分之密著性；但是’在本方式中 ，加熱時間僅爲通過加熱壓黏滾筒5、6之一瞬間，尤其 是在線速度高之情況、黏著層（B )之Tg高的情況，轉 印薄膜與熱塑性樹脂薄片之密著性，亦有不能充分獲得的 情形；因此之故，加熱壓黏滾筒5、6的溫度，以設定在 複合薄片之表面溫度可達Tg+10°C〜Tg+70°C之範圍爲 佳。 通過加熱壓黏滾筒5、6時之複合薄片的表面溫度， 低於熱塑性樹脂之Tg + 1 0 °C時，轉印之薄膜層（A )與基 材之熱塑性樹脂薄片的密著性低，超過熱塑性樹脂之Tg + 70 °C時，於製品階段，基材之熱塑性樹脂薄片容易產生 變形、彎曲或外觀不良，極爲不適；又，熱塑性樹脂薄片 之板厚爲低於2 mm之薄板時，在上述溫度範圍內，複合 薄片的表面溫度達熱塑性樹脂之T g + 5 0 °C以上.，亦可能 產生變形、彎曲或外觀不良；因而，通過加熱壓黏滾筒5 、6時之複合薄片的表面溫度，以設定在可達熱塑性樹脂 之Tg+l〇°C〜Tg+40°C的範圍之加熱壓黏滾筒5、6的溫 度更佳。 加熱壓黏滾筒5、6之表面材質的具體例有，耐熱性 樹脂材料、各種金屬、陶瓷等。 使用耐熱性樹脂材料時，在芯材之金屬滾筒表面施行 -15- (12) 1247639 耐熱性樹脂材料之襯裏’而成加熱壓黏滾筒；又，此耐熱 丨生棱f g曰材料有砂、氯丁橡膠、氨基甲酸酯、聚四氟乙烯等 ’以5夕之耐熱性高、加工性良好、各種硬度之材料在工業 上容易取得，最爲理想。 金屬材料有，碳鋼、不銹鋼、鋁等；價格比較便宜、 硬度及表面平滑性高，以碳鋼等鐵系金屬爲佳；又，爲更 提I%硬度及表面平滑性，更提升耐磨損性、耐腐蝕性，以 在表面施行鍍鉻更佳。 使用陶瓷材料時，在芯材之金屬滾筒表面，將陶瓷火 焰噴塗至可達100〜3 00微米左右之厚度，形成加熱壓黏 滾筒；又’此陶瓷材料有，氧化鋁、二氧化鈦、鎢、碳化 物等；價格便宜、熱傳導率高，以氧化鋁最爲理想。 轉印薄膜接觸加熱壓黏滾筒時，薄膜因熱膨脹容易產 生IS紋；因而’加熱壓黏滾筒表面之材質，與金屬、陶瓷 相比’具有適度彈性之矽橡膠等耐熱性樹脂材料，能有效 抑制薄膜之因熱膨脹產生的皺紋。 施行矽橡膠襯裏之加熱壓黏滾筒（以下稱爲矽橡膠加 熱11黏滾筒），一般而言，依使襯裏與芯材之金屬黏著的 黏著劑之耐熱溫度而決定最高的設定溫度，設定溫度以 1 80 °C以下爲宜；而且，生產結束時、因故障而停止加熱 壓黏步驟之際，必要釋放加熱壓黏滾筒之外加壓力，以去 除來自押出成型薄片之加熱壓黏滾筒的負載；押出成型薄 片與加熱壓黏滾筒之接觸放開時，由加熱器而來之熱在加 熱壓黏滾筒表面蓄熱，加熱壓黏滾筒表面之溫度，會上升 -16- (13) 1247639 到設定溫度以上；此時，加熱壓黏滾筒表面之溫度，會達 到使襯裏與芯材黏著之黏著劑的耐熱溫度以上，會發生使 襯裏由芯材脫落等之損傷；因而，矽橡膠加熱壓黏滾筒’ 爲防止滾筒之損傷、能進行安定的生產，設定溫度以在 16(TC以下更適合。1247639 (1) Description of the Invention [Technical Fields of the Invention] The present invention relates to a surface-modified resin composite sheet; more specifically, in the fields of motors, electronic products, vehicle components, displays, etc. It is also difficult to cause warpage and deformation of the resin composite sheet due to the influence of the environment. [Prior Art] In general, a transparent resin is softer than an inorganic glass and the surface is easily damaged. On the other hand, the transparent resin has excellent practical strength such as bending strength and impact strength, molding processability, and light weight; In the field of the use of inorganic glass in the past, it has been widely used instead. In recent years, in the field of liquid crystal televisions, personal computer monitors, protective covers for mobile phone display windows, vehicle measuring device covers, electric lighting with signs, and commercial kitchen cabinets for storefronts, there is a strong demand for portraits. The sheet-like transparent resin molded product which can maintain the surface gloss, has excellent scratch resistance and is not easily damaged on the surface, and has an anti-static function to prevent dust from adhering in the air and prevent it from being observed. The high-function function of the anti-surface reflection function such as the external light. In the past, in order to modify the surface of the resin material, a method of forming a surface layer having a function of scratch resistance or the like by performing secondary processing such as coating or vapor deposition is performed. Japanese Laid-Open Patent Publication No. SHO-A No. 5-3 - No. 1 0463-A No. 5-3, the disclosure of which is incorporated herein by reference to the provision of a layer which is harder than the base resin, a so-called hard coat layer; by irradiation with an active energy ray having -5-(2) 1247639 acryloxy group Or a method of forming a hardened film by a mixture of a multifunctional polymerizable monomer of (meth)acryloxyloxy group and a photosensitizing agent; and Japanese Patent Laid-Open Publication No. SHO-53-103933 -2 3 6 8 3 No. 2, a mixture of a multifunctional polymerizable monomer having an acryloxy group or a (meth)acryloxy group as a main component, an organic solvent, and a photosensitizer After coating, the organic solvent is volatilized and removed; and the method of forming a hardened film by irradiation with an active energy ray is disclosed. On the other hand, Japanese Laid-Open Patent Publication No. SHO-62-45669 and JP-A No. 2001-23-2728 have formed a hard coating film layer of an organic siloxane oxide resin to improve scratch resistance. The disclosure of the technology; however, in this case, it is necessary to be hardened by heat, and when it is hardened, a large amount of heat energy is required, which is extremely uneconomical; and, heating at the time of hardening causes problems such as deformation of the base resin. Therefore, the active energy ray hardening method in which the hardened film is formed only by irradiation with an active energy ray such as ultraviolet rays is advantageous in obtaining a product. In general, it is necessary to carry out the pretreatment of the resin material such as washing, drying, and head treatment; as a result, the steps are complicated, and it is necessary to prevent the incorporation of dust which impairs the appearance and design; Production, a large amount of equipment must be invested, and it is difficult to implement. Japanese Patent Publication No. Hei 1 1 - 3 09 8 1 3 discloses a modification of the surface of a resin sheet to facilitate continuous production. When the extruded sheet of the thermoplastic resin is molded, it is prepared to be formed on one side of the resin film in advance. a surface layer having functions such as abrasion resistance, antistatic property, antireflection property, etc.; a resin film provided with an adhesive layer of -6 - (3) 1247639 on the other side, a method of continuous lamination, and an adhesive layer which can be used therewith The hard coat film is revealed. Further, there is a proposal of a thermal lamination method in which a resin layer is not provided with an adhesive layer, and a material of the resin film is selected from a resin having the same kind as the extruded sheet and a resin having high affinity, and the sheet is directly extruded in a temperature range of a melting temperature or higher; On the other surface of the laminated surface of the film extrusion sheet, a surface layer having various functions is formed, and an extruded composite sheet having a desired target scratch resistance and the like can be obtained. However, in the case where the film of the adhesive layer is provided in the former, the adhesive layer is affected by the so-called environmental change of temperature change and temperature change, and when used for a long period of time, it is liable to cause discoloration, peeling, etc., and the appearance of the latter; In the case of direct thermal lamination, the surface layer having the above various functions undergoes cracking damage and appearance due to the influence of deformation at the time of melting of the film, and the desired properties cannot be obtained; and the surface of the obtained product is difficult to avoid. Deformation such as bumps. Japanese Laid-Open Patent Publication No. Hei 5-5 723-5 discloses that, in addition to applying a curable resin composition to an article as a coating film, it is used for attaching an adhesive layer to the other side of the film, and attaching or making it to the article. The disclosure for the outermost layer of the transfer layer; however, there is no disclosure of the specific conditions of the transfer method. Further, in Japanese Laid-Open Patent Publication No. Hei 5 - 1 6 2 2 3 0, a method of pressing a transfer film provided with an antistatic layer in a heated state to obtain a cosmetic material having an antistatic function is disclosed. The condition of the machine indicates the engineering drawing of the manufacturing method of the cosmetic material; however, there is no description of the specific conditions of the heating and pressure bonding of the transfer film. (4) 1247639 These resin materials are basically used after being subjected to molding processing; when the stress (forming strain) inside the molded article is large, it becomes a cause of warpage and deformation at the product stage. In particular, in the use of the above liquid crystal display window, in order to reduce the weight, a thin sheet molded article having a thickness of 〇·8 to 1.5 mm is required, whereby the strength thereof is relatively lowered as compared with a molded article having a relatively thick thickness. There is a difficulty in increasing the strain at the time of molding. [Disclosure of the Invention] One of the objects of the present invention is to provide transparency, excellent optical characteristics, excellent scratch resistance, antistatic property, antireflection property, and the like, and it is difficult to use the environment or the like. A resin composite sheet which affects warpage, deformation, and the like; another object of the present invention is to provide a method for producing such a resin composite sheet which can be stably and continuously produced. The working colleagues of the present invention first focus on the complex refracting enthalpy of the resin material; in general, the structural unit (polymer molecule) constituting the resin is anisotropic, and the anisotropy cancels each other when the structural unit is irregularly present. There is no internal stress; however, the resin material is basically subjected to the molding process and is supplied for practical use. The molded article generates internal stress; the internal stress is the cause of the optical phase difference (Retardation) of the transparent resin material; The large internal stress is the meaning of the complex refraction that is converted by the optical phase difference; that is, the complex refractive enthalpy is an index of the internal stress of the resin molded product; the birefringence, the directional birefringence and the stress birefringence (5) 1247639 species. The directional birefringence is a cause of aligning the polymer molecules constituting the resin when the molded article is obtained by injection molding, for example, a strong shear force at the time of injection molding. The stress birefringence is a cause of residual stress (shear stress, etc.) caused by the difference in shrinkage speed caused by cooling and hardening of the resin in the metal mold; in general, when the resin is molded, the molded body The skin layer is solidified by cooling in the direction of the inner layer; at this time, the temperature difference between the skin layer and the inner layer is too large and the volume shrinkage is uneven, and there is a tendency for shear stress to occur between the skin layer and the inner layer. The manifestation of the birefringence of this temple can be suppressed to a certain extent by the optimum molding conditions, but