200403288 ⑴ 玖、發明說明 【發明所屬之技術領域】 本發明爲關於經由應用於工廠、住宅等建築物之屋頂 和外壁、容器、冷凍車等搬運車輛之蓋頂和外板、船舶、 車庫、倉庫、畜舍等屋頂和外壁等，則可抑制起因於太陽 光之內部溫度上升的隔熱性薄片。 【先前技術】 以往，容器、冷凍車等搬運車輛爲了抑制起因於太陽 光之內部溫度上升，乃於屋頂和外板貼附隔熱性薄片。此 類隔熱性薄片以往爲使用熱塑性樹脂中混練入隔熱性顏料 的隔熱性薄片。例如於專利文獻1及專利文獻2中，已提案 將氯乙烯樹脂、聚乙烯系樹脂、聚酯系樹脂、（甲基）丙 烯酸系樹脂等之熱塑性樹脂中，含有特定之隔熱性顏料之 組成物成形爲薄片狀者。又，最近，提案於塑膠等基材上 塗佈隔熱性塗料的隔熱性薄片。例如於專利文獻3、專利 文獻4、專利文獻5中，提案於氯乙烯、聚烯烴、聚碳酸酯 ' (甲基）丙烯酸系樹脂等之薄片和薄膜上形成由隔熱性 顏料和黏合劑所構成的隔熱層。此些隔熱性薄片爲透過接 黏層或黏著層，貼附至欲阻斷來自外部熱之對象（被黏體 )上供使用。 專利文獻1特開平8- 8 1 5 67號公報 專利文獻2特開平2002_ 1 2679號公報 專利文獻3特開平1 0 - 2 5 0 0 0 2號公報 (2) (2)200403288 專利文獻4特開2 0 0 2 - 1 2 6 8 3號公報 專利文獻5特開200 1 -27002 1號公報 此類隔熱性薄片爲具有充分的隔熱性，並且要求追隨 被黏體之形狀，即具有可撓性。特別於被黏體爲彎曲面之 情況，期望具有高的延伸率。但是，爲了取得充分的遮熱 性，而於隔熱性薄片或隔熱層中大量含有隔熱性顏料時， 損害柔軟性且難以貼附，具有易發生斷裂等之問題。因此 ，先前的隔熱性薄片一般爲使用可撓性高的氯乙烯系樹脂 做爲基材。但是，使用氯乙烯系樹脂的隔熱性薄片具有下 列問題。 首先’氯乙儲系樹脂於焚燒處理時具有發生有毒氣體 之問題’於塑膠材料之領域中已發展出脫氯乙烯化。又， 於被黏體爲具有彎曲面等之要求高可撓性之用途中，必須 於氯乙嫌樹脂中添加大量的可塑劑，但此類氯乙燃系樹脂 之薄片若長期使用，則於表面析出可塑劑，伴隨著亦發生 隔熱層龜裂的問題。 於是’本發明爲以提供不使用氯乙烯系樹脂，於被黏 體爲彎曲面等之情況亦可良好貼附之隔熱性薄片爲其目的 〇 【發明內容】 解決:上述目的之本發明的隔熱性薄片爲將含有胺基甲 酸乙_系樹脂及隔熱性顏料的隔熱層，與胺基甲酸乙酯系 -5- (3) (3)200403288 樹脂所形成之樹脂層予以層合爲其特徵。 由胺基甲酸乙酯系樹脂所構成的樹脂層爲具備接近氯 乙烯系樹脂薄片的可撓性，且經由與隔熱層疊層作成多層 構造，則可更加提高可撓性，特別可減少開始延伸所需要 之力量（拉伸屈服強度）。藉此，可一邊配合被黏體形狀 而延伸，且一邊於貼附時可以良好作業性貼附，且亦不會 發生斷裂。又，即使隔熱層本身之柔軟性低，亦可追隨被 黏體之形狀而貼附。更且，因爲未使用氯乙烯系樹脂，故 不會發生可塑劑析出造成的隔熱層惡化和龜裂，且亦無廢 棄時之環境污染問題。 又，令隔熱層中含有與構成樹脂層之胺基甲酸乙酯系 樹脂同樣之樹脂，則可使得樹脂層與隔熱層之接黏性良好 ，並且令可撓性良好，且於貼附時即使延伸亦可抑制龜裂 的發生。 又，本發明之隔熱性薄片較佳爲拉伸屈服強度 ΙΟΝ/mm2以下，較佳爲5 N/mm2以下，更佳爲3.5 N/mm2以 下。經由令拉伸屈服強度爲上述範圍，則可在貼附被黏體 時配合其形狀而輕易地延伸貼附。 還有’所謂「拉伸屈服強度」爲指根據Π S K 7 1 1 3 -1 98 1 (塑膠之拉伸試驗方法）所計測之値，定義爲負重-延拉曲線上，於負重增加且察見延伸增加之最初點的拉伸 應力。又，「拉伸破壞強度」爲指破壞試驗片之瞬間的拉 伸應力。 更且，本發明之隔熱性薄片爲於上述構成中，於具有 -6 - K fe： (4) (4)200403288 樹脂層之隔熱層之面的反側面，具有黏著層。 又，本發明之隔熱性薄片較佳於遮熱層與樹脂層之間 具有防止溶劑滲透層。由胺基甲酸乙酯系樹脂所構成的樹 脂層爲溶劑之滲透性高，經由設置此類防止溶劑滲透層， 則可防止塗佈形成隔熱層時之隔熱層塗佈液中所含的溶劑 ，和隔熱層形成後之隔熱層中所含的殘留溶劑爲通過樹脂 層到達黏著層，並且令黏著性降低。 又，本發明之隔熱性薄片爲具有黏著層時，較佳爲以 其他基材形成黏著層後，對樹脂層進行層合所形成。黏著 層並非直接塗佈至樹脂層而形成，爲將預先形成的黏著層 對樹脂層進行層合，則可減少對樹脂層和隔熱層加熱之次 數，並且可減輕樹脂層及隔熱層之熱所造成的收縮。又， 不管胺基甲酸乙酯系樹脂所構成之樹脂層之硬化如何完成 ，亦可形成黏著層，使得製造容易。更且，因爲可防止黏 著層塗佈液之溶劑滲透至樹脂層，故難引起樹脂層浸透溶 劑所造成的經時性黏著力的降低。 【實施方式】 〔用以實施發明之最佳形態〕 以下，詳述本發明之隔熱性薄片的實施形態。 圖1 ( a )〜（c )爲示出本發明之隔熱性薄片的實施形 態圖。本發明之隔熱性薄片爲如圖1 ( a )所示般’具備隔 熱層1 1和胺基甲酸乙酯系樹脂所構成的樹脂層1 2做爲基本 構成，一個實施形態爲如圖1 ( b )所示般，於樹脂層1 2之 (5) (5)200403288 形成隔熱層1 1之面的反側面具有黏著層1 3。又，其他實施 形態爲如圖1 ( c )所示般，於樹脂層1 2與隔熱層1 1之間， 具備防止溶劑滲透之層（防止溶劑滲透層）1 4。又，於黏 著層1 3設置可剝離的間隔件1 5。 本發明之隔熱性薄片爲作成將隔熱層1 1與胺基甲酸乙 酯系樹脂所形成之樹脂層予以層合之層合構造爲其特徵， 經由作成此類層構造，則即使被黏體爲彎曲面等之情況亦 可良好貼附。 以下，說明混練隔熱性顏料之薄片（以下，稱爲混練 薄片），與隔熱層和樹脂層所層合之本發明之隔熱性薄片 (多層薄片）之性能的差異。 一般薄片狀物爲經由含有隔熱性顏料，令延伸率降低 。因此，於加以令隔熱性薄片破壞爲止之力量予以延伸之 情形中，以薄片全體均勻含有隔熱性顏料之混練薄片，比 隔熱性薄片表面含有高密度隔熱性顏料之多層薄片延伸更 長。即，拉伸破壞延伸度爲呈較大値。另一方面，開始延 伸所需的力量（即，拉伸屈服強度）以隔熱層全體含有隔 熱性顏料之混練薄片比多層薄片需要更大之力量。其係因 多層薄片爲不含有阻礙樹脂層延伸之隔熱性顏料等’故以 較弱的力量即可開始延伸。此時’含有高密度隔熱性顏料 之隔熱層爲被層合於樹脂層’故追隨樹脂層的延伸且以較 弱的力量延伸。 將隔熱性薄片貼附至被黏體時’特別於追隨彎曲面貼 附時，上述特性中以拉伸屈服強度爲重要的。即’拉伸屈 -8- (6) (6)200403288 服強度小的多層薄片即使以較弱的力量拉伸亦可令樹脂層 追隨_曲面延伸，故可輕易貼附至被黏體。並且，隨著樹 脂層之延伸於隔熱層亦不會發生延伸龜裂。 若根據本發明者的詳細檢討，則得知拉伸屈服強度爲 ΙΟΝ/mm2以下，較佳爲5 N/mm2以下，更佳爲3.5 N/mm2以 下之情況，可以良好作業性貼附至被黏體，且亦不會發生 貼附後之薄片倒退。具有此類特性之隔熱性薄片爲使用胺 基甲酸乙酯系樹脂做爲非氯乙烯系的樹脂並且予以多層化 則可構成。 其次，說明關於構成本發明之隔熱性薄片的各層。 構成樹脂層之胺基甲酸乙酯系樹脂爲經由令胺基甲酸 乙酯系樹脂主劑與聚異氰酸酯等之硬化劑予以交聯則可取 得’其構造上，彈力充裕，具有自我治癒性，且強韌並且 耐磨損性優良。此類樹脂層之特性可根據胺基甲酸乙酯系 主劑之酸値、羥基値和分子量、聚異氰酸酯之分子構造和 異氰酸酯基含量及其聚合度予以適當調整。 樹脂層若在不損害本發明機能之範圍，則可含有其他 樹脂、和顏料、滑劑、著色劑、防靜電劑、難燃劑、抗菌 劑、防黴劑、紫外線吸收劑、光安定劑、抗氧化劑、勻塗 劑、流動調整劑、消泡劑等各種添加劑。 樹脂層爲將胺基甲酸乙酯系樹脂，視需要加上其他成 分及稀釋溶劑混合作成塗佈液，並將此塗佈液以公知的塗 佈方法於指定之基材（亦有隔熱層之情況）上塗佈，且經 由加熱令其乾燥、硬化則可形成。一般所使用之胺基甲酸 -9- (7) (7)200403288 乙酯薄片亦可使用做爲樹脂層。 樹脂層厚度之下限較佳爲20 μιη以上，更佳爲50 μηι 以上。又，上限較佳爲3 00 μιη以下，更佳爲1〇〇 μιη以下 。樹脂層厚度爲2 0 μηι以上，則在將隔熱性薄片貼至被黏 體而予以延伸時，可防止隔熱層發生龜裂等。又，經由令 樹脂層之厚度爲3 00 μιη以下，則可以較弱之力量將隔熱性 薄片貼附至被黏體。 於考慮上述材料及厚度等上，使用樹脂層本身之拉伸 屈服強度爲1〜7N/mm2之樹脂層爲佳。 隔熱層爲含有隔熱性顏料之層，例如由含有胺基甲酸 乙酯系樹脂之黏合劑和隔熱性顏料所構成。所謂隔熱性顏 料爲指具有難以傳遞來自太陽光之熱能的隔熱性，和不會 吸收來自太陽光之熱能並且令其反射之熱反射性，將吸收 之熱能以紅外線型式再放射至外部之長波放射性等性能之 無機、有機顏料，且可使用公知之材料。具體而言，可列 舉陶瓷、氧化鐵、氧化鉛、氧化鈦、滑石、硫酸鋇等之無 機顏料、和酞菁藍、Syncacia Red等之有機顏料，其可使 用一種或適當組合二種以上。其中以隔熱性、熱反射性、 長波放射性優良之陶瓷微粒子，特別以透明中空陶瓷微粒 子、熱反射性優良且具有自我洗淨性之氧化鈦等爲較佳使 用。 用以黏著隔熱性顏料的黏合劑可使用至少含有胺基甲 酸乙酯系樹脂的物質。胺基甲酸乙酯系樹脂可使用與樹脂 層所用之胺基甲酸乙酯系樹脂相同之物質，經由令隔熱層 -10- (8) (8)200403288 中含有，則可取得延伸良好且難損傷的隔熱層。又，與胺 基甲酸乙酯系樹脂所構成之樹脂層的接黏性優良，且無層 間剝離。 隔熱層在不阻礙上述胺基甲酸乙酯系樹脂效果之範圍 下，亦可摻混其他樹脂做爲黏合劑。其他樹脂可使用例如 聚乙烯、聚丙烯、乙烯系共聚物、丙烯系共聚物等之烯烴 系樹脂、（甲基）丙烯酸酯共聚物等之丙烯酸系樹脂、聚 酯系樹脂等之公知樹脂。隔熱層之黏合成分中之胺基甲酸 乙酯系樹脂含量雖無特別限定，但較佳爲2 0重量％以上 ，更佳爲50重量％以上，再佳爲90重量％以上。經由令 隔熱層之黏合成分中之胺基甲酸乙酯系樹脂含量爲20重 量％以上，則即使於作成隔熱性薄片時之被黏體形狀爲彎 曲面之情形中，亦可追隨後述樹脂層的延伸，故於隔熱層 不會發生龜裂。 隔熱層中之隔熱性顏料的含量爲根據隔熱層之厚度， 目的隔熱性之效果等而異，並無法一槪而論，但下限較佳 以10重量％以上，更佳爲20重量％以上。又，因爲隔熱 性薄片貼至被黏體上，故於延伸時可防止於隔熱層發生龜 裂等，其上限爲60重量％以下，較佳爲40重量％以下左 右爲佳。 又，隔熱層除了黏合劑及隔熱性顏料以外，若在不損 害本發明機能之範圍，則亦可含有與上述樹脂層相同之其 他成分。 此類隔熱層爲將黏合劑，隔熱性顏料及視需要加上其 -11 - (9) (9)200403288 他成分和稀釋成分混合調製，作成隔熱層塗佈液，並將此 隔熱層塗佈液以先前公知的塗敷方法，例如，以棒塗器、 型板塗層器、刮刀塗層器、旋塗器、輥塗器、照相凹版塗 層器' 流塗器、噴霧器、網版印刷等塗佈至指定基材（亦 有樹脂層之情況），並經由加熱令其乾燥、硬化則可形成 隔熱層。又，隔熱層可使用對至少含有胺基甲酸乙酯系樹 脂之黏合成分混練隔熱性顏料，並且形成爲薄片狀之物質 〇 隔熱層之厚度爲根據隔熱性顏料之添加量，目的之隔 熱性效果等而異，無法一槪論之，但以塗層法予以設置時 ’以50 μηι〜700 μηι，較佳爲1〇〇 μιη〜500 μηι左右。隔熱層 之厚度未滿5 0 μπι，則爲了取得充分的隔熱性乃令隔熱性 顏料之含量變高，於延伸時易造成龜裂。樹脂層之厚度和 隔熱層之厚度比例亦根據薄片全體之厚度及目的之隔熱特 性而異’但於全體厚度爲200 μπι〜400 μιη左右時，樹脂層： 隔熱層爲40:60〜10:90左右。 黏著層爲令本發明之隔熱性薄片貼附至被黏體之層， 於樹脂層之形成隔熱層面之反側面上形成。構成黏著層之 黏著劑可使用一般所用的丙烯酸系黏著劑、聚矽氧系黏著 劑、胺基甲酸乙酯系黏著劑、橡膠系黏著劑等。又，亦可 使用具有抗靜電等性能之黏著劑。 黏著層一般爲將上述黏著劑視需要於稀釋溶劑中溶解 或分散作成塗佈液，並將此塗佈液以先前公知之塗佈方法 予以塗佈、乾燥則可形成。黏著層之厚度爲根據被黏體而 -12- (10) (10)200403288 異，無法一槪而論，但若考慮貼附性等，則下限爲20 μπι 以上，較佳爲30 μηι以上，上限爲200 μιη以下，較佳爲 1 00 μηι以下左右。 防止溶劑滲透層爲用以防止形成隔熱層時之隔熱層塗 佈液所含的溶劑及隔熱層中殘留的溶劑成分滲透樹脂層， 並且到達黏著層令黏著性降低之層，被設置於隔熱層與樹 脂層之間。 構成防止溶劑滲透層之材料可使用柔軟性良好且耐溶 劑性高的樹脂。此類樹脂具體而言以聚醯胺系樹脂、胺基 甲酸乙酯丙烯酸系樹脂、改質聚酯等爲適當，特別以聚醯 胺系樹脂爲適當。防止溶劑滲透層爲了提高與隔熱層及樹 脂層之接黏性，以含有少量的胺基甲酸乙酯系樹脂爲佳。 提高接黏性之胺基甲酸乙酯系樹脂以水系胺基甲酸乙酯丙 烯酸樹脂爲適當。爲了取得更高的防止溶劑滲透效果，較 佳令胺基甲酸乙酯系樹脂之添加量相對於聚醯胺系樹脂 100重量份爲不超過50重量份。 防止溶劑滲透層可經由將水系塗佈液塗佈至樹脂層而 形成。其厚度雖亦關連於隔熱性薄片之各要素的厚度，但 爲了取得上述效果乃以1 μηι〜20 μηι左右爲適當，更佳爲1 μηι〜10 μιη左右，再佳爲1 μιη〜5 μιη左右。 其次，說明上述構成之本發明之隔熱性薄片的製造方 法。 本發明之隔熱性薄片之基本性構成的隔熱層/樹脂層 (隔熱層/防止溶劑滲透層/樹脂層）爲經由共同擠壓、乾 -13- (11) (11)200403288 式層合、或塗佈形成。於塗佈之情形中，將隔熱層或樹脂 層任一者形成薄片狀者，或於間隔件等之上以塗佈層型式 設置者做爲基材，並於此基材上塗佈另一者即可形成。黏 著層可於樹脂層與隔熱層層合前形成，且亦可於層合後形 成。特別，將黏著層於間隔件等之基材上塗佈形成者，貼 附至樹脂層爲佳。此時，可減少塗佈及乾燥步驟之重覆次 數’並且可減輕樹脂層和隔熱層因熱所造成的收縮。又， 不管胺基甲酸乙酯系樹脂所構成之樹脂層的硬化如何完成 ，亦可形成黏著層，令製造容易。 若列舉製造方法之一例，則爲將黏合劑、隔熱性顏料 及視需要加入之其他成分和稀釋溶劑混合調製的隔熱層塗 佈液’於間隔件上以先前公知的塗層方法予塗佈，並經由 加熱令其乾燥、硬化形成隔熱層。其次於此隔熱層上，將 胺基甲酸乙酯系樹脂，視需要加入其他成分、及稀釋溶劑 混合作成塗佈液並且於該隔熱層上，同上述以先前公知之 塗層方法予以塗佈，並經由加熱令其乾燥、硬化則可形成 樹脂層。於設置防止溶劑滲透層之情形中，於形成隔熱層 後，將構成防止溶劑滲透層之樹脂的水系塗佈液以公知的 塗層法予以塗佈、乾燥，於其上同上述形成樹脂層。 更且，於此樹脂層之上，將黏著層溶解於稀釋溶劑之 塗佈液同上述以先前公知的塗佈方法予以塗佈，令其乾燥 形成黏著層，並且取得本發明之隔熱性薄片。 其他例爲以一般市售的胺基甲酸乙酯薄片做爲樹脂層 ，並於此胺基甲酸乙酯薄片之一面形成隔熱層，且於另一 -14- (12) (12)200403288 面形成黏著層進行製作亦可。 還有，以上說明之製造方法單爲例示，本發明之隔熱 性薄片之製造方法並非被限定於此些製造方法。例如，於 隔熱層之上，不將樹脂層、黏著層依序層合，而爲令隔熱 層、樹脂層、黏著層以何種順序形成均可。 如此所製造之本發明之隔熱性薄片可透過黏著層而貼 附至所欲的被黏體。此時，即使被黏體爲彎曲面等之情況 亦可以良好之作業性貼附。又，因爲未使用添加可塑劑的 氯乙烯系樹脂，故於焚燒時不會發生有毒氣體，又，即使 長期使用亦不會於隔熱層發生龜裂等。 實施例 以下，根據實施例更加詳細說明本發明。還有，本實 施例中之「份」，「％」只要無特別指示則爲重量基準。 [實施例1] 對厚度100 μΐΏ之紙間隔件（Binasheet 70S-218T:藤 森工業公司）塗佈下述配方的隔熱層塗佈液，且於90 °C ，乾燥1 0分鐘形成2 0 0 κ m的隔熱層。其次，於此隔熱層 上塗佈下述配方的樹脂層塗佈液，並於1 00 °C ，乾燥6 分鐘形成厚度8〇 μηι的樹脂層，取得隔熱性薄片。 其次，對上述同樣之間隔件塗佈下述配方的黏著層塗 佈液，且於1〇〇 °C，乾燥5分鐘形成厚度6〇 黏著層 ，取得黏著薄片。將此黏著薄片之黏著層與上述隔熱性薄 -15- (13) 200403288 片之樹脂層予以層合，且於60 °c之環境下放置7 熟化，製作實施例1的隔熱性薄片。 <實施例1之隔熱層塗佈液用隔熱性顏料分散液> 將隔熱性顏料（τ i t a n C R 9 7 :石原T i t a η工業公 份、甲基乙基酮29份、分散劑（Disperbyk ι61 Chem Japan公司）3份以分散機（Dinomill KDL型： B a c 〇 f e η公司）分散成粒度5 μ m以下，取得隔熱性 6 8 %分散液（隔熱性顏料分散液（a ))。 <實施例1之隔熱層塗佈液> •隔熱性顏料分散液（a ) •丙烯酸系胺基甲酸乙酯樹脂主劑（固形成分3 5 % ) (Neopaint #8500 Clear:亞細亞工業公司 •聚異氰酸酯（固形成分5 3 % ) (Neopaint #8 5 00用硬化劑：亞細亞工業公司） <實施例1之樹脂層塗佈液〉 •丙烯酸系胺基甲酸乙酯樹脂主劑（固形成分3 5 %) (Neopaint #8500 Clear:亞細亞工業公司） •聚異氰酸酯（固形成分5 3 % ) (Neopaint #8 5 00用硬化劑：亞細亞工業公司） <實施例1之黏著層塗佈液> 日予以 司）68 :B YK Willey 顏料的 28份 73份 9 0份 3 0份 -16- (14) (14)200403288 •丙烯酸系黏著劑（固形成分4 0 % ) 6 2份 (NisetsuKP-2074:日本 Cabide 工業公司） •聚異氰酸酯 1份 (Nisetsu CK-117:日本 Cabide 工業公司） •醋酸乙酯 37份 [實施例2] 將厚度80 μιη之胺基甲酸乙酯薄片（Silchron MT93: 大倉工業公司）所構成之樹脂層，與同實施例1製作之黏 著薄片的黏著層予以層合。其次，對前述胺基甲酸乙酯薄 片之黏著層未層合之面，塗佈於含有隔熱性顏料40%之市 售隔熱性塗料中添加做爲黏合成分之胺基甲酸乙酯系樹脂 的隔熱層塗佈液（下述所示之配方），且於90 °C、乾燥 1〇分鐘形成200 μπι的隔熱層，並60 t之環境放置7曰予 以熟化，製作實施例2的隔熱性薄片。 <實施例2之隔熱層塗佈液> •市售之隔熱性塗料主劑（固形成分65%) 56份 (MiraculeS5007F:長島特殊塗料公司） •上述隔熱性塗料用硬化劑（固形成分60% ) 1 9份 (Miracule S5 007F用硬化劑：長島特殊塗料公司） •丙烯酸系胺基甲酸乙酯樹脂主劑（固形成分35%) 18份 (Neopaint #8500 Clear:亞細亞工業公司） •聚異氰酸酯（固形成分53%) 6份 -17- (15) (15)200403288 (Neopaint #8 5 00用硬化劑：亞細亞工業公司） [實施例3] 將實施例2相同之胺基甲酸乙酯薄片所構成的樹脂層 ，與同實施例1製作之黏著薄片的黏著層予以層合。其次 ，對前述胺基甲酸乙酯薄片之黏著層未層合之面，塗佈下 述配方之防止溶劑滲透層塗佈液，且於1 1 0 °C、乾燥3 分鐘，形成厚度3 μιη的防止溶劑滲透層。於此防止溶劑滲 透層上，同實施例2處理形成隔熱層，並於6 0 °C之環境 放置7日予以熟化，製作實施例3之隔熱性薄片。 <實施例3之防止溶劑滲透層塗佈液> •水系胺基甲酸乙酯丙烯酸樹脂 8份 (固形成分37%) ( NeoRez R-9676:亞細亞公司） •聚醯胺6/6、6/6、13共聚物 12份 (固形成分100% ) (Ultramid IC: BASF 日本公司） •甲基改質乙醇 5 6份 •自來水 2 4份 [比較例1] 對實施例1之紙間隔件塗佈下述配方的隔熱層塗佈液 ，且於9 0 °C、乾燥1 0分鐘形成厚度2 8 0 Mm的隔熱層。 其次將此隔熱層與實施例1之黏著薄片的黏著層層合’並 -18- (16) (16)200403288 於60 t之環境放置7日予以熟化，製作比較例1的隔熱性 薄片。 <比較例1之隔熱層塗佈液> •市售之隔熱性塗料主劑（固形成分65%) 33份 (Miracule S5007F:長島特殊塗料公司） •上述隔熱性塗料用硬化劑（固形成分60% ) 1 1份 (Miracule S 5 007F用硬化劑：長島特殊塗料公司） •丙烯酸系胺基甲酸乙酯樹脂主劑（固形成分35%) 42份 (Neopaint # 8 5 00 Clear:亞細亞工業公司） •聚異氰酸酯（固形成分5 3 % ) (Neopaint #8 5 00用硬化劑：亞細亞工業公司） [比較例2] 將氯乙烯系樹脂、隔熱性顏料所構成之隔熱層（厚度 22 0 μιη )，及黏著層（厚度1 10 μηι )所構成之隔熱性薄 片（ATTSU-9: Likentenos公司）視爲比較例2的隔熱性薄 片。 [比較例3 ] 對實施例1之紙間隔件塗佈下述配方的隔熱層塗佈液 ，且於90 °C、乾燥1〇分鐘形成厚度200 μιη的隔熱層。 其次於上述隔熱層上塗佈下述配方的樹脂層塗佈液，且於 10 0 °C、乾燥6分鐘形成厚度8 0 μ m的樹脂層，取得隔熱 •19- (17)200403288 性薄片。其次將此隔熱性薄片之樹脂層與實施例1 薄片的黏著層層合，且於60 °c之環境放置7曰予 ，製作比較例3之隔熱性薄片。 <比較例3之隔熱層塗佈液> •實施例1之隔熱性顏料分散液（a ) •丙烯酸系樹脂主劑（固形成分5 0 %) (Acridic A801-P:大日本油墨化學工業公司） •聚異氰酸酯（固形成分7 5 % ) (Banoc DN-950:大曰本油墨化學工業公司） <比較例3之樹脂層塗佈液> •丙烯酸系樹脂主劑（固形成分50%) (Acridic A8(H-P:大日本油墨化學工業公司） •聚異氰酸酯（固形成分75%) (Banoc DN-950:大日本油墨化學工業公司） 對於實施例、及比較例所得之隔熱性薄片，評 性，對於被黏體的貼附性、防損傷性。又，對於實 隔熱性薄片評價黏著性。評價結果示於表1。 (1 ) 隔熱性之評價 將實施例及比較例之隔熱性薄片，透過黏著層 厚度25 μιη的聚酯薄膜，並切成110mm xllOmm的 之黏者 以熟化 28份 59份 12份 84份 16份 價隔熱 施例之 貼附至 大小， -20- (18) (18)200403288 作成試驗片，且使用如圖2所示般之試驗裝置2 5 ’如下評 價隔熱性。 將試驗片2 1切出1 0 0 m m X 1 0 0 m m之大小並於試驗箱2 4 之上方以隔熱層爲上側般安裝，且以試驗2 1上方所設置之 白熱燈22照射試驗片21，並以試驗片21裏面所設置之溫度 感應器23測定並記錄溫度。 此處，試驗箱爲使用厚度爲30mm，且尺寸爲「縱」X 「橫」X「高度」=250mm ><350mm x250mm的發泡苯乙稀 箱。又，試驗片21與白熱燈22之距離爲150mm。白熱燈22 爲使用RF100 V180 WHC (東芝Litech公司）。溫度感應 器 23爲使用 Thermal Coder RT-11 ( TABIESPECK 公司）。 又，試驗爲以23 t、50% R.H.之恆溫恆濕室之無風狀態 下實施。 評價爲以測定開始至30分鐙後之溫度感應器23的溫 度爲未滿5 0 °C者視爲「〇」，5 0 °C以上者視爲「X」。 還有，此時，試驗片2 1之照射面側的溫度爲約80 °C ° -21 - (19) (19)200403288 ，超過3·5 N/mm2且爲10 N/mm2以下者視爲「△」，超過 1 0 N/mm2者視爲「X」。 (3 ) 防損傷性之評價 將實施例及比較例之隔熱性薄片，透過黏著層貼附至 厚度2 mm的玻璃基板，並於其上將半徑〇 · 1 mm，尖端角 6 0 °的藍石英針垂直放下。其次於藍石英針之上放上砝 碼，並且令隔熱性薄片以2600mm/min之速度移動，並且 以2 5倍透鏡g平價確認損傷時之5去碼重量。 評價爲以600克以下無損傷者視爲「◦」，3 00克以下 造成損傷者視爲「x」。 (4) 黏著性之評價200403288 玖 玖, description of the invention [Technical field to which the invention belongs] The present invention relates to the roofs and outer panels of ships, garages, warehouses, etc., which are applied to the roofs and outer walls of buildings such as factories, houses, containers, and refrigerated vehicles. Roofs and outer walls, such as houses, and barns, are heat-resistant sheets that suppress the rise in internal temperature caused by sunlight. [Prior Art] In the past, in order to suppress an increase in the internal temperature due to sunlight, a transportation vehicle such as a container or a refrigerated vehicle has attached a heat-insulating sheet to a roof or an outer panel. Such a heat-insulating sheet has conventionally been a heat-insulating sheet in which a heat-insulating pigment is mixed with a thermoplastic resin. For example, in Patent Literature 1 and Patent Literature 2, it has been proposed that a thermoplastic resin such as vinyl chloride resin, polyethylene resin, polyester resin, (meth) acrylic resin and the like contain a specific heat-insulating pigment composition The object is shaped into a sheet. In addition, recently, a heat-resistant sheet having a heat-resistant coating applied to a substrate such as plastic has been proposed. For example, in Patent Document 3, Patent Document 4, and Patent Document 5, it is proposed to form a sheet made of a heat-resistant pigment and an adhesive on sheets and films such as vinyl chloride, polyolefin, and polycarbonate (meth) acrylic resin. Composition of heat insulation layer. These heat-insulating sheets are attached to an object (substrate) to be blocked from external heat through an adhesive layer or an adhesive layer for use. Patent Document 1 JP 8- 8 1 5 67 Patent Document 2 JP 2002_ 1 2679 Patent Document 3 JP 1 0-2 5 0 0 0 2 (2) (2) 200403288 Patent Document 4 Open 2 0 0 2-1 2 6 8 3 Patent Document 5 Japanese Patent Laid-Open No. 200 1 -27002 1 This type of heat-insulating sheet has sufficient heat insulation properties, and is required to follow the shape of the adherend, that is, to have Flexible. Especially when the adherend is a curved surface, a high elongation is desired. However, in order to obtain a sufficient heat-shielding property, when a heat-shielding pigment is contained in a large amount in a heat-shielding sheet or a heat-shielding layer, flexibility is impaired, adhesion is difficult, and problems such as breakage easily occur. Therefore, the conventional heat-insulating sheet has generally used a highly flexible vinyl chloride resin as a base material. However, the heat-insulating sheet using a vinyl chloride resin has the following problems. Firstly, 'the vinyl chloride storage resin has a problem of generating toxic gas during incineration treatment' has been developed in the field of plastic materials. In addition, in applications where the adherend is required to have a high degree of flexibility such as a curved surface, a large amount of plasticizer must be added to vinyl chloride resin. However, if such a vinyl chloride-based resin sheet is used for a long time, it will be used in The plasticizer precipitates on the surface, and the heat insulation layer cracks. Therefore, the present invention aims to provide a heat-insulating sheet that can be adhered well when the adherend is a curved surface without using a vinyl chloride resin. [Summary of the Invention] Solution: The present invention has the above-mentioned object. The heat-shielding sheet is a heat-shielding layer containing a urethane-based resin and a heat-shielding pigment, and a resin layer formed of a urethane-based 5- (3) (3) 200403288 resin. For its characteristics. The resin layer composed of a urethane-based resin has flexibility close to that of a vinyl chloride-based resin sheet, and by forming a multilayer structure with a heat-insulating laminated layer, the flexibility can be further improved, and in particular, the start of extension can be reduced. Required strength (tensile yield strength). Thereby, it can be extended while conforming to the shape of the adherend, and it can be attached with good workability during attachment without breaking. In addition, even if the heat-insulating layer has low flexibility, it can be adhered in accordance with the shape of the adherend. In addition, since no vinyl chloride resin is used, deterioration of the heat insulation layer and cracking due to precipitation of plasticizers do not occur, and there is no problem of environmental pollution during disposal. In addition, if the heat-insulating layer contains the same resin as the urethane-based resin constituting the resin layer, the adhesion between the resin layer and the heat-insulating layer can be improved, and the flexibility can be improved. It is possible to suppress the occurrence of cracks even when extended. The heat-insulating sheet of the present invention preferably has a tensile yield strength of 100 N / mm2 or less, more preferably 5 N / mm2 or less, and more preferably 3.5 N / mm2 or less. By setting the tensile yield strength to be in the above range, the adherence can be easily extended and adhered to the shape of the adherend. In addition, the so-called "tensile yield strength" refers to 値 measured according to Π SK 7 1 1 3 -1 98 1 (tensile test method for plastics), which is defined as the load-delay curve. See tensile stress at the initial point of elongation increase. The "tensile breaking strength" refers to the tensile stress at the moment when the test piece is broken. Furthermore, the heat-insulating sheet of the present invention has an adhesive layer on the side opposite to the surface of the heat-insulating layer having a resin layer of -6-K fe: (4) (4) 200403288 in the above configuration. The heat-insulating sheet of the present invention preferably has a solvent permeation prevention layer between the heat shielding layer and the resin layer. A resin layer composed of a urethane-based resin is highly permeable to solvents. By providing such a solvent-permeable layer, it is possible to prevent the coating layer from being contained in the heat-shielding layer coating liquid when the heat-shielding layer is formed. The solvent and the residual solvent contained in the heat-shielding layer after the heat-shielding layer is formed pass through the resin layer to the adhesive layer, and reduce the adhesiveness. When the heat-insulating sheet of the present invention has an adhesive layer, it is preferably formed by laminating a resin layer after forming an adhesive layer with another base material. The adhesive layer is not formed by directly coating the resin layer. In order to laminate the resin layer with a pre-formed adhesive layer, the number of times the resin layer and the heat insulation layer are heated can be reduced, and the resin layer and the heat insulation layer can be lightened. Shrink caused by heat. In addition, no matter how the hardening of the resin layer composed of the urethane-based resin is completed, an adhesive layer can also be formed, making it easy to manufacture. Furthermore, since the solvent of the coating liquid of the adhesive layer can be prevented from penetrating into the resin layer, it is difficult to cause a decrease in the adhesive force with time due to the resin layer being impregnated with the solvent. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, an embodiment of the heat-insulating sheet according to the present invention will be described in detail. Figs. 1 (a) to (c) are diagrams showing embodiments of the heat-insulating sheet of the present invention. As shown in FIG. 1 (a), the heat-insulating sheet of the present invention has a resin layer 12 including a heat-insulating layer 11 and a urethane-based resin as a basic structure. One embodiment is as shown in FIG. 1. As shown in Fig. 1 (b), an adhesive layer 13 is provided on the opposite side of the surface where the heat-insulating layer 11 is formed in (5) (5) 200403288 of the resin layer 12. In another embodiment, as shown in FIG. 1 (c), a solvent permeation preventing layer (solvent permeation preventing layer) 14 is provided between the resin layer 12 and the heat-insulating layer 11. A peelable spacer 15 is provided on the adhesive layer 13. The heat-insulating sheet of the present invention is characterized by a laminated structure in which a heat-insulating layer 11 and a resin layer formed of a urethane-based resin are laminated. By forming such a layer structure, It can also be attached well when the body is a curved surface. In the following, the difference in performance between a sheet of kneaded heat-insulating pigment (hereinafter referred to as a kneaded sheet) and the heat-shielding sheet (multilayer sheet) of the present invention in which a heat-insulating layer and a resin layer are laminated will be described. Generally, flakes are made of heat-insulating pigments to reduce elongation. Therefore, in the case where the strength until the heat-shielding sheet is broken is extended, the kneaded sheet with the heat-shielding pigment uniformly in the entire sheet is extended more than the multi-layer sheet containing a high-density heat-shielding pigment on the surface of the heat-shielding sheet. long. In other words, the tensile elongation at break is relatively large. On the other hand, the strength required to start the extension (i.e., the tensile yield strength) requires more strength for the kneaded sheet containing the heat-insulating pigment as a whole than the multilayer sheet. This is because the multi-layered sheet does not contain a heat-insulating pigment or the like that prevents the resin layer from being stretched, and thus the stretching can be started with a weak force. At this time, the 'heat-insulating layer containing a high-density heat-insulating pigment is laminated on the resin layer', so it follows the extension of the resin layer and extends with a weak force. When attaching a heat-insulating sheet to an adherend ', especially when following a curved surface, the tensile yield strength is important among the above characteristics. That is, “tensile flexion -8- (6) (6) 200403288 The multilayer sheet with low strength can make the resin layer follow the surface even if it is stretched with a weaker force, so it can be easily attached to the adherend. In addition, as the resin layer is extended to the heat insulation layer, extension cracks do not occur. According to the detailed review by the inventors, it is known that the tensile yield strength is 10N / mm2 or less, preferably 5 N / mm2 or less, and more preferably 3.5 N / mm2 or less. Adhesive, and the sheet does not regress after attachment. A heat-shielding sheet having such characteristics can be formed by using a urethane resin as a non-vinyl chloride resin and multilayering it. Next, each layer constituting the heat-insulating sheet of the present invention will be described. The urethane-based resin constituting the resin layer can be obtained by cross-linking a urethane-based resin main agent with a hardener such as polyisocyanate, and the structure thereof has sufficient elasticity and self-healing properties, and Tough and excellent abrasion resistance. The characteristics of such resin layers can be appropriately adjusted according to the acid base, hydroxy base, and molecular weight of the urethane-based base agent, the molecular structure of the polyisocyanate, the content of the isocyanate group, and the degree of polymerization thereof. The resin layer may contain other resins, pigments, lubricants, colorants, antistatic agents, flame retardants, antibacterial agents, antifungal agents, ultraviolet absorbers, light stabilizers, as long as the function of the present invention is not impaired. Various additives such as antioxidants, leveling agents, flow regulators, and defoamers. The resin layer is a urethane-based resin, and if necessary, other components and a diluent are mixed to prepare a coating liquid, and this coating liquid is applied to a specified substrate (also has a heat-insulating layer) by a known coating method. (Case) can be formed by coating and drying and hardening by heating. Commonly used urethane -9- (7) (7) 200403288 Ethyl flakes can also be used as the resin layer. The lower limit of the thickness of the resin layer is preferably 20 μm or more, and more preferably 50 μm or more. The upper limit is preferably not more than 300 μm, and more preferably not more than 100 μm. When the thickness of the resin layer is 20 μm or more, when the heat-insulating sheet is attached to the adherend and extended, it is possible to prevent cracks and the like in the heat-insulating layer. In addition, by making the thickness of the resin layer less than or equal to 300 μm, the heat-insulating sheet can be attached to the adherend with a relatively weak force. In consideration of the above materials and thickness, it is preferable to use a resin layer having a tensile yield strength of 1 to 7 N / mm2. The heat-insulating layer is a layer containing a heat-insulating pigment, and is composed of, for example, a binder containing a urethane resin and a heat-insulating pigment. The so-called heat-insulating pigments are heat-insulating properties that make it difficult to transfer heat energy from sunlight, and heat reflectivity that does not absorb and reflect heat energy from sunlight, and re-radiates the absorbed heat energy to the outside in infrared rays. Inorganic and organic pigments with properties such as long-wave radioactivity, and known materials can be used. Specific examples include inorganic pigments such as ceramics, iron oxide, lead oxide, titanium oxide, talc, and barium sulfate; and organic pigments such as phthalocyanine blue and Syncacia Red. One or two or more of them may be appropriately combined. Among them, ceramic fine particles having excellent thermal insulation, thermal reflectivity, and long-wave radioactivity, particularly transparent hollow ceramic fine particles, and titanium oxide having excellent thermal reflectivity and self-cleaning properties are preferably used. As the adhesive for adhering the heat-insulating pigment, a substance containing at least an urethane-based resin can be used. The urethane-based resin can be the same as the urethane-based resin used in the resin layer. By including the heat-insulating layer -10- (8) (8) 200403288, it is possible to obtain a good extension and difficult Damaged insulation. In addition, it has excellent adhesion to a resin layer composed of a urethane-based resin, and has no interlayer peeling. The heat-shielding layer may be blended with other resins as an adhesive as long as the effects of the urethane-based resin are not hindered. For other resins, known resins such as olefin-based resins such as polyethylene, polypropylene, ethylene-based copolymers, and propylene-based copolymers, acrylic resins such as (meth) acrylate copolymers, and polyester resins can be used. Although the content of the urethane resin in the adhesive composition of the heat-shielding layer is not particularly limited, it is preferably 20% by weight or more, more preferably 50% by weight or more, and even more preferably 90% by weight or more. By setting the content of the urethane resin in the adhesive composition of the heat-insulating layer to be 20% by weight or more, the resin can be traced even when the shape of the adherend when the heat-shielding sheet is made is a curved surface. Extension of the layer, so no cracks will occur in the heat insulation layer. The content of the heat-shielding pigment in the heat-shielding layer varies depending on the thickness of the heat-shielding layer, the purpose of the heat-shielding effect, and the like, and cannot be said at one glance, but the lower limit is preferably 10% by weight or more, more preferably 20 Above weight%. In addition, since the heat-insulating sheet is attached to the adherend, cracks and the like in the heat-insulating layer can be prevented during stretching. The upper limit is preferably 60% by weight or less, and preferably 40% by weight or less. In addition, the heat-shielding layer may contain other components similar to those of the resin layer as long as it does not impair the function of the present invention, in addition to the adhesive and heat-shielding pigment. This type of heat-insulating layer is made by mixing the adhesive, heat-insulating pigment, and other components as necessary. -11-(9) (9) 200403288 The hot-layer coating liquid is coated by a conventionally known coating method, for example, a bar coater, a die coater, a blade coater, a spin coater, a roll coater, a gravure coater, a flow coater, and a sprayer. , Screen printing, etc. can be applied to a specified substrate (there is also the case of a resin layer), and it can be dried and hardened by heating to form a heat insulation layer. In addition, the heat-shielding layer can be made by mixing and kneading heat-shielding pigments containing at least an urethane-based resin, and formed into a thin sheet. The thickness of the heat-shielding layer is based on the amount of heat-shielding pigments added. The thermal insulation effect and the like are different, and it cannot be said at all, but when it is set by the coating method, it is about 50 μm to 700 μm, preferably about 100 μm to 500 μm. The thickness of the heat-shielding layer is less than 50 μm. In order to obtain sufficient heat-shielding properties, the content of the heat-shielding pigment becomes high, which is liable to cause cracks during stretching. The thickness ratio of the resin layer and the thickness of the heat insulation layer also vary according to the thickness of the entire sheet and the heat insulation characteristics of the purpose. However, when the overall thickness is about 200 μm to 400 μm, the resin layer: the heat insulation layer is 40: 60 ~ Around 10:90. The adhesive layer is a layer for attaching the heat-insulating sheet of the present invention to an adherend, and is formed on the opposite side of the resin layer from which the heat-insulating layer is formed. As the adhesive constituting the adhesive layer, commonly used acrylic adhesives, silicone adhesives, urethane adhesives, rubber adhesives, and the like can be used. Also, an adhesive having antistatic properties can be used. The adhesive layer is generally formed by dissolving or dispersing the above-mentioned adhesive in a diluent solvent as a coating liquid, and coating and drying the coating liquid by a conventionally known coating method. The thickness of the adhesive layer varies from -12 to (10) (10) 200403288 depending on the adherend. It cannot be said at once, but if the adhesion is taken into consideration, the lower limit is 20 μm or more, preferably 30 μm or more. The upper limit is 200 μm or less, and preferably about 100 μm or less. The solvent permeation prevention layer is provided to prevent the solvent contained in the heat-insulating layer coating liquid and the solvent components remaining in the heat-insulating layer from penetrating the resin layer when the heat-insulating layer is formed, and reaches the layer where the adhesiveness is reduced, and is provided. Between the heat insulation layer and the resin layer. As the material constituting the solvent permeation prevention layer, a resin having good flexibility and high solvent resistance can be used. Specific examples of such resins include polyamine resins, urethane acrylic resins, modified polyesters, and the like, and particularly polyamine resins are suitable. In order to improve the adhesion with the heat-insulating layer and the resin layer, the solvent-permeation preventing layer preferably contains a small amount of a urethane-based resin. The urethane-based resin for improving adhesion is preferably an aqueous urethane-acrylic resin. In order to achieve a higher effect of preventing solvent penetration, it is preferable that the amount of the urethane resin added is not more than 50 parts by weight relative to 100 parts by weight of the polyamide resin. The solvent permeation prevention layer can be formed by applying an aqueous coating liquid to a resin layer. Although its thickness is also related to the thickness of each element of the heat-insulating sheet, in order to obtain the above effect, it is appropriate to use about 1 μm to 20 μm, more preferably about 1 μm to 10 μm, and even more preferably 1 μm to 5 μm. about. Next, a method for manufacturing the heat-insulating sheet of the present invention having the above-mentioned configuration will be described. The heat-insulating layer / resin layer (heat-insulating layer / solvent-proof layer / resin layer) of the basic composition of the heat-insulating sheet of the present invention is a dry layer through co-extrusion -13- (11) (11) 200403288 Forming or coating. In the case of coating, either a heat-shielding layer or a resin layer is formed into a thin sheet, or a coating layer type is set on a spacer or the like as a base material, and another base material is coated on the base material. One can be formed. The adhesive layer may be formed before the resin layer and the heat insulation layer are laminated, or may be formed after the lamination. In particular, it is preferable that the adhesive layer is formed on a substrate such as a spacer, and the resin layer is attached. In this case, it is possible to reduce the number of repeated coating and drying steps' and to reduce the shrinkage of the resin layer and the heat-insulating layer due to heat. In addition, no matter how the hardening of the resin layer composed of the urethane-based resin is completed, an adhesive layer can also be formed, making it easy to manufacture. If an example of the manufacturing method is listed, a heat-insulating layer coating liquid prepared by mixing an adhesive, a heat-insulating pigment, and other ingredients added as needed and a diluting solvent, is applied on the spacer by a conventionally known coating method. Cloth, and dried and hardened by heating to form a heat-insulating layer. Next, on this heat-shielding layer, a urethane-based resin, if necessary, is added with other components, and a diluent solvent is mixed to prepare a coating solution, and the heat-shielding layer is coated with the previously-known coating method as described above. Cloth, which can be dried and hardened by heating, can form a resin layer. In the case where a solvent-permeation preventing layer is provided, after forming the heat-insulating layer, an aqueous coating liquid of a resin constituting the solvent-permeation preventing layer is coated and dried by a known coating method, and a resin layer is formed thereon as described above. . Furthermore, on this resin layer, the coating solution in which the adhesive layer is dissolved in a diluent solvent is applied in the same manner as the above-mentioned known coating method, and it is dried to form an adhesive layer, and the heat-insulating sheet of the present invention is obtained. . In other examples, a commercially available urethane sheet is used as a resin layer, and a heat-shielding layer is formed on one side of the urethane sheet, and the other -14- (12) (12) 200403288 side It is also possible to form an adhesive layer for fabrication. The manufacturing methods described above are merely examples, and the manufacturing method of the heat-insulating sheet of the present invention is not limited to these manufacturing methods. For example, instead of sequentially laminating the resin layer and the adhesive layer on the heat insulation layer, any order may be used to form the heat insulation layer, the resin layer, and the adhesive layer. The heat-insulating sheet of the present invention thus manufactured can be attached to a desired adherend through the adhesive layer. In this case, even if the adherend is a curved surface, it can be attached with good workability. In addition, since no vinyl chloride-based resin added with a plasticizer is used, no toxic gas is generated during incineration, and no cracks or the like occur in the heat insulation layer even if it is used for a long time. Examples Hereinafter, the present invention will be described in more detail based on examples. In addition, "part" and "%" in this embodiment are based on weight unless otherwise specified. [Example 1] A 100 μΐΏ thick paper spacer (Binasheet 70S-218T: Fujimori Kogyo Co., Ltd.) was coated with a heat-insulating layer coating solution of the following formula, and dried at 90 ° C for 10 minutes to form 2000. κ m insulation. Next, a resin layer coating solution of the following formula was applied on this heat-shielding layer, and dried at 100 ° C for 6 minutes to form a resin layer having a thickness of 80 μm to obtain a heat-shielding sheet. Next, the same spacers as described above were coated with an adhesive layer coating solution of the following formula, and dried at 100 ° C. for 5 minutes to form an adhesive layer with a thickness of 60 to obtain an adhesive sheet. The adhesive layer of this adhesive sheet was laminated with the resin layer of the above-mentioned thin heat-insulating sheet (15- (13) 200403288), and it was aged at 60 ° C for 7 days to prepare the heat-insulating sheet of Example 1. < Heat-insulating pigment dispersion for heat-insulating layer coating liquid of Example 1 > A heat-insulating pigment (τ itan CR 9 7: Ishihara Tita η industrial formula, 29 parts of methyl ethyl ketone, dispersed 3 parts (Disperby Chem 61 Chem Japan) is dispersed with a disperser (Dinomill KDL type: B ac 〇fe η) to a particle size of 5 μm or less to obtain a thermal insulation 68% dispersion (heat-insulating pigment dispersion ( a)). < The heat-shielding layer coating liquid of Example 1 > • heat-shielding pigment dispersion liquid (a) • acrylic urethane resin main agent (solid content: 35%) (Neopaint # 8500 Clear: Asiatic Industries Co., Ltd. • Polyisocyanate (53% solids content) (hardener for Neopaint # 8 5 00: Asiatic Industries Co., Ltd.) < Resin layer coating liquid of Example 1> • Acrylic urethane resin Main agent (35% solids content) (Neopaint # 8500 Clear: ASIA Industries) • Polyisocyanate (53% solids) (Hardener for Neopaint # 8 5 00: ASIA Industries) < Adhesion of Example 1 Layer coating liquid> Nissho Division) 68: 28 parts of B YK Willey pigment 73 parts 9 0 parts 3 0 parts -16- (14) (14) 200403288 • Acrylic adhesive (40% solid content) 6 2 parts (NisetsuKP-2074: Japan Cabide Industries) • 1 part polyisocyanate (Nisetsu CK-117 : Cabide Industries, Japan) • 37 parts of ethyl acetate [Example 2] A resin layer composed of an urethane sheet (Silchron MT93: Okura Industrial Co., Ltd.) with a thickness of 80 μm was adhered to the resin produced in the same manner as in Example 1. The adhesive layer of the sheet was laminated. Next, the non-layered surface of the aforementioned adhesive layer of the urethane sheet was applied to a commercially available heat-insulating paint containing 40% of the heat-insulating pigment as an adhesion component. Insulation coating solution (formula shown below) of urethane-based resin, dried at 90 ° C for 10 minutes to form a 200 μm insulation layer, and left in an environment of 60 t for 7 days It was cured to produce a heat-insulating sheet of Example 2. < Heat-insulating layer coating liquid of Example 2 > • 56 parts of commercially available heat-insulating coating main agent (65% solids content) (MiraculeS5007F: Long Island Special Coating company) • Hardener for heat-insulating coating (60% solid content) 1 9 parts (Miracule S5 007F hardener: Nagashima Special Coatings Co., Ltd.) • Acrylic urethane resin base (solid content: 35%) 18 parts (Neopaint # 8500 Clear: Asia Industrial Co., Ltd.) • Polyisocyanate (solid content 53%) 6 parts -17- (15) (15) 200403288 (Neopaint # 8 5 00 Hardener: Asia Industrial Corporation) [Example 3] Resin composed of the same urethane sheet as in Example 2 The layer is laminated with the adhesive layer of the adhesive sheet prepared in the same manner as in Example 1. Next, on the non-laminated side of the adhesive layer of the aforementioned urethane sheet, apply the coating solution of the solvent permeation prevention layer described below, and dry it at 110 ° C for 3 minutes to form a 3 μm thick Prevent solvent from penetrating the layer. On this solvent permeation preventing layer, the same heat treatment layer as in Example 2 was formed to form a heat insulation layer, and it was left to mature in an environment of 60 ° C for 7 days to produce a heat insulation sheet of Example 3. < Solvent penetrating layer coating liquid of Example 3 > • 8 parts of aqueous urethane acrylic resin (37% solids content) (NeoRez R-9676: ASIA Corporation) • Polyamide 6/6, 6 12 parts of / 6, 13 copolymer (100% solids content) (Ultramid IC: BASF Japan) • Methyl modified ethanol 5 6 parts • Tap water 2 4 parts [Comparative Example 1] The paper spacer of Example 1 was coated A heat-insulating layer coating solution of the following formula was applied, and dried at 90 ° C for 10 minutes to form a heat-insulating layer having a thickness of 280 Mm. Next, this heat-insulating layer was laminated with the adhesive layer of the adhesive sheet of Example 1. '-18- (16) (16) 200403288 It was aged in an environment of 60 t for 7 days and matured to produce a thermal-insulating sheet of Comparative Example 1. . < The heat-insulating layer coating liquid of Comparative Example 1 > • 33 parts of commercially available heat-insulating coating main agent (65% solids content) (Miracule S5007F: Nagashima Special Coatings Co., Ltd.) • Hardener for the above-mentioned heat-insulating coating (60% solids content) 11 parts (hardener for Miracule S 5 007F: Nagashima Special Coatings Co., Ltd.) • Acrylic urethane resin main agent (35% solids content) 42 parts (Neopaint # 8 5 00 Clear: Asia Industries Corporation) • Polyisocyanate (53% solids content) (Neopaint # 8 5 00 Hardener: Asia Industries Corporation) [Comparative Example 2] A heat-insulating layer made of vinyl chloride resin and heat-insulating pigment ( A thermal insulation sheet (ATTSU-9: Likentenos, Inc.) composed of a thickness of 22 0 μm) and an adhesive layer (thickness of 1 10 μm) was regarded as a thermal insulation sheet of Comparative Example 2. [Comparative Example 3] The paper spacer of Example 1 was coated with a heat-shielding layer coating solution of the following formula, and dried at 90 ° C for 10 minutes to form a heat-shielding layer having a thickness of 200 μm. Next, the resin layer coating solution of the following formula was applied on the heat-shielding layer, and dried at 100 ° C for 6 minutes to form a resin layer with a thickness of 80 μm, thereby obtaining heat-insulating properties. 19- (17) 200403288 Flakes. Next, the resin layer of this heat-insulating sheet was laminated with the adhesive layer of the sheet of Example 1, and it was left to stand at 60 ° C for 7 days to prepare a heat-insulating sheet of Comparative Example 3. < Heat-shielding layer coating liquid of Comparative Example 3 > • Heat-shielding pigment dispersion liquid (a) of Example 1 • Acrylic resin base agent (solid content 50%) (Acridic A801-P: Dainippon Ink Chemical Industry Co., Ltd.) • Polyisocyanate (75% solids content) (Banoc DN-950: Daiyoshi Ink Chemical Co., Ltd.) < Resin layer coating liquid of Comparative Example 3 > • Acrylic resin base agent (solid content 50%) (Acridic A8 (HP: Dainippon Ink Chemical Industry Co., Ltd.) • Polyisocyanate (75% solids content) (Banoc DN-950: Dainippon Ink Chemical Industry Co., Ltd.) Insulation properties obtained for Examples and Comparative Examples Sheets, evaluation properties, adhesion to adherends, and damage resistance. In addition, evaluation of adhesion properties for solid heat insulation sheets. The evaluation results are shown in Table 1. (1) Evaluation of heat insulation properties Examples and comparisons The heat-insulating sheet of Example passed through a polyester film with an adhesive layer thickness of 25 μm, and was cut into a 110 mm x 110 mm stick to cure 28 parts 59 parts 12 parts 84 parts 16 parts of the value of the example of thermal insulation. -20- (18) (18) 200403288 Make a test piece, and use as shown in Figure 2 The test device 25 was evaluated as follows. The test piece 21 was cut out to a size of 100 mm X 100 mm, and installed above the test box 24 with the heat insulation layer as the upper side, and the test 2 The incandescent lamp 22 provided above 1 irradiates the test piece 21, and the temperature is measured and recorded by the temperature sensor 23 provided in the test piece 21. Here, the test box is 30 mm thick and has a size of "vertical" X " "Horizontal" X "height" = 250mm < 350mm x 250mm foamed styrene vinyl box. The distance between the test piece 21 and the incandescent lamp 22 is 150mm. The incandescent lamp 22 uses RF100 V180 WHC (Toshiba Litech). The temperature sensor 23 was a Thermal Coder RT-11 (TABIESPECK). The test was carried out in a windless state at a constant temperature and humidity chamber of 23 t and 50% RH. The evaluation was based on the temperature from the beginning of the measurement to 30 minutes after the start of the measurement. If the temperature of the sensor 23 is less than 50 ° C, it is regarded as "0", and if it is 50 ° C or more, it is regarded as "X". In this case, the temperature of the irradiation surface side of the test piece 21 is about 80 ° C ° -21-(19) (19) 200403288, those exceeding 3.5 N / mm2 and below 10 N / mm2 are regarded as "△", Those exceeding 