the 'injection molding' basically produces a large shear force, and the manipulation of the orientation of the polymer molecules is limited; especially in Near the gate, compared with other parts, the internal stress increases and exhibits a large complex refraction 値. In order to prevent the warpage and deformation of the resin composite sheet from actually occurring at the product stage, the internal stress is reduced as much as possible, and it is important that it is not ubiquitous; that is, the birefringence of the resin composite sheet is less than the appropriate enthalpy, and the surface is The deviation of the complex refracting enthalpy of the direction is within an appropriate range, and it is possible to prevent overall warpage, local contraction deformation, and the like in the actual use phase. The work of the present invention has been intensively studied from the above viewpoints, and it has been found that (i) a transfer film formed by continuously supplying a film layer and an adhesive layer on a base film on a stretched sheet of a thermoplastic resin, (U) the transfer film is extruded onto the surface of the formed sheet, transferred to a composite sheet at a predetermined temperature, and then (iii) the base film is peeled off. 9-(6) 1247639, and it is confirmed that the resin composite sheet can be continuously produced; Further, in the work of the present invention, it has been found that by suppressing the internal stress of the molded article of the resin (that is, it is a birefringence 尺度 of a scale) within a certain range, it is possible to form an environment which does not actually occur due to the use environment, etc. a warped and deformed resin composite sheet; thus, it has been found that in order to maintain good appearance and design (transparent, good optical properties) of the obtained resin composite sheet, and to be simple and stable, it is necessary to have specific manufacturing conditions; When the resin composite sheet is formed of a specific layer, it is possible to produce a surface resistant to scratch resistance, charge resistance, antireflection, and the like. Excellent composite sheet can be resin, thereby completing the present invention. That is, the constitution of the present invention is as follows. (1) A transparent thermoplastic resin composite sheet characterized in that a transfer film comprising a film layer (A) containing a hard resin and an adhesive layer (B) is sequentially formed on a surface of a base film having releasability And at least one surface of the surface of the extruded sheet formed by the thermoplastic resin is continuously transferred by using a heated pressure-sensitive adhesive roller, and the adhesive layer (B) is interposed therebetween, and the base film and the film layer (A) are laminated and extruded. On the surface of the sheet, the base film is peeled off thereafter, and the surface of the formed sheet is extruded to cover the film layer (A). (2) The transparent thermoplastic resin composite sheet according to the item (1), wherein the complex enthalpy of the complex refracting enthalpy is 5 X 1 or less in a plurality of locations in the plane direction of the transparent thermoplastic resin composite sheet; Any one of the complex refracting 在 in the plural space is within ± 5% of the average 。. (3) A manufacturing method, a transparent thermoplastic resin composite sheet - 10· 1247639 (7) a manufacturing method comprising: extruding and forming a step of forming a thermoplastic resin; extruding the surface temperature of the formed sheet and cooling to a temperature of a peripheral temperature of Tg + 10 ° C (however, Tg system) According to the procedure of the range of J1S-K7121; the step of sequentially supplying the film layer (A) of the resin and the adhesive layer (B) on the surface of the base film having the release property, and continuously supplying the film supply roller The adhesive layer (B) is interposed therebetween, and the base film and the thin film are laminated on the surface of the extruded molding sheet; the transfer film is continuously transferred to the surface temperature by using a roller to a temperature of four weeks, and the thermoplastic donor + l〇t is extruded. Forming a composite step on at least one side of the formed sheet; temperature of the surface of the composite sheet to heat the Tg + 1 of the pressure-sensitive adhesive resin (TC~Tg + 70 ° C; and by using the self-composite sheet The film is peeled off to form a transparent thermoplastic resin coated with the film layer (A). (4) The production method according to the above (3), wherein the surface of the thermoplastic resin composite sheet is in a plurality of places The average 値 is 5 X 1 0_5 or less; and, in any of the plural refracting 値, the deviation of the average 値 is at any time. (5) The manufacturing method described in the above item (3), the medium-sized sheet Degree ~ thermoplastic standard) into a hard-printed film, the film layer (A heat-pressed Tg sheet of the step heat to the thermoplastic sheet laminate in the above-mentioned transparent, birefringent position in the ± 5% In the step of continuously feeding the film to -11 - 1247639 (8), the transfer film is supplied in a stretch corresponding to a unit length of 0·01 to 0.1 kg / cm in the width direction of the film supply roller; Use heat pressure bonding In the step of continuously transferring the transfer film to at least one side of the surface of the extruded sheet, the 'heating pressure roller is press-pressed at a line length of 1 to kg/cm corresponding to the width direction of the roller. (6 The production method according to the above item (3), wherein the film layer (A) is a multi-functional polymerizable single containing at least two or more of a C. alkoxy group or a (meth) acryloxy group in a molecule. The surface of the film (A) has a surface hardness of 3H or more; and the surface hardness is measured according to the standard of JIS-K5400. (7) The method according to the above (3), wherein the surface resistance 薄膜 of the film layer (A) is 1012 Ω or less; and the surface resistance 値 is measured according to the standard of JIS-K691 1 . (8) The method according to the above (3), wherein the surface layer reflectance is 3% or less; and the surface reflectance is the lowest reflectance in the visible light wavelength region. (9) The method according to the above (3), wherein the thermoplastic resin is a laminate of one or more resins selected from the group consisting of acrylic resins, MS resins, and PC resins. (1 〇) A transparent thermoplastic resin composite sheet produced by the method according to any one of the items (3) to (9) above. In addition, in the present specification, the Tg' is measured by the differential scanning calorimetry test (DSC) of jIS_K7121. When the resin is heated, -12-(9) 1247639 is transferred from a glassy solid to a rubbery elastic. Body temperature. [Best Mode for Carrying Out the Invention] The present invention will be specifically described below. First, the method for producing the transparent thermoplastic resin composite sheet of the present invention will be described in detail below. A film layer formed on the surface of the transfer film is transferred onto the surface of the thermoplastic resin sheet to form a resin composite sheet, and the above two are separately prepared and pressurized under appropriate conditions to be batch-type transferred. The method of compressing; in addition, the method of continuously transferring the transfer film of the roll to the roll and applying the pressure to the roll at a certain point in the temperature range defined by the extruded sheet. In the latter method, the method of simultaneous transfer of the applied pressure of the drum is easier to continuously produce compared with the method of compressing and integrating the former, and has superior mass productivity; and, in addition, it can be stably obtained without the incorporation of bubbles or the like. A resin composite sheet having excellent defects and excellent appearance quality is more suitable for industrial use; and the thermoplastic resin sheet (extrusion molded sheet) which is a substrate does not require a washing step, the steps are greatly simplified, and continuous production is easy; In the present invention, the resin composite sheet having excellent appearance quality due to irregularities caused by the incorporation of bubbles and air dust is not preferable, and is more suitable for industrial use. Therefore, in the present invention, the latter is applied as a roller. The method of simultaneous pressure transfer. Referring to Fig. 1, a manufacturing apparatus of a resin composite sheet of the present invention will be described at the same time; in an extruder (not shown), a sheet extrusion die 1, a polishing-13-(10) 1247639 roller 2, and a take-up roller 7 are formed. In the usual resin sheet extruding apparatus, a thermoplastic resin sheet 3 subjected to extrusion molding is formed; between the polishing cylinder 2 and the take-up drum 7, a heating press roller 5 is provided; and for the thermoplastic resin sheet 3, by the drum power source 9 The transfer film 4 is pulled out; the transfer film 4 is supplied to the thermoplastic pressure-sensitive adhesive roll 5' via the film supply roll 1 G under tension and transferred to the thermoplastic resin sheet 3 (this is due to the case) The base film is peeled off from the transfer film to form a resin composite sheet 8. Between the polishing roller 2 and the take-up roller 7, the surface temperature of the thermoplastic resin sheet is Tg + lOt of the thermoplastic resin: the following [four-week temperature (for example, 20 ° C) ~ T g + 1 〇 ° C; It is preferable to provide a heating press roller 5 at a position where T g - 40 ° C to T g + 10 ° C is suitable for the following position; the surface temperature of the thermoplastic resin sheet is Tg + 1 (TC or more of the thermoplastic resin) When the pressure-adhesive roller 5 is placed in the position of the product, the thermoplastic resin sheet of the substrate is liable to be deformed, bent, or poor in appearance, and is extremely unsuitable. Also, in order to control the surface temperature of the thermoplastic resin sheet, it is possible to set a radiation far Infrared disk heater (not shown) can be easily and effectively carried out for step management; in addition to heating the pressure roller 5, the heating and pressure roller 6 having the same function is provided in a multi-stage structure, which is advantageous for heating as described later. The temperature of the pressure-sensitive adhesive rollers 5 and 6 is set, and the composite sheet (the base film and the film layer (A), which is interposed with the adhesive layer (B), is laminated on the thermoplastic resin when the pressure-sensitive roller is heated. The surface temperature of the composite sheet on the surface of the formed sheet can reach the range of Tg + 1 〇 ° C to Tg + 70 ° C of the thermoplastic resin. -14 - 1247639 (11) In general, the transfer film used in the present mode The Tg of the adhesive layer (B) is lower than the Tg of the thermoplastic resin sheet of the substrate; therefore, the transfer film and the thermoplastic resin sheet are heated to a Tg or more of the thermoplastic resin sheet to be heated and pressure-bonded, and sufficient Adhesiveness; but 'in this mode, the heating time is only a moment when one of the pressure-adhesive rollers 5, 6 is heated, especially when the line speed is high, and the Tg of the adhesive layer (B) is high, the transfer film is The adhesion of the thermoplastic resin sheet may not be sufficiently obtained; therefore, the temperature of the pressure-sensitive adhesive rollers 5, 6 is heated to set the surface temperature of the composite sheet to reach Tg + 10 ° C to Tg + 70 °. The range of C is preferably. When the surface temperature of the composite sheet by heating the pressure-sensitive adhesive rolls 5, 6 is lower than the Tg + 10 ° C of the thermoplastic resin, the transferred film layer (A) and the thermoplastic resin sheet of the substrate Low adhesion, exceeding the Tg of thermoplastic resin At 70 °C, in the product stage, the thermoplastic resin sheet of the substrate is prone to deformation, bending or poor appearance, which is extremely uncomfortable; and when the thickness of the thermoplastic resin sheet is less than 2 mm, within the above temperature range The surface temperature of the composite sheet is up to Tg + 50 ° C. of the thermoplastic resin, and may also be deformed, bent or poor in appearance; thus, the surface temperature of the composite sheet when the pressure roller 5 and 6 are heated is set to set The temperature of the heated pressure-sensitive adhesive rolls 5 and 6 in the range of Tg + l ° ° C to Tg + 40 ° C of the thermoplastic resin is better. Specific examples of the surface material of the heated pressure-sensitive adhesive rolls 5 and 6 are heat resistance. Resin materials, various metals, ceramics, etc. When a heat-resistant resin material is used, a -15-(12) 1247639 heat-resistant resin material lining is applied to the surface of the metal roller of the core material to form a heated pressure-sensitive roller; further, the heat-resistant rib-shaped material has sand and chlorine. Butadiene rubber, urethane, polytetrafluoroethylene, etc. are most desirable because they have high heat resistance and good workability, and various hardness materials are industrially easy to obtain. Metal materials, carbon steel, stainless steel, aluminum, etc.; cheaper price, high hardness and surface smoothness, preferably iron-based metals such as carbon steel; in addition, to improve I% hardness and surface smoothness, and improve wear resistance Damage, corrosion resistance, and chrome plating on the surface is better. When using a ceramic material, the ceramic flame is sprayed to a thickness of about 100 to 300 μm on the surface of the metal roller of the core material to form a heated pressure-sensitive roller; and the ceramic material is alumina, titania, tungsten, carbonization. The price is low, the thermal conductivity is high, and alumina is the most ideal. When the transfer film is in contact with the heating and pressure-adhesive roller, the film is likely to be IS-patterned due to thermal expansion. Therefore, the material of the surface of the pressure-sensitive roller can be effectively suppressed by the heat-resistant resin material such as rubber having moderate elasticity compared with metal or ceramic. Wrinkles caused by thermal expansion of the film. A heating and pressure-adhesive roller (hereinafter referred to as a rubber-heated 11-adhesive roller) which is lining the rubber lining. Generally, the highest set temperature is determined according to the heat-resistant temperature of the adhesive which adheres the metal of the lining to the core material, and the set temperature is set. 1 80 °C or less is suitable; moreover, at the end of production, when the heating and pressing step is stopped due to failure, it is necessary to release the pressure of the heated pressure-sensitive roller to remove the load from the heated pressure-sensitive roller that pushes the formed sheet; When the contact between the formed sheet and the heated pressure-sensitive roller is released, the heat from the heater accumulates heat on the surface of the heated pressure-sensitive roller, and the temperature of the surface of the pressure-sensitive roller is increased by -16-(13) 1247639 to a set temperature or higher; At this time, the temperature of the surface of the pressure-sensitive adhesive roller is heated to a temperature higher than the heat-resistant temperature of the adhesive which adheres the lining to the core material, and the lining is damaged by the core material; therefore, the ruthenium rubber heat-pressing roller is prevented. Damage to the drum, stable production, and set temperature to be more suitable for 16 (TC or less).
又，矽橡膠與金屬、陶瓷相比，熱傳導率大幅度降低 ，約爲〇. 2 W / m · K ;因此之故，提高轉印溫度，欲獲得 更充分之密著性時，在矽橡膠加熱壓黏滾筒之下游，再配 置加熱壓黏滾筒，如此可進行追加之加熱，能提高密著性 ，極爲理想；矽橡膠加熱壓黏滾筒之下游，配置表面爲金 屬或陶瓷等之熱傳導率高達30〜200 W/m· K的材質之 加熱壓黏滾筒，可爲加熱壓黏滾筒的二段構成；此時，矽 橡膠加熱壓黏滾筒爲抑制皺紋之發生，在設定溫度1 60 °C 以下進行第一次加熱，其後可在更高溫之下游加熱壓黏滾 筒進行第二次加熱；藉此，黏著層（B )之Tg高、轉印 溫度高之薄膜亦可獲得良好的密著性，極爲理想。 使用黏著層（B )之Tg爲60〜80°C左右之轉印薄膜 時，加熱壓黏滾筒以二段構成，上游爲矽橡膠加熱壓黏滾 筒，下游可爲陶瓷或金屬之加熱壓黏滾筒；藉此，可降低 上游之矽橡膠加熱壓黏滾筒的設定溫度，從上述防止滾筒 之損傷的觀點而言，値得推薦。 又，因應需求在上述金屬或陶瓷加熱壓黏滾筒之下游 ，可以再配置多段之加熱壓黏滾筒。 對熱塑性樹脂薄片3，連續供應轉印薄膜之際，藉由 -17- (14) 1247639 轉印薄膜之張力在0.01〜0.1 kg/ cm (相當於薄膜供給滾 筒1 〇之寬度方向的單位長度）的拉伸下，以加熱壓黏滾 筒5、6之滾筒壓1〜1〇 kg/ cm (相當於滾筒之寬度方向 的單位長度）之線壓轉印，可使轉印接合面之應變減小、 能均勻層合，極爲理想；轉印薄膜之張力低於0.01kg/ cm時，薄膜容易產生皺紋，超過0.1 kg/cm時，轉印薄 膜4之延伸，易使薄膜龜裂，極不適合·，另一方面，加熱 壓黏滾筒5、6之滾筒壓低於1 kg/ cm時，易使空氣混入 ，超過10 kg/cm時，會產生光學應變，極不適合。 還有，薄膜供給滾筒1 0之外，在薄膜供給滾筒1 0與 加熱壓黏滾筒5之間，藉由增設膨脹滾筒、或螺旋滾筒， 能有效防止熱塑性樹脂押出薄片與薄膜層層合時之薄膜皴 紋，極適宜。 如上所述而得之轉印硬化樹脂薄膜層的樹脂複合薄片 ，外觀優美、轉印後薄膜之密著性亦良好、耐擦傷性等優 異 〇 對熱塑性樹脂薄片3，轉印薄膜4轉印後之基底薄膜 的剝離，亦可做爲製造樹脂複合薄片8的一個階段，又， 在實際使用樹脂複合薄片8之前亦可。 又，製造樹脂複合薄片的方法爲，形成熱塑性樹脂之 押出成型薄片，押出成型薄片在所定溫度範圍內〔四周溫 度（例如 20°C )〜Tg+ 10t，以 Tg — 4〇t 〜Tg+ l〇°C 爲 佳〕的某點，以供給滾筒將對其連續供給之筒捲轉印薄膜 施加熱與壓力，同時轉印的方法極適合於工業上使用，業 -18- 1247639 (15) 已述及；但是’難以如此連,續加熱1 ®黏而轉印時’將以常 法之押出步驟而得的熱塑性樹脂薄片’重新再連續供應轉 印薄膜，於加熱壓黏滾筒加熱、加壓’亦可獲得樹脂複合 薄片。 其次，就本發明之透明的熱塑性樹脂複合薄片’說明 如下。 本發明之透明的熱塑性樹脂複合薄片爲’其至少單面 以黏著層（B)介入其間而將含有硬化樹脂之薄膜層（A )被覆，厚度大約爲〇.5〜5mm之透明薄片者，以厚度薄 至0.5〜3 mm之透明薄片特別理想；本說明書中所謂「透 明」，係指依JIS-K7 105之標準，測得的厚度方向之全光 線透射率在80 %以上，以在85%以上者更佳而言。 又，在本發明之熱塑性樹脂複合薄片的複數處所中， 面方向之複折射値的平均値爲 5 X 1 (Γ5以下者，而且在 其複數場所中面方向之複折射値的各別偏差之範圍，必要 在對平均値± 5 0%以內取得；複折射値爲，厚度方向之光 學相位差除以厚度而得之無因次數者；又，.所謂面方向之 複折射値的平均値，係指將複合薄片在40mm X 5 0mm之 範圍的面方向平均劃分爲5 〇等分以上，各劃分區之複折 射値的算術平均値之意。 本發中所使用之熱塑性樹脂，爲選自可押出薄片成 型之熱塑性樹脂’例如有丙烯酸系樹脂、苯乙烯、丙烯 酸-苯乙_共聚物（以下稱爲MS )、聚碳酸酯（以下稱爲 PC) '氯乙嫌 '丙燒腈-丁二烯-苯乙烯共聚物、聚對苯二 -19- (16) 1247639 甲酸乙二醇醋（以下稱爲PET )系樹脂之單獨，及 物。 此等熱塑性樹脂，在以黏著層（B )介入其間 含有硬化樹脂的薄膜層（A )之際，與黏著層（B 著性較大是其優點；又，將選自此等熱塑性樹脂之 熱塑性樹脂’藉由共押出薄片成型，能形成層合結 片；聚乙烯（以下稱爲PE )、聚丙烯（以下稱爲 環狀聚烯烴等之烯烴系樹脂，自基底薄膜將薄膜層 轉印之際，與薄膜層之密著性相對的小，不適合使 能獲得影像機器之正面板、鏡框面板、分隔板 求的具有高透明性與充分之機械強度、及耐久性的 精確度押出薄片之丙烯酸系樹脂、MS系樹脂、PC 等，爲在附加表面硬化功能方面，値得推薦的最適 塑性樹脂。 丙烯酸系樹脂有，以（甲基）丙烯酸甲酯爲主 脂，此包含（甲基）丙烯酸甲酯之單獨聚合物、或 )丙烯酸甲酯與丙烯酸甲酯、丙烯酸乙酯、丙烯酸 、丙烯酸異丙酯、丙烯酸丁酯、丙烯腈、丙烯酸、 )丙烯酸、2-羥基丙烯酸酯、馬來酸酐、或者 乙烯等之可共聚合單體的任一種以上之共聚物。 此等可單獨使用或混合使用。 爲提升丙烯酸系樹脂之衝擊強度’將在丙烯酸 物芯材料之四周，藉由以丙烯酸丁酯爲主成份之彈 及以（甲基）丙烯酸甲酯爲主成份之非彈性層交互 其混合 、被覆 )之密 複數的 構之薄 ΡΡ )、 1(A) 用。 等所要 高表面 系樹脂 用之熱 體之樹 (甲基 正丙酯 (甲基 甲基苯 系聚合 性層、 生成的 -20- (17) 1247639 多階段依次聚合法，製造而成之橡膠彈性體，混合於做爲 基質樹脂之丙烯酸系樹脂中者，亦包含在本發明的丙烯酸 系樹脂之內。 MS系樹脂爲，丙烯酸-苯乙烯共聚物，更詳細的說， 是（甲基）丙烯酸甲酯與苯乙烯之共聚物者；亦包含以（ 甲基）丙烯酸甲酯與苯乙烯爲主成份，與上述丙烯酸系樹 脂中例示之可共聚合單體的多元共聚物；此等可單獨使用 或混合使用；爲提升M S系樹脂之衝擊強度，將在丙烯酸 系聚合物芯材料之四周，藉由以丙烯酸丁酯爲主成份之彈 性層、及以（甲基）丙烯酸甲酯爲主成份之非彈性層交互 生成的多階段依次聚合法，製造而成之橡膠彈性體、或丁 二烯系橡膠彈性體，混合於做爲基質樹脂之MS系樹脂中 者，亦包含在本發明的MS系樹脂之內。 PC系樹脂有，代表雙酚A型之芳香族聚碳酸酯，及 具有芳香環而羥基不直接連結於芳香環型之芳香族-脂肪 族聚碳酸酯。 本發明之熱塑性樹脂所成押出成型薄片，在不損及其 特性之範圍，可以含有其他之成份，例如著色顏料、著色 染料、熱安定劑、防氧化劑、光安定劑、吸收紫外線劑等 等。 熱塑性樹脂薄片之厚度，依用途而決定，通常使用在 0.5〜5mm之範圍者。 本發明之黏著層（B )係，在將含有硬化樹脂之薄膜 (A )被覆時，爲確保生產之安全性所必要者；又，能使 -21 - 1247639 (18) 具有耐擦傷性、防帶電性、防反射性等之表面功能性的薄 膜層（A )之交換更爲簡便。 爲採用黏著層（B )所使用之樹脂’由一般之丙烯酸 系、醋酸乙烯系、苯乙烯-丁二烯系、聚酯系、乙烯-醋酸 乙烯系、氨基甲酸酯系等樹脂之單獨、或此等之混合物爲 主成份而成之乳膠系、有機溶劑型樹脂之中，適當選擇使 用。 黏著層（B )係，以將上述樹脂用水、有機溶劑稀釋 之塗液，經塗佈乾燥而形成者；黏著層（B )之厚度，因 應被加工薄片之表面狀態，通常在0.3〜20 // m之範圍內 ，適當選擇。 又，黏著層（B )之Tg，一般在l〇〇°C以下，爲比熱 塑牲樹脂薄片之Tg低値者；不過，在本方式中，由於加 熱壓黏時間僅爲通過加熱壓黏滾筒之一瞬間，黏著層（B )之Tg對密著性有很大的影響；因而，轉印薄膜之黏著 層（B)的Tg，以較低者爲佳，以60〜80 X：最爲適合。 黏著層（B )爲，將上述樹脂以冰、有機溶劑稀釋而 成之塗液，使用照相凹版印刷法、網版印刷法、膠版印刷 法，在薄膜上塗佈、乾燥而形成；黏著層（B)之厚度， 因應被轉印薄片之表面狀態，通常在0.3〜20 // m之範圍 內適當選擇。 本發明之轉印薄膜中的具有脫模性之基底薄膜，係指 對形成於其表面之含有硬化樹脂的薄膜層（A )，具有脫 模性’具有無鬆緩、龜裂等不適宜之自保持性強度者；例 -22- (19) 1247639 如 PET、PE、PP、PC、纖維素醋酸酯等之單獨或此等之 複合薄膜狀物；亦包含此等表面施行脫模處理者。 基底薄膜之厚度，通常使用5〜150ym之範圍內者 ，以1 〇〜1 〇〇 m之範圍更佳；以在轉印薄膜之製造步驟 中，形成無皴紋、龜裂等之薄膜層（A )、及藉由轉印形 成外觀良好之複合薄片者最爲適宜。 本發明之含硬化樹脂的薄膜層（A )，除耐擦傷性優 越之硬化樹脂以外，亦可爲含有防帶電性、防表面反射性 、或防污染性優越之不活性樹脂層、光催化劑二氧化鈦之 樹脂層等各種功能的複合之構成；薄膜層（A )以含有， 分子中至少具有兩個以上之丙烯醯氧基或（甲基）丙烯醯 氧基的多功能聚合性單體之聚合硬化物爲佳；該多功能聚 合性單體之例示有，乙二醇二（甲基）丙烯酸酯、三乙二 醇二（甲基）丙烯酸酯、1，4-丁二醇二（甲基）丙烯酸酯 、二丙二醇二（甲基）丙烯酸酯等之分子中具有二個丙烯 醯氧基、或（甲基）丙烯醯氧基之化合物；三羥甲基丙烷 三（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、季 戊四醇四（甲基）丙烯酸酯等之多醇三或四（甲基）丙烯 酸酯化合物；三羥甲基丙烷二（甲基）丙烯酸酯、季戊四 醇三（甲基）丙烯酸酯、2-羥基丙基（甲基）丙烯酸酯、 2-羥基-3-甲氧基丙基（甲基）丙烯酸酯等之具有活性氫 原子之丙烯酸酯化合物，與丙二酸、丁二酸、己二酸等二 羧酸之組合而成的聚酯三或四（甲基）丙烯酸酯化合物； 上述之具有活性氫原子之丙烯酸酯化合物，與二、三、或 -23- 1247639 (20) 四異氰酸酯化合物，及氨基甲酸酯三、或四（甲基）丙烯 酸酯化合物等等。 此等硬化樹脂與硬化劑（光敏化劑）一起溶解於溶劑 中，以k相凹版塗佈法、滾輪塗佈法、逆滾輪法等通常之 方法，塗佈於上述之基底薄膜的單面，經乾燥、紫外線照 射而硬化之方法，極爲理想。 做爲薄膜層（A )之主成份的上述多功能聚合性單量 體之選擇，以塗佈時之黏度調節等的處理性、在空氣中之 硬化的難易’硬化後之硬度等著眼，大部份的情況是以此 等適當混合使用；又，爲改善硬化薄膜之密著性、改善在 空氣中之硬化特性，亦可配合單功能性之聚合性單體及安 定劑等等。 如此而形成之薄膜層（A )，表面硬度（以JIS-K 5 4 0 0之手寫法測得之値）以3 Η以上爲宜，厚度爲由1 〜1 0 A m之範圍適當選擇；厚度低於1 # m時，不能顯現 充分之性能；又，超過l〇//m時，會發生硬化不良、硬 化後之塗膜會產生裂紋等，極爲不佳。 薄膜層（A )，由於其做爲交聯體之特性，對各種藥 劑之耐性大，例如防止油類之污染；又，能防止由各種醇 類、酮類、石油類等有機溶劑而起之表面白化、龜裂之發 生，使基材薄片之適用性大爲提高。 還有，爲提升薄膜層（A)與黏著層（B)中間之密 著性、可撓性，亦可以眾所周知的環氧化合物，形成1〜 1 〇 // πι之範圍的中間薄膜。 -24- (21) 1247639 將獲得本發明表面電阻値在1 〇 12以下的防帶電性能 優越之轉印薄膜的方法，例示如下；首先，在基底薄膜之 上，將含有上述硬化樹脂之氧化錫等導電性微粉末分散的 塗佈液塗佈、乾燥，接著以U V硬化，形成厚度爲1〜1 0 // m之薄膜層（A );其後，依順序形成丙烯酸系黏著層 (B )。 > 將如此而得之轉印薄膜的薄膜層（A )，轉印於熱塑 性樹脂薄片之單面或兩面；藉此形成，能有效防止一般塵 埃附著、與具有表面電阻値在1 0 1 2以下之性能的防帶電 性優越、而且同時具有耐擦傷性之複合薄片，可同時防止 塵埃之附著及防止表面之損傷。 進而，本發明之表面反射率爲3 %以下者；就獲得防 止表面反射功能優越之轉印薄膜的方法，以下示之例說明 〇 首先，將含有烷基烷氧基矽烷、與聚醚、及有機溶媒 之溶液，塗佈於基底薄膜上，烷基烷氧基矽烷之一部份或 全部，經脫水縮合而成塗佈膜；接著，其後，上述聚醚自 塗佈膜藉由有機溶媒而溶出，成多孔質化而得最終厚度爲 0.3〜3 // m之多孔質烷基烷氧基矽烷的脫水縮合膜。 促進此脫水層縮合反應之催化劑，可以添加鹽酸、硫 酸、硝酸等之無機酸水溶液，醋酸等之有機酸水溶液；使 用之有機溶媒，可以使用能將聚醚溶解之各種醇類、酮類 、醚類。 在如此而得之多孔質烷基烷氧基矽烷脫水縮合膜上， •25- (22) 1247639 依順序形成上述之耐擦傷性硬化樹脂皮膜、丙烯酸系黏著 層’即使轉印薄膜；將此轉印薄膜之薄膜層（A )轉印於 樹脂薄片面上，可獲得表面反射率在3%以下之防表面反 射性能優越的複合薄片。 所謂防止表面反射性能，係指在表面反射之光的比率 低之狀態而言；在表面反射之光的比率低，能減少使用於 影像機器之正面板、鏡框面板等用途的樹脂薄片之表面上 映照的外光。 【實施方式】 〔實施例〕（實施例1〜1 〇及比較例1〜2 ) 以實施例、比較例更具體的說明本發明如下；本發明 對此等實施例，沒有任何限制；還有，各實施例、比較例 之評估及試驗方法，如下述之說明。 (1 )薄片表面溫度之測定： 將線徑爲〇.2mm之K型熱電偶，以厚度0.07mm之聚 醯亞胺製耐熱膠黏帶，膠黏於熱塑性樹脂之押出成型薄片 表面，測定並記錄在通過加熱壓黏滾筒前（圖1中之a部 )押出成型薄片之表面溫度，及通過加熱壓黏滾筒時（圖 1中之bl部、b2部）押出成型薄片之表面溫度；在通過 加熱壓黏滾筒時（b 1部、b2部）複合薄片（轉印薄膜轉 印後之押出成型薄片）的表面溫度，與在通過加熱壓黏滾 筒時（b 1部、b 2部）複合薄片中之押出成型薄片部份的 表面溫度，可視爲近似者。 -26- 1247639 (23) (2 )外觀之判定： 樹脂複合薄片之表面平滑性、及其他有無損及外觀之 異常，以目視判定之；良好時爲〇、稍有不良但實際上沒 有問題之情況爲△、貫際上不能接受之異常情況爲χ。 (3 )密著性之判定： 依JIS-K5400之棋盤目黏膠帶試驗法的標準進行；即 ’在樹脂複合薄片之薄膜層被覆面，使用美工刀，劃成 1mm2正方形之100格的棋盤目，以賽璐玢膠帶黏著後， 用手強力拉起，判定薄膜層有無剝離；1 00格完全未剝離 時爲〇、全部被剝離時爲X。 (4 )全光線透射率： 依JIS-K7105之標準測定。 (5 )表面硬度： 依JIS-K5400手寫法之標準測定。 (6 )表面電阻値： 依JIS-K691 1之標準測定。 (7 )表面反射率： 使用日立製作所股份有限公司製之UV3 100測定，記 錄在可視光波長區域之最低反射率。 (8 )複折射値之測定= 在偏光顯微鏡（來茲股份有限公司製，DMRP型’附 帶補償器）上，準備預先測定光學相位差之薄片狀標準試 使用具備有水平相對之兩片偏光板、與在其下方可照 -27- (24) 1247639 明之裝置的偏差測定器（新東科學股份有限公司製），昭 明照射之同時，調整單方之偏光板的偏振光鏡角度最暗之 角度而固定，在該兩片偏光板之間，將薄片狀之標準試料 ，固定在同一水平。 將薄片狀之標準試料在水平上旋轉，同時固定於最明 亮之角度，以在垂直上部之亮度測定器（密諾魯達股份有 限公司製，測定液晶色分佈之測定裝置，CA-〗000型）測 定売度。 還有，採取在薄片狀標準試料之厚度爲1mm面方向 的測定範圔爲40mm x50mm，面方向劃分爲200等份的 亮度數據。 以測定光學相位差相異之複數薄片狀標準試料的亮度 ，能掌握此等試料之亮度的關係。 測定對象之樹脂複合薄片試料（與上述相同的，在厚 度爲 1mm之面方向的測定範圍爲40mm x50mm者）， 依同樣的方法測定亮度，換算成光學相位差後，除以厚度 求出複折射値。. (9 )環境試驗： 在保持溫度60 °C、相對濕度90%之恆溫恆濕槽中， 將1mm厚，50mm x 7 0mm大小之樹月旨複合薄片試料，靜 置24 0小時，觀察並記錄試驗前後之狀態。 〔實施例1〕 準備厚度1mm、寬300mm、長lm之得拉古拉a (旭 -28 · (25) 1247639 化成化學品股份有限公司製之丙烯酸系樹脂押出成型薄片 )做爲押出成型薄片。 另一方面，在厚度38//m之PET薄膜之單面上，將 二乙二醇二（甲基）丙烯酸酯1 0重量份、季戊四醇三丙 烯酸酯與六甲烯二異氰酸酯之附加生成物的氨基甲酸酯丙 烯酸酯20重量份、苯偶因異丙醚1重量份、甲苯40重量 份、甲乙酮（以下稱爲MEK ) 20重量份、異丙醇1 〇重量 份所成之溶液，以逆輥法塗佈、及乾燥後，用UV燈照射 硬化，即形成厚5 // m之硬化樹脂薄膜。 在此硬化樹脂薄膜之上，將以脂環式環氧化合物謝洛 奇賽得2 0 2 1 (賴伊謝魯股份有限公司製）7 5重量份、 1,4-環己烷二羥甲基二乙烯基醚3重量份、酚醛型環氧樹 月旨（旭奇巴股份有限公司製）15重量份、光陽離子聚合 引發劑（優尼甕卡拜得股份有限公司製）4重量份所成塗 料塗佈，使用水銀燈照射而硬化，即形成厚度丨.5 # m之 中間膜；於此中間膜上，塗佈丙烯酸系塗料（樹脂份2 〇 重量份、甲苯5 0重量份、Μ E K 3 0重量份），乾燥後，形 成厚度l//m之黏著層，即得轉印薄膜。 還有’此轉印薄膜爲，藉由將基底薄膜自捲出滾筒經 塗佈部、乾燥部等之加工部，供應至捲取滾筒的加工裝置 ’以最終之寬度300m、長度50m之滾筒捲取狀態而準備 〇 以調整薄膜供給滾筒之驅動速度，使轉印時押出成型 薄片之移動速度爲1 m/min，而配置加熱壓黏滾筒；黏 -29 - (26) 1247639 著層對準薄片表面側，將上述滾筒捲取形態之轉印薄膜， 以薄膜供給滾筒、加熱壓黏滾筒介入其間連續供應，轉印 於同時供應至加熱壓黏滾筒之押出成型薄片的兩面，而成 複合薄片；還有，轉印之前（a部）的押出成型薄片之表 面溫度爲2 3 C者。 又，爲去除塵埃，可在加熱壓黏滾筒之前設置除靜電 空氣供給器（奇元斯股份有限公司製，SJ-R0 3 6 )。 加熱壓黏滾同’爲使用以角氏硬度爲Hs60之砂橡膠 在金屬滾筒的表面襯裏3mm厚者。 轉印薄膜之供應，係在〇.〇3 kg/ cm (相當於薄膜供 給滾筒之寬度方向的單位長度）之拉伸應力（張力）下、 加熱壓黏滾筒之溫度爲170 °C、加熱壓黏滾筒之壓力爲6 kg/cm (相當於加熱壓黏滾筒之寬度方向的單位長度） 之線壓下加壓同時施行。 通過加熱壓黏滾筒時（bl部）之複合薄片（轉印薄 膜轉印於押出成型薄片者）的表面溫度爲1 3 (TC。 將此轉印完成之複合薄片，切成60 cm長度，剝去基 底薄膜；所得樹脂複合薄片爲，全光線透射率高、實際上 無表面凹凸等損及外觀之缺點、具有與依常法所得丙烯酸 樹脂薄片相同之良好的外觀者。 又，可獲得表面硬度比形成複合薄片之前大幅度的提 高、耐擦傷性良好、表面保護性優越之樹脂複合薄片。 〔實施例2〜4〕 -30- 1247639 (27) 實施例2使用丙烯酸樹脂（旭化成化學品股份有限公 司製，商品名爲得魯佩特7 Ο Η，透明，T g 1 0 4 °C )做爲熱 塑性樹脂； 實施例3使用M S樹脂（新日鐵化學股份有限公司製 ，商品名爲耶是奇連MS600，透明，Tg 100°C )做爲熱塑 性樹脂； 實施例4使用橡膠彈性體混合於丙烯酸系樹脂之耐衝 擊性丙烯酸系樹脂（旭化成化學品股份有限公司製，商品 名爲得魯佩特SR8200，透明，基質Tg 1 1(TC )做爲熱塑 性樹脂； 採用押出機（螺旋徑5〇mm0、L/D = 32、單軸）、薄 片擠壓模、及冷卻與擦光用之磨光滾筒三支所成之裝置， 與取出滾筒，依常法進行押出薄片成型，即製成寬 300mm之押出成型薄片。 還有，使用之上述各樹脂押出成型時的樹脂溫度爲調 整至，丙烯酸樹脂2 6 0 °C、M S樹脂2 3 (TC、耐衝擊性丙烯 酸樹脂25 0°C。 調整薄片擠壓模排出口與磨光滾筒之間隔，及磨光滾 筒與取出滾筒之轉速，使押出成型薄片之厚度爲1.0 mm， 薄片押出速度爲3 m/分鐘。 押出成型薄片之各別的表面硬度爲，丙烯酸樹脂2H 、M S樹脂1 Η、耐衝擊性丙烯酸樹脂1 Η ;表面電阻値爲 ，任一種均超過1〇16Ω者。 另一方面，準備與實施例1相同之轉印薄膜。 -31 - (28) 1247639 在上述磨光滾筒與取出滾筒的中間，設置以去除塵埃 爲目的之除靜電空氣供給器（奇元斯股份有限公司製， SJR-R03 6 );黏著層對準薄片表面側，將上述滾筒捲取形 態之轉印薄膜，以薄膜供給滾筒、加熱壓黏滾筒介入其間 連續供應，即製成轉印於押出成型單面之複合薄片。 加熱壓黏滾筒爲使用以肖氏硬度Hs60之矽橡膠在金 屬浪筒的表面襯裏3mm厚者。 轉印薄膜之供應，係在0.0 3 k g / c m (相當於薄膜供 給滾筒之寬度方向的單位長度）之拉伸應力（張力）下， 加熱壓黏滾筒之溫度爲170 °C、加熱壓黏滾筒之壓力爲6 kg / cm (相當於加熱壓黏滾筒之寬度方向的單位長度） 之線壓下加壓同時施行。 將此轉印完成之複合薄片，切成60cm長度，剝去基 底薄膜；所得樹脂複合薄片爲，全光線透射率高、實際上 無表面凹凸等損及外觀之缺點、具有與依常法所得丙烯酸 樹脂、MS樹脂、耐衝擊丙烯酸系樹脂各薄片相同之良好 的外觀者。 又’可獲得轉印面側之表面硬度比形成複合薄片之前 大幅度的提高、耐擦傷性良好、表面保護性能優越之樹脂 複合薄片。 〔實施例5〕 使用PC樹脂（帝人化成股份有限公司製，商品名爲 帕恩來特K-1 3 〇〇，透明）做爲熱塑性樹脂，薄片押出成 -32- (29) 1247639 型時之樹脂溫度調節爲290 °C，其他都和實施例2相同的 製得薄片之表面硬度爲B，表面電阻値爲以上者。 另一方面，在厚度38//m之PET薄膜的單面上，使 用在實施例1中使用之硬化樹脂薄膜形成用溶液1 〇〇重量 份中，加入氧化錫微粉末2 0重量份，以球磨機分散者之 外，其他都和實施例1同樣的製得轉印薄膜。 在磨光滾筒與取出滾筒的中間，設置使押出成型薄片 加熱之遠紅外線盤式加熱器，以保持押出成型薄片表面在 1 1 0 °C ( a部），同時在押出成型薄片之兩面轉印以外， 其他都和實施例2同樣的製得樹脂複合薄片；如此而得之 樹脂複合薄片的表面硬度爲3H、表面電阻値爲109Ω者， 與依常法所得PC薄膜相比，具有充分的表面硬度與防帶 電性。 〔實施例6〕 在厚50//m之表面平滑性優越的光學用pet薄膜之 單面上’依下述之方法形成厚〇 · 8 // m之多孔質烷基烷氧 基矽烷脫水縮合薄膜。 在單甲基三乙氧基矽烷1〇〇重量份中，加入乙醇與丁 醇之容積比1對2之混合物2 0 0重量份混合，更於此溶液 中加入水6 0重量份與磷酸3重量份混合；其後，再增加 乙醇與丁醇之容積比1對2的混合物2 0 0重量份與聚乙二 醇（日本油脂股份有限公司製，PEG#1540) 80重量份， 攪拌均勻，即調製成塗佈溶液。 -33- (30) 1247639 在上述光學用PET薄膜之單面上，將此塗佈溶液之 滾輪塗佈法塗佈，藉由乾燥後浸漬於乙醇中，將聚乙二醇 自塗佈膜溶出去除，接著再乾燥。 以上爲使用在實施例5使用之含有氧化錫微粉末的硬 化樹脂薄膜形成用之溶液，形成1 // m之硬化層；更與實 施例1同樣的形成5 // m之硬化樹脂薄膜，接著形成黏著 層，即得轉印薄膜。 將此轉印薄膜，與實施例2同樣的轉印於丙烯酸樹脂 之押出成型薄片後，剝去基底薄膜，即得樹脂複合薄片； 此樹脂複合薄片，實際上沒有表面凹凸等損及外觀之缺點 、具有與依常法所得丙烯酸系樹脂薄片相同之良好的外觀 ，全光線透射率95%、表面硬度4H、表面電阻値爲1010 Ω ’表面反射率爲2%，爲透明性高、難受損傷、塵埃等 甚難附著、而且外光之映照甚少，極適合使用於影像機器 、鑑賞繪畫用鏡框面板等之樹脂複合薄片。 實施例1〜6之樹脂複合薄片的複折射値，其平均在 5 X 以下，又對該平均値之偏差的大小爲±50%以下 ，在環境試驗中亦沒有任何問題。 〔實施例7〕 在厚度爲38 // m之PET薄膜的單面上，將二乙二醇 二（甲基）丙烯酸酯20重量份、環氧丙烯酸酯10重量份 、苯偶因異丙醚1重量份、甲苯40重量份、甲乙酮（以 下稱爲Μ E K ) 2 0重量份、異丙醇1 〇重量份所成之溶液， -34- (31) 1247639 以逆輥法塗佈、及乾燥；接著以U V燈照射硬化，即形成 厚3 · 5 // m之硬化樹脂薄膜；更以丙烯酸系塗料塗佈，乾 燥，即得形成厚1 // m之黏著層的轉印薄膜；又，在使用 以肖氏硬度Hs60之矽橡膠於金屬滾筒的表面襯裏3mm之 加熱壓黏滾筒的下游，設置以陶瓷（含3重量°/。二氧化鈦 之以氧化鋁爲主成份的組成）火焰噴塗於金屬滾筒之表面 0· 2 m ηι厚的加熱壓黏滾同’使加熱壓黏滾同成爲_段構成 ;矽橡膠滾筒之設定溫度爲160°C、陶瓷滾筒之設定溫度 爲200 °C ;除此等之點以，其他都和實施例2相同的製 得樹脂複合薄片。 通過加熱壓黏滾筒時之複合薄片表面溫度（b2部） 爲1 4 3 °C ;所得複合薄片爲，全光線透射率高，實際上無 表面凹凸等損及外觀之缺點，具有與依常法所得丙烯酸樹 脂薄片相同之良好的外觀者；又，確認爲表面硬度比形成 複合薄片之前大幅度的提升、且耐擦傷性良好、表面保護 性優越之樹脂複合薄片。 〔實施例8〕 在擠壓模之排出口的兩端，安裝流路遮蔽板，使押出 成型薄片之寬度成爲10 0mm，藉由調整押出機排出量、 薄片擠壓模出口、及磨光滾筒之間隔，使押出成型薄片之 厚度調整爲3.0mm;除矽橡膠滾筒之設定溫度爲16(TC、 陶瓷滾筒之設定溫度爲220 °C以外，其他都和實施例7相 同的製得樹脂複合薄片。 -35- 1247639 (32) 所得樹脂複合薄片爲，全光線透射率高 表面凹凸等損及外觀之缺點、具有與依常法 樹脂薄片同樣的良好之外觀者。 又，確認爲表面硬度比形成複合薄片之 升，且耐擦傷性良好、表面保護性優越之樹 〔實施例9〕 除矽橡膠滾筒之設定溫度爲1 8 0 °C，陶 溫度爲220 °C以外，其他都和實施例7同樣 合薄片。 通過加熱壓黏滾筒時之複合薄片表面禮 爲1 63 °C ;所得複合薄片，雖稍有彎曲起伏 有任何問題；又，確認爲全光線透射率高、 成複合薄片之前大幅度的提升，且耐擦傷良 性優越之樹脂複合薄片。 〔實施例1 0〕 除使用實施例7所用相同之轉印薄膜， 僅爲陶瓷火焰噴塗之滾筒的一段構成，加熱 定溫度爲1 6 (TC以外，其他都和實施例2同 複合薄片。 通過加熱壓黏滾筒時之複合薄片表面怒 爲133°C;所得複合薄片，在薄膜端面上雖 ’但做爲製品供應之部份，實際上沒有損及 、實際上沒有 而得之丙烯酸 前大幅度的提 指複合薄片。 瓷滾筒之設定 的製得樹脂複 .度（b2部） ，但實用上沒 表面硬度比形 好、表面保護 加熱壓黏滾筒 壓黏滾筒之設 樣的製得樹脂 .度（b2部） 梢有皺紋產生 外觀之缺點， -36- (33) 1247639 實用上沒有任何問題；又，確認爲全光線透射率高、表面 硬度比形成複合薄片之前大幅度的提升，且耐擦傷性良好 、表面保護性優越之樹脂複合薄片。 〔比較例1及2〕 以射出成型，製作成厚1mm、50mm x 7 0mm,各角 之彎曲半徑R爲2.5mm的成型品。 使用丙烯酸系透明樹脂（旭化成化學品股份有限公司 製，商品名爲得魯佩特6 0N，透明），射出成型條件：比 較例1之樹脂溫度爲2 1 0°C、比較例2之樹脂溫度爲240 °C，其他之共通條件爲：金屬模具溫度60 °C、樹脂壓力 8 0 MPa ;還有，上述樹脂溫度，從樹脂流動性之觀點而言 ，係在標準的溫度領域之上下施行者。 如此所得之成型品的表面硬度，兩者均爲1 Η。 進而，將實施例1所用之轉印薄膜的黏著層做爲成型 品側安裝於金屬模具內，在同條件下依常法進行射出成型 ，將薄膜層轉印於被轉印物之射出成型的表面後，剝離基 底薄膜。 此等成型品之表面硬度均高達5 Η ;但是，閘門附近 之複折射値，比平均値高出甚多，顯示有內部應變存在； 又，環境試驗後’觀察到其發生變形，比較例1更發現硬 化樹脂薄膜之密著性不良。 -37- 1247639 £ 實施例 〇 一 U I c:!60 1 m m △薄膜皺紋 〇 (N Ο X 未測定 1未測定I 未測定 未測定 未測定 1未測定| ON 一 S+C s:180 c:220 ο m \〇 △表面波紋 〇 (N 〇 未測定i 未測定 未測定| 未測定 未測定 未測定 〇〇 m S+C s:160 c:220 g (N VO 〇 〇 (N 〇 1未測定1 1未測定 未測定 未測定 未測定 未測定 卜 一 S+C s:!60 c:200 〇〇 〇 〇 (N 〇 1未測定I 未測定 未測定 未測定 細定 未測定 v〇 一 tn s:170 1 g 2 1 〇 〇 〇s X 〇 *〇 Λ (Ν — + 〇 1 無變化 一 s:170 1 o (N VO 1 〇 〇 ON 00 >109 未測定 +35 〇 (N 無變化 - C/5 s:!70 « s (N 1 〇 〇 5； 3： rr >10,6 1未測定1 (N +20 1 無變化 m 一 in i s:170 1 g 1 〇 〇 g X TT *〇 7\ 1未測定1 一 +25 〇 (N 無變化1 (N — in s:170 1 g tn (N 1 〇 〇 CN ON Ό Λ 未測定 一 + 16 〇 1 無變化 一 一 C/D s:170 1 1 〇 〇 (N 〇\ X 〇 Λ 1未測定1 一 + 10 〇 1 無變化 薄片厚度（mm) 加熱加壓滾筒 cn o §n cd b丨部 b2部 外觀 密著性 全光線透射率（％) 表面硬度 表面電阻値 （Ω) 表面反射率 （％) 平均値 (X 10-5) 對該平均値之偏差的最大値 (%) 對該平均値之偏差的最小値 (%) 環境試驗 滾筒設定溫度 /^S 普 r-v P 薄片表面溫度 /^N fN s P 複折射値 -IK1 ^ l^iilsmi0+--1^^ ^ I- C* -38- 1247639Moreover, compared with metals and ceramics, the thermal conductivity of niobium rubber is greatly reduced, which is about 〇. 2 W / m · K ; Therefore, to increase the transfer temperature, in order to obtain more sufficient adhesion, the heating press roller is disposed downstream of the 矽 rubber heating pressure roller, so that additional heating can be performed. It is ideal for improving the adhesion; the rubber is heated to the downstream of the pressure-adhesive roller, and the surface is made of a metal or ceramic material with a thermal conductivity of 30~200 W/m·K, which can be heated and pressed. The second section of the drum is formed; at this time, the 矽 rubber heating pressure roller prevents the occurrence of wrinkles, and the first heating is performed at a set temperature of 1 60 ° C or lower, and then the pressure roller is heated at a lower temperature for the second time. By this, it is preferable that the film of the adhesive layer (B) having a high Tg and a high transfer temperature can obtain good adhesion. When the transfer film of the adhesive layer (B) is about 60 to 80 ° C, the heating pressure roller is composed of two stages, the upstream is a rubber heating pressure roller, and the downstream is a ceramic or metal heating pressure roller. Thereby, the set temperature of the rubber heating and pressure roller upstream of the crucible can be lowered, and it is recommended from the viewpoint of preventing the damage of the roller. In addition, in response to the demand, downstream of the above metal or ceramic heating and pressure roller, a plurality of sections of the heating and pressure roller can be disposed. For the thermoplastic resin sheet 3, when the transfer film is continuously supplied, the tension of the transfer film by -17-(14) 1247639 is at 0. 01~0. 1 kg/cm (corresponding to the unit length in the width direction of the film supply roller 1 )), and the roller pressure of the pressure-adhesive rollers 5 and 6 is 1 to 1 〇 kg/cm (corresponding to the width direction of the roller) The linear pressure transfer of the unit length can make the strain of the transfer joint surface reduce and uniform lamination, which is ideal; the tension of the transfer film is lower than 0. At 01kg/cm, the film is prone to wrinkles, exceeding 0. At 1 kg/cm, the extension of the transfer film 4 tends to cause cracking of the film, which is extremely unsuitable. On the other hand, when the pressure of the heated pressure-sensitive adhesive rollers 5, 6 is less than 1 kg/cm, air is easily mixed in. At 10 kg/cm, optical strain is generated and it is extremely unsuitable. Further, in addition to the film supply roller 10, between the film supply roller 10 and the heating and pressure roller 5, by adding an expansion roller or a spiral roller, it is possible to effectively prevent the thermoplastic resin from being laminated on the film layer and the film layer. Film crepe, very suitable. The resin composite sheet of the transfer-hardened resin film layer obtained as described above is excellent in appearance, excellent in adhesion of the film after transfer, and excellent in scratch resistance, etc. After the transfer of the thermoplastic resin sheet 3 and the transfer film 4 The peeling of the base film can also be used as a stage for producing the resin composite sheet 8, and it is also possible before the resin composite sheet 8 is actually used. Further, a method of producing a resin composite sheet is to form a stretched formed sheet of a thermoplastic resin, and extruding the formed sheet within a predetermined temperature range [four-week temperature (for example, 20 ° C) to Tg + 10 t, to Tg - 4 〇 t 〜 Tg + l 〇 ° At a point where C is better, the supply roller applies heat and pressure to the continuous transfer film of the roll, and the transfer method is very suitable for industrial use. -18-1247639 (15) However, it is difficult to continue to supply the transfer film when the heating is continued, and the thermoplastic resin sheet obtained by the normal extrusion step is re-continuously supplied to the transfer film, and heated and pressurized on the heated pressure roller. A resin composite sheet can be obtained. Next, the transparent thermoplastic resin composite sheet 'of the present invention' will be described below. The transparent thermoplastic resin composite sheet of the present invention is coated with a film layer (A) containing a hardening resin at least on one side with an adhesive layer (B) interposed therebetween, and has a thickness of about 〇. For 5~5mm transparent sheets, the thickness is as thin as 0. A transparent sheet of 5 to 3 mm is particularly desirable; the term "transparent" as used in the specification means that the total light transmittance in the thickness direction measured by the standard of JIS-K7 105 is 80% or more, and is more than 85%. Good. Further, in the plural places of the thermoplastic resin composite sheet of the present invention, the average enthalpy of the complex refracting enthalpy in the plane direction is 5 X 1 (Γ5 or less, and the respective deviations of the complex refracting enthalpy in the plane direction in the plural places) The range must be obtained within ±0.5% of the average ;; the complex refracting 値 is the optical phase difference in the thickness direction divided by the thickness and the number of non-caused times; The average enthalpy of the complex refracting enthalpy in the plane direction means that the composite sheet is equally divided into 5 〇 equal parts or more in the plane direction of the range of 40 mm X 50 mm, and the arithmetic mean 値 of the complex 値 of each divided area is intended. The thermoplastic resin used in the present invention is a thermoplastic resin selected from extrudable sheets, for example, an acrylic resin, styrene, acrylic-styrene copolymer (hereinafter referred to as MS), or polycarbonate (hereinafter referred to as PC) 'Synthesis of a mixture of nitrile-butadiene-styrene copolymer, polyparaphenylene-19-(16) 1247639 formate glycol (hereinafter referred to as PET) resin. When the adhesive layer (B) is interposed between the film layer (A) containing the cured resin, the adhesive layer (B) is advantageous in that the adhesive layer (B) is large; and the thermoplastic resin selected from the thermoplastic resins is selected. The resin is formed by co-extruding a sheet to form a laminated sheet; polyethylene (hereinafter referred to as PE), polypropylene (hereinafter referred to as an olefin-based resin such as a cyclic polyolefin, and a film layer is transferred from the base film) In contrast, it is relatively small in adhesion to the film layer, and is not suitable for obtaining the high transparency and sufficient mechanical strength and durability of the front panel, the frame panel, and the partition plate of the image forming machine. Acrylic resin, MS resin, PC, etc., are the most suitable plastic resins recommended for the addition of the surface hardening function. Acrylic resins include methyl (meth) acrylate as the main resin, which includes (methyl) A single polymer of methyl acrylate, or) methyl acrylate with methyl acrylate, ethyl acrylate, acrylic acid, isopropyl acrylate, butyl acrylate, acrylonitrile, acrylic acid, acrylic acid, 2- Any one or more of the monomers acrylate copolymer, maleic anhydride, or ethylene, etc. may be copolymerized. These can be used alone or in combination. In order to improve the impact strength of the acrylic resin, it will be mixed and coated on the periphery of the acrylic core material by using a butyl acrylate-based bomb and an inelastic layer containing methyl (meth) acrylate as a main component. ) The dense and complex structure of the thin ΡΡ ), 1 (A). A hot body tree for high surface resin (methyl n-propyl ester (methyl methyl benzene polymerizable layer, formed -20- (17) 1247639 multi-stage sequential polymerization method, manufactured by rubber elastic The body is mixed with the acrylic resin as a matrix resin and is also included in the acrylic resin of the present invention. The MS resin is an acrylic-styrene copolymer, and more specifically, (meth)acrylic acid. a copolymer of a methyl ester and styrene; a multicomponent copolymer comprising a methyl methacrylate and styrene as a main component and a copolymerizable monomer exemplified in the above acrylic resin; these may be used alone Or in combination; in order to improve the impact strength of the MS resin, the elastic layer mainly composed of butyl acrylate and the main component of methyl (meth) acrylate are used around the acrylic polymer core material. A rubber elastomer or a butadiene rubber elastomer produced by a multi-stage sequential polymerization method in which non-elastic layers are alternately produced, and mixed in an MS resin as a matrix resin, is also included in the present invention. The PC-based resin includes an aromatic polycarbonate which is a bisphenol A type, and an aromatic-aliphatic polycarbonate which has an aromatic ring and the hydroxyl group is not directly bonded to the aromatic ring type. The thermoplastic resin is extruded into a formed sheet, and may contain other components such as a coloring pigment, a coloring dye, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorbing agent, etc., without impairing its characteristics. The thickness is determined by the use and is usually used at 0. 5 to 5mm range. The adhesive layer (B) of the present invention is necessary for ensuring the safety of production when the film (A) containing the cured resin is coated; and the abrasion resistance of the -2147639 (18) can be prevented. The exchange of the film layer (A) having surface functional properties such as chargeability and antireflection is simpler. The resin used in the adhesive layer (B) is composed of a resin such as a general acrylic, vinyl acetate, styrene-butadiene, polyester, ethylene-vinyl acetate or urethane resin. The latex-based or organic solvent-based resin in which the mixture is a main component is appropriately selected and used. The adhesive layer (B) is formed by coating and drying the coating liquid diluted with water or an organic solvent; the thickness of the adhesive layer (B) is usually at 0 depending on the surface state of the processed sheet. Within the range of 3~20 // m, choose as appropriate. Moreover, the Tg of the adhesive layer (B) is generally below 10 ° C, which is lower than the Tg of the thermoplastic resin sheet; however, in this embodiment, since the heating and pressing time is only by heating the pressure roller In one instant, the Tg of the adhesive layer (B) has a great influence on the adhesion; therefore, the Tg of the adhesive layer (B) of the transfer film is preferably lower, 60 to 80 X: most Suitable for. The adhesive layer (B) is a coating liquid obtained by diluting the above resin with ice or an organic solvent, and is formed by coating and drying on a film by gravure printing, screen printing, or offset printing; and an adhesive layer ( B) The thickness, depending on the surface state of the sheet to be transferred, is usually 0. Choose within the range of 3~20 // m. The base film having releasability in the transfer film of the present invention means a film layer (A) containing a hardened resin formed on the surface thereof, and has a mold release property of being unsuitable, such as no looseness or cracking. Self-retaining strength; Example-22-(19) 1247639 A composite film such as PET, PE, PP, PC, cellulose acetate, or the like, or a release film of such surfaces. The thickness of the base film is usually in the range of 5 to 150 μm, preferably in the range of 1 〇 to 1 〇〇m; in the manufacturing step of the transfer film, a film layer free from crepe, cracks, or the like is formed ( A), and by transfer to form a composite sheet having a good appearance is most suitable. The hardened resin-containing film layer (A) of the present invention may be an inactive resin layer excellent in antistatic property, surface reflection resistance, or antifouling property, and a photocatalyst titanium oxide, in addition to a cured resin excellent in scratch resistance. a composite of various functions such as a resin layer; the film layer (A) is cured by polymerization of a multifunctional polymerizable monomer having at least two or more acryloxy groups or (meth) acryloxy groups in the molecule; Preferably, the multifunctional polymerizable monomer is exemplified by ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and 1,4-butanediol di(methyl). a compound having two acryloxy groups or (meth) propylene oxime groups in a molecule such as acrylate or dipropylene glycol di(meth) acrylate; trimethylolpropane tri(meth) acrylate or pentaerythritol; Polyol tri or tetra (meth) acrylate compound such as tris(meth) acrylate or pentaerythritol tetra(meth) acrylate; trimethylolpropane di(meth) acrylate, pentaerythritol tri(methyl) Propylene An acrylate compound having an active hydrogen atom such as an acid ester, 2-hydroxypropyl (meth) acrylate or 2-hydroxy-3-methoxypropyl (meth) acrylate, and malonic acid and dibutyl a polyester tri- or tetra(meth)acrylate compound obtained by combining a dicarboxylic acid such as an acid or adipic acid; the above-mentioned acrylate compound having an active hydrogen atom, and two, three, or -23-1247639 (20) a tetraisocyanate compound, and a urethane tri- or tetra(meth) acrylate compound or the like. These hardened resins are dissolved in a solvent together with a curing agent (photosensitizer), and are applied to one side of the above-mentioned base film by a usual method such as a k-phase gravure coating method, a roll coating method, or a reverse roller method. The method of hardening by drying and ultraviolet irradiation is extremely desirable. The selection of the above-mentioned multifunctional polymerizable single body as the main component of the film layer (A) is focused on the handling property such as viscosity adjustment at the time of coating, the difficulty in hardening in the air, the hardness after hardening, and the like. In some cases, it is used in such a suitable mixture; in order to improve the adhesion of the cured film and to improve the hardening property in air, it is also possible to mix a monofunctional polymerizable monomer and a stabilizer. The film layer (A) thus formed has a surface hardness (measured by the handwriting method of JIS-K 5400) of preferably 3 Å or more, and a thickness of suitably selected from the range of 1 to 10 mA; When the thickness is less than 1 #m, sufficient performance cannot be exhibited. When the thickness exceeds 1 〇//m, hardening failure occurs, and cracking of the coating film after hardening occurs, which is extremely poor. The film layer (A), because of its characteristics as a crosslinked body, has high resistance to various chemicals, for example, prevention of oil contamination, and can prevent organic solvents such as various alcohols, ketones, and petroleum. The occurrence of surface whitening and cracking greatly improves the applicability of the substrate sheet. Further, in order to improve the adhesion and flexibility between the film layer (A) and the adhesive layer (B), a well-known epoxy compound can be formed to form an intermediate film in the range of 1 to 1 〇 // πι. -24- (21) 1247639 A method for obtaining a transfer film having an excellent antistatic property with a surface resistance of 1 to 12 or less in the present invention is exemplified as follows. First, a tin oxide containing the above-mentioned hardened resin is provided on the base film. The coating liquid in which the conductive fine powder is dispersed is applied, dried, and then cured by UV to form a film layer (A) having a thickness of 1 to 10 // m; thereafter, an acrylic adhesive layer (B) is sequentially formed. . > The film layer (A) of the transfer film thus obtained is transferred onto one or both sides of the thermoplastic resin sheet; thereby being formed, it is possible to effectively prevent the adhesion of general dust and the surface resistance at 10 1 2 The following properties are excellent in anti-chargeability and at the same time have a scratch-resistant composite sheet, which simultaneously prevents dust from adhering and prevents damage to the surface. Further, the surface reflectance of the present invention is 3% or less; and a method for obtaining a transfer film having excellent surface reflection preventing function is exemplified by the following examples: First, an alkyl alkoxy decane, a polyether, and a solution of an organic solvent, which is applied to a base film, and a part or all of the alkyl alkoxy decane is dehydrated and condensed to form a coating film; and then, the polyether self-coating film is coated with an organic solvent. And the dissolution is made porous and the final thickness is 0. A dehydration condensation film of a porous alkyl alkoxysilane of 3 to 3 // m. A catalyst for promoting the condensation reaction of the dehydration layer may be an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an aqueous solution of an organic acid such as acetic acid; or an organic solvent to be used, various alcohols, ketones and ethers capable of dissolving the polyether may be used. class. On the thus obtained porous alkyl alkoxydecane dehydration condensation film, • 25-(22) 1247639 forms the above-mentioned scratch-resistant hardening resin film and acrylic adhesive layer in sequence, even if the transfer film is transferred; The film layer (A) of the printed film is transferred onto the surface of the resin sheet, and a composite sheet having excellent surface reflection resistance with a surface reflectance of 3% or less can be obtained. The surface reflection resistance is a state in which the ratio of the light reflected on the surface is low, and the ratio of the light reflected on the surface is low, and the surface of the resin sheet used for the front panel or the frame panel of the image device can be reduced. Photograph of the external light. [Embodiment] [Examples] (Examples 1 to 1 and Comparative Examples 1 to 2) The present invention will be more specifically described by way of Examples and Comparative Examples; the present invention is not limited thereto; The evaluation and test methods of the respective examples and comparative examples are as described below. (1) Determination of the surface temperature of the sheet: The wire diameter is 〇. 2mm K-type thermocouple with a thickness of 0. A heat-resistant adhesive tape of 07mm polytheneimide is adhered to the surface of the extruded sheet of thermoplastic resin, and the surface temperature of the formed sheet is measured and recorded before passing through the heated pressure-sensitive roller (part a in Fig. 1). When the pressure-sensitive adhesive roller is heated (the bl portion and the b2 portion in Fig. 1), the surface temperature of the molded sheet is pushed out; when the pressure-sensitive adhesive roller is heated (b1, b2), the composite sheet (the transfer film is transferred and extruded) The surface temperature of the sheet and the surface temperature of the extruded sheet portion in the composite sheet (b1, b2) when heated by the pressure roller can be regarded as approximation. -26- 1247639 (23) (2) Judgment of appearance: The surface smoothness of the resin composite sheet, and other abnormalities that are non-destructive and appearance are judged visually; when it is good, it is awkward, slightly bad, but there is no problem. The abnormal situation in which the situation is △ and is unacceptable in a continuous manner is χ. (3) Judgment of adhesion: According to the standard of JIS-K5400's checkerboard adhesive tape test method; that is, 'on the film layer of the resin composite sheet, using a utility knife, the board is divided into 100 squares of 1 mm2 square. After the adhesive tape was adhered to the celluloid, the hand was pulled up vigorously to determine whether the film layer was peeled off; when 100 g was not peeled off at all, it was x, and when it was peeled off, it was X. (4) Total light transmittance: Measured in accordance with JIS-K7105. (5) Surface hardness: Measured according to the standard of JIS-K5400 handwriting method. (6) Surface resistance 値: Measured according to JIS-K691 1 standard. (7) Surface reflectance: The lowest reflectance recorded in the visible light wavelength region was measured using UV3 100 manufactured by Hitachi, Ltd. (8) Measurement of birefringence = = In the polarized light microscope (DMRP type 'with compensator), a sheet-like standard test for pre-measurement of optical phase difference is prepared. And the deviation measuring device (manufactured by Shinto Scientific Co., Ltd.) of the device -27-(24) 1247639, which is under the illumination, adjusts the angle of the polarizer of the single polarizing plate to the darkest angle Fixed, between the two polarizing plates, the flaky standard sample is fixed at the same level. The flaky standard sample is rotated horizontally and fixed at the brightest angle to the vertical upper brightness measuring device (manufactured by Minoruda Co., Ltd., measuring liquid crystal color distribution measuring device, CA-〗 〖000 ) Determine the twist. In addition, the measurement range of the sheet-like standard sample having a thickness of 1 mm in the plane direction was 40 mm x 50 mm, and the surface direction was divided into brightness data of 200 equal parts. The relationship between the brightness of these samples can be grasped by measuring the brightness of a plurality of flaky standard samples having different optical phase differences. The resin composite sheet sample to be measured (the measurement range of 40 mm x 50 mm in the surface direction of the thickness of 1 mm is the same as described above), and the brightness is measured by the same method, and converted into an optical phase difference, and then the thickness is determined by dividing the thickness. value. . (9) Environmental test: In a constant temperature and humidity chamber with a temperature of 60 °C and a relative humidity of 90%, a 1 mm thick, 50 mm x 70 mm tree-shaped composite sheet sample was allowed to stand for 24 hours, observed and recorded. State before and after the test. [Example 1] A Lagola a (Xu-28 (25) 1247639 Chemicals Chemicals Co., Ltd. extruded sheet formed by Chemicals Co., Ltd.) having a thickness of 1 mm, a width of 300 mm, and a long length of lm was prepared as an extruded sheet. On the other hand, on one side of a PET film having a thickness of 38/m, 10 parts by weight of diethylene glycol di(meth)acrylate, an amino group of an additional product of pentaerythritol triacrylate and hexamethylene diisocyanate 20 parts by weight of formate acrylate, 1 part by weight of benzoin isopropyl ether, 40 parts by weight of toluene, 20 parts by weight of methyl ethyl ketone (hereinafter referred to as MEK), and 1 part by weight of isopropyl alcohol, in the form of a reverse roll After coating and drying, the film is hardened by irradiation with a UV lamp to form a hardened resin film having a thickness of 5 // m. On the hardened resin film, 7 5 parts by weight of alicyclic epoxy compound Xerox is obtained, (manufactured by Reychelen Co., Ltd.), 1,4-cyclohexane dimethylol 2 3 parts by weight of a vinyl ether, 15 parts by weight of a phenolic epoxy resin (manufactured by Asahi Kasei Co., Ltd.), and 4 parts by weight of a photocationic polymerization initiator (manufactured by Unica Kabide Co., Ltd.) Coating, using a mercury lamp to harden, that is, forming a thickness 丨. An interlayer film of 5 #m; on the intermediate film, an acrylic coating (2 parts by weight of resin, 50 parts by weight of toluene, and 30,000 parts by weight of EK) was applied, and after drying, a thickness of l//m was formed. Adhesive layer, that is, transfer film. Further, the transfer film is a roll of a final width of 300 m and a length of 50 m by winding the base film from the processing portion of the coating portion, the drying portion, and the like, which is wound out of the drum, to the processing device of the winding drum. The state is prepared to adjust the driving speed of the film supply roller so that the moving speed of the extruded sheet at the time of transfer is 1 m/min, and the heating press roller is disposed; the adhesive -29 - (26) 1247639 layer alignment sheet On the surface side, the transfer film of the above-mentioned drum winding form is continuously supplied by the film supply roller and the heating and pressure-sensitive roller, and is transferred to both sides of the extruded molding sheet which is simultaneously supplied to the heating and pressure roller to form a composite sheet; Further, the surface temperature of the extruded sheet before the transfer (part a) was 2 3 C. Further, in order to remove dust, a static electricity supply air supply (SJ-R0 3 6 manufactured by Qiyuansi Co., Ltd.) may be provided before the pressure roller is heated. The heat-pressing roll is the same as the sand rubber with a corner hardness of Hs60. The surface of the metal drum is 3 mm thick. The supply of transfer film is based on 〇. The tensile stress (tension) of 〇3 kg/cm (equivalent to the unit length in the width direction of the film supply roller), the temperature of the heated pressure roller is 170 °C, and the pressure of the heated pressure roller is 6 kg/cm ( The line is pressed and pressurized at the same time as the unit length in the width direction of the pressure-sensitive adhesive roller. When the pressure-sensitive adhesive roller is heated (bl portion), the surface temperature of the composite sheet (the transfer film is transferred to the extruded molded sheet) is 1 3 (TC. The transferred composite sheet is cut into a length of 60 cm, and peeled off. The base resin film is obtained; the obtained resin composite sheet has a high total light transmittance, has no surface unevenness and the like, and has a good appearance, and has a good appearance similar to that of the acrylic resin sheet obtained by the usual method. Resin composite sheet which is improved greatly, has excellent scratch resistance and excellent surface protection before forming a composite sheet. [Examples 2 to 4] -30 - 1247639 (27) Example 2 using acrylic resin (Asahi Kasei Chemicals Co., Ltd.) Company-made, the product name is Drupet 7 Ο Η, transparent, T g 1 0 4 ° C) as a thermoplastic resin; Example 3 uses MS resin (Nippon Steel Chemical Co., Ltd., the product name is yeah Qilian MS600, transparent, Tg 100 ° C) as a thermoplastic resin; Example 4 using a rubber elastomer mixed with acrylic resin, impact-resistant acrylic resin (Asahi Kasei Chemicals Co., Ltd. Co., Ltd., the product name is Drupe SR8200, transparent, matrix Tg 1 1 (TC) as thermoplastic resin; using extruder (spiral diameter 5〇mm0, L/D = 32, single axis), sheet extrusion The apparatus for forming the mold and the polishing roller for cooling and polishing is formed by extruding the sheet by taking out the drum, and forming a stretched sheet having a width of 300 mm. Further, the above-mentioned resin is extruded. The resin temperature at the time was adjusted to an acrylic resin of 2 60 ° C, MS resin 2 3 (TC, impact resistant acrylic resin 25 ° C. Adjust the interval between the sheet extrusion die discharge port and the polishing roller, and polish The rotation speed of the drum and the take-out drum is such that the thickness of the extruded sheet is 1. 0 mm, the sheet extrusion speed is 3 m/min. The respective surface hardness of the extruded sheet was 1, 2 Å for acrylic resin, 1 Å for M S resin, 1 Η for impact resistant acrylic resin, and 表面 for surface resistance, and any one of them exceeded 1 〇 16 Ω. On the other hand, the same transfer film as in Example 1 was prepared. -31 - (28) 1247639 In the middle of the above-mentioned polishing roller and take-out roller, a static electricity supply air purifier for removing dust (SJR-R03 6 manufactured by Qiyuansi Co., Ltd.) is provided; the adhesive layer is aligned with the sheet. On the surface side, the transfer film of the above-described roll-wound form is continuously supplied with a film supply roll and a heated press-bonding roll interposed therebetween, that is, a composite sheet which is transferred onto one side of the extrusion molding. The heated pressure-sensitive roller was used to have a Shore hardness of Hs60 and a rubber thickness of 3 mm thick on the surface of the metal wave. The supply of transfer film is based on 0. Under the tensile stress (tension) of 0 3 kg / cm (corresponding to the unit length in the width direction of the film supply roller), the temperature of the heated pressure roller is 170 ° C, and the pressure of the heated pressure roller is 6 kg / cm ( The line is pressed and pressurized at the same time as the unit length in the width direction of the pressure-sensitive adhesive roller. The transferred composite sheet was cut into a length of 60 cm, and the base film was peeled off; the obtained resin composite sheet was characterized by high total light transmittance, practically no surface unevenness, and the like, and had acrylic acid obtained by the usual method. The resin, the MS resin, and the impact-resistant acrylic resin each have the same good appearance. Further, a resin composite sheet having a surface hardness on the transfer surface side which is greatly improved before the formation of the composite sheet, excellent scratch resistance, and excellent surface protection performance can be obtained. [Example 5] A PC resin (trade name: Parnite K-1 3 〇〇, transparent) was used as a thermoplastic resin, and the sheet was extruded into a -32- (29) 1247639 type. The resin was adjusted to a temperature of 290 ° C, and the other sheet obtained in the same manner as in Example 2 had a surface hardness of B and a surface resistance 値 of the above. On the other hand, on one side of the PET film having a thickness of 38/m, 20 parts by weight of the tin oxide fine powder was added to the 1 part by weight of the solution for forming a cured resin film used in Example 1. A transfer film was produced in the same manner as in Example 1 except that the ball mill was dispersed. In the middle of the polishing roller and the take-up roller, a far-infrared disk heater for heating the extruded sheet is provided to keep the surface of the extruded sheet at 110 ° C (part a) while transferring on both sides of the extruded sheet. A resin composite sheet was obtained in the same manner as in Example 2; the resin composite sheet thus obtained had a surface hardness of 3H and a surface resistance 値 of 109 Ω, and had a sufficient surface as compared with the PC film obtained by the usual method. Hardness and anti-chargeability. [Example 6] Dehydration condensation of a porous alkyl alkoxy decane having a thickness of //·8 // m was formed on one surface of an optical pet film having a surface smoothness of 50/m thick. film. Adding 200 parts by weight of a mixture of ethanol and butanol to a volume ratio of 1 to 2 in a monovalent portion of monomethyltriethoxydecane, and adding 60 parts by weight of water and phosphoric acid 3 to the solution. Mixing parts by weight; thereafter, adding 200 parts by weight of a mixture of ethanol to butanol in a ratio of 1 to 2, and 80 parts by weight of polyethylene glycol (made by Nippon Oil & Fat Co., Ltd., PEG #1540), and stirring uniformly. That is, it is prepared into a coating solution. -33- (30) 1247639 On the single side of the above-mentioned optical PET film, the coating solution was applied by a roll coating method, and after drying, it was immersed in ethanol to dissolve the polyethylene glycol from the coating film. Remove and then dry again. The solution for forming a cured resin film containing the tin oxide fine powder used in Example 5 was used to form a hardened layer of 1 // m; and a cured resin film of 5 // m was formed in the same manner as in Example 1, and then The adhesive layer is formed, that is, the transfer film is obtained. This transfer film was transferred to an extruded sheet of an acrylic resin in the same manner as in Example 2, and then the base film was peeled off to obtain a resin composite sheet. The resin composite sheet was practically free from surface unevenness and the like. It has the same good appearance as the acrylic resin sheet obtained by the usual method, and has a total light transmittance of 95%, a surface hardness of 4H, and a surface resistance 値 of 1010 Ω. The surface reflectance is 2%, which is high in transparency and difficult to be damaged. Dust and the like are hard to adhere to, and the external light is rarely reflected. It is very suitable for use in a resin composite sheet such as an image machine or a frame for painting. The birefringence enthalpy of the resin composite sheets of Examples 1 to 6 was 5 X or less on average, and the deviation of the average enthalpy was ± 50% or less, and there was no problem in the environmental test. [Example 7] 20 parts by weight of diethylene glycol di(meth)acrylate, 10 parts by weight of epoxy acrylate, benzoin isopropyl ether on one side of a PET film having a thickness of 38 // m 1 part by weight, 40 parts by weight of toluene, 20 parts by weight of methyl ethyl ketone (hereinafter referred to as Μ EK ), and 1 part by weight of isopropyl alcohol, -34- (31) 1247639, coated by reverse roll method, and dried Then, it is hardened by irradiation with a UV lamp, that is, a hardened resin film having a thickness of 3 · 5 // m is formed; and the acrylic film is coated and dried to form a transfer film of an adhesive layer having a thickness of 1 // m; In the downstream of a heated pressure-bonding roller having a Shore hardness of Hs60 and a rubber lining of 3 mm on the surface of the metal drum, a ceramic (containing 3 weight%/. of titanium oxide as a main component of the alumina composition) is flame sprayed on the metal. The surface of the drum is 0· 2 m ηι thick and the pressure-bonding roll is the same as the 'heating pressure-bonding roll. The set temperature of the rubber roller is 160 ° C, and the set temperature of the ceramic drum is 200 ° C. Other than that, the resin composite sheet was produced in the same manner as in Example 2. When the pressure-sensitive adhesive roller is heated, the surface temperature (b2 portion) of the composite sheet is 1 4 3 ° C; the obtained composite sheet has high total light transmittance, and practically has no surface unevenness and the like, and has the disadvantage of appearance. In addition, it was confirmed that the obtained acrylic resin sheet had a good appearance, and it was confirmed that the surface hardness was significantly higher than that before the formation of the composite sheet, and the resin composite sheet having excellent scratch resistance and surface protection was excellent. [Example 8] At both ends of the discharge port of the extrusion die, a flow path shielding plate was attached so that the width of the extruded molded sheet became 100 mm, by adjusting the discharge amount of the extruder, the exit of the sheet extrusion die, and the polishing roller. The interval is such that the thickness of the extruded sheet is adjusted to 3. 0 mm; a resin composite sheet obtained in the same manner as in Example 7 except that the set temperature of the ruthenium rubber roller was 16 (TC, the set temperature of the ceramic cylinder was 220 ° C.) -35 - 1247639 (32) Resin composite sheet obtained In addition, it has a good overall light transmittance, such as surface unevenness and the like, and has a good appearance similar to that of the conventional resin sheet. Moreover, it is confirmed that the surface hardness is higher than that of the composite sheet, and the scratch resistance is good, and the surface is good. Tree with superior protection (Example 9) The sheet was laminated in the same manner as in Example 7 except that the setting temperature of the rubber roller was 180 ° C and the pot temperature was 220 ° C. The composite was obtained by heating the pressure roller. The surface of the sheet was 1 63 ° C; the obtained composite sheet had any problems with slight bending and undulation; and it was confirmed that the total light transmittance was high, the plastic sheet was greatly improved before the composite sheet was formed, and the resin composite sheet excellent in scratch resistance was confirmed. [Example 1 0] Except that the same transfer film used in Example 7 was used, it was only a section of a ceramic flame sprayed drum, and the heating temperature was set to 16 (other than TC). Example 2 is the same as the composite sheet. The surface anger of the composite sheet when heating the pressure-sensitive roller is 133 ° C; the obtained composite sheet, although it is a part of the product supply, is not actually damaged, actually There is no large amount of acrylic composite sheet before the acrylic. The setting of the porcelain roller is made of resin. Degree (b2), but practically, the surface hardness is better than that of the surface, and the surface of the pressure-adhesive roller is pressed to form a resin. Degree (b2) The wrinkles of the tip have the disadvantage of appearance, -36- (33) 1247639 There is no practical problem; further, it is confirmed that the total light transmittance is high, the surface hardness is greatly improved before the composite sheet is formed, and the resistance is improved. A resin composite sheet with good scratch resistance and excellent surface protection. [Comparative Examples 1 and 2] By injection molding, a thickness of 1 mm, 50 mm x 70 mm was produced, and the bending radius R of each corner was 2. 5mm molded product. An acrylic transparent resin (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Ruppet 60 N, transparent) was used, and injection molding conditions were obtained: the resin temperature of Comparative Example 1 was 2 10 ° C, and the resin temperature of Comparative Example 2 was used. For 240 °C, the other common conditions are: metal mold temperature 60 °C, resin pressure 80 MPa; also, the above resin temperature, from the viewpoint of resin fluidity, is above the standard temperature field. . The surface hardness of the molded article thus obtained was 1 Η. Further, the adhesive layer of the transfer film used in Example 1 was attached to a mold as a molded article, and injection molding was carried out by a usual method under the same conditions, and the film layer was transferred to an injection molded article. After the surface, the base film is peeled off. The surface hardness of these molded products is as high as 5 Η; however, the complex refraction enthalpy near the gate is much higher than the average enthalpy, indicating the presence of internal strain; and, after the environmental test, 'the deformation is observed, Comparative Example 1 Further, it was found that the cured resin film was poor in adhesion. -37- 1247639 £ Example UI UI c:!60 1 mm △ Film wrinkles 〇 (N Ο X Not determined 1 Not determined I Not determined Not determined Not determined 1 Not determined | ON One S+C s: 180 c: 220 ο m \〇△surface ripple〇(N 〇Not determined i Not determined not determined | Not determined Not determined Not determined 〇〇m S+C s:160 c:220 g (N VO 〇〇(N 〇1 not determined 1 1 Not measured Not measured Not measured Not measured Not measured Bu S+C s: !60 c:200 〇〇〇〇(N 〇1 Not measured I Not measured Not measured Not determined Fine not determined v〇-tn s :170 1 g 2 1 〇〇〇s X 〇*〇Λ (Ν — + 〇1 No change one s: 170 1 o (N VO 1 〇〇ON 00 >109 not measured +35 〇 (N no change - C/5 s:!70 « s (N 1 〇〇5; 3: rr >10,6 1 not determined 1 (N +20 1 no change m one in is:170 1 g 1 〇〇g X TT * 〇7\ 1 not measured 1 +25 〇 (N no change 1 (N — in s:170 1 g tn (N 1 〇〇CN ON Ό Λ not measured one + 16 〇1 no change one one C/D s :170 1 1 〇〇(N 〇\ X 〇Λ 1 not measured 1 + 10 〇1 No change Sheet thickness (mm) Heated pressure roller cn o §n cd b 丨 part b2 part appearance adhesion total light transmittance (%) Surface hardness surface resistance 値 (Ω) Surface reflectance (%) Average 値 (X 10- 5) The maximum 値 (%) of the deviation of the average 値 The minimum 値 (%) of the deviation of the average 环境 The environmental test roller set temperature / ^ S pu P sheet surface temperature / ^ N fN s P complex refracting 値 - IK1 ^ l^iilsmi0+--1^^ ^ I- C* -38- 1247639
S 比較例 (N ， 1叫 1 1 1 1 1 1 〇 〇 >1016 未測定 1—^ +100 〇 發生變形 1 雪 意 1 喔 1 〇 〇 Η ON X >10 丨6 i 未測定 ▼—Η +230 發生變形 密著性z X 薄片厚度（mm) 加熱加壓滾筒 C/3 〇 hCL •m cd bl部 : b2部 外觀 密著性 全光線透射率（％) 表面硬度 表面電阻値 （Ω) 表面反射率 （％) 平均値 (X 10-5) 對該平均値之偏差的最大値 (%) 對該平均値之偏差的最小値 (%) 環境試驗*3) . 滾筒設定溫度 ▼— * P 薄片表面溫度 /^s (N * /^N P 複折射値 #0M僻2Π1蔬异围賴霞爺2 ,lq，猛^诞链？1癒运©賴職插0(^ sgil ^ ot- I^ ^ —1 - - Γ -39- 1247639 (36) 〔產業上利用性〕 本發明之表面改質樹脂複合薄片的製造方法，適合使 用於要求樹脂薄片之表面改質的全部用途領域。 即，適合使用於電機·電子製品、車輛內外裝用構件 、顯示器等之領域；此等領域之要求爲，能在不損及外觀 及設計性下、連續且安定的生產樹脂複合薄片時，賦予耐 擦傷性、耐污染性、耐溶劑性等之表面保護性能；尤其是 ’能適合使用於以影像機器之正面板、鏡框面板、分隔板 爲代表的透明樹脂之使用領域，此等領域中強力要求，能 賦予防帶電性能、防表面反射性能；進而，依本發明，可 提供透明、具有良好的光學特性，很難由於使用環境等之 影響發生翹曲及變形，耐擦傷性優異之透明熱塑性樹脂複 合薄片·，依本發明，可安定的連續生產樹脂複合薄片之故 ’尤其是能適合使用於液晶方式之電視、個人電腦監控器 、行動電話顯示窗之保護蓋、及車輛用計測器蓋、電照明 附帶招牌、鏡框、店面之商品櫥櫃等使用透明樹脂之領域 【圖式簡單說明】 圖1爲’本發明實施之一例的押出薄片製造機之槪念 圖。 主要元件對照表 1 :薄片擠壓模 -40- 1247639 (37) 2 :磨光滾筒 3 :熱塑性樹脂薄片 4 :轉印薄膜 5 :加熱壓黏滾筒 6 :加熱壓黏滾筒 7 :取出滾筒 8 :樹脂複合薄片S Comparative example (N, 1 is called 1 1 1 1 1 1 〇〇 > 1016 Not determined 1 - ^ +100 〇 Deformation 1 Snow 1 喔 1 〇〇Η ON X > 10 丨 6 i Not determined ▼ — Η +230 Deformation tightness z X Sheet thickness (mm) Heated pressure roller C/3 〇hCL •m cd bl part: b2 appearance Adhesive total light transmittance (%) Surface hardness surface resistance 値 (Ω Surface reflectance (%) Average 値(X 10-5) The maximum 値(%) of the deviation from the mean The minimum 値(%) of the deviation from the mean 环境(%) Environmental test*3) . Roller set temperature ▼— * P sheet surface temperature / ^ s (N * / ^ NP complex refraction 値 # 0M secluded 2 Π 1 vegetable different Wai Lai Xia 2, lq, fierce ^ birthday chain? 1 more transport © Laijia plug 0 (^ sgil ^ ot- I^^^1 - - Γ -39- 1247639 (36) [Industrial Applicability] The method for producing a surface-modified resin composite sheet of the present invention is suitably used in all fields of application where surface modification of a resin sheet is required. It is suitable for use in the fields of motors, electronic products, components for vehicles inside and outside, displays, etc.; the requirements in these fields are that they can not damage the appearance and design. When the resin composite sheet is produced under the condition of continuous, stable and stable, it provides surface protection properties such as scratch resistance, stain resistance, solvent resistance, etc.; in particular, it can be suitably used for the front panel, the frame panel, and the image machine. The field of use of the transparent resin represented by the separator is strong in these fields, and can impart anti-charge performance and surface reflection resistance. Further, according to the present invention, it can provide transparency, has good optical characteristics, and is difficult to use due to the use environment. A transparent thermoplastic resin composite sheet excellent in scratch resistance and deformation and excellent in scratch resistance. According to the present invention, it is possible to stably produce a resin composite sheet continuously, which is particularly suitable for use in a liquid crystal television or personal computer monitor. The protective cover of the mobile phone display window, the measuring device cover for the vehicle, the electric lighting with the signboard, the frame, the product cabinet of the storefront, and the like, the field of using the transparent resin [Simplified illustration of the drawings] FIG. 1 is an example of the embodiment of the present invention. Execution of the sheet making machine. Main components comparison table 1: sheet extrusion die -40 - 1247639 (37) 2 : polishing Roller 3: Thermoplastic resin sheet 4: Transfer film 5: Heated pressure roller 6: Heated pressure roller 7: Takeout roller 8: Resin composite sheet
9 :滾筒動力源 1 〇 :薄膜供給滾筒 a部：通過加熱壓黏滾筒之前 bl部：通過加熱壓黏滾筒時 b2部：通過加熱壓黏滾筒時9: drum power source 1 〇 : film supply roller a: before heating the pressure roller bl: when heating the pressure roller b2: when heating the pressure roller
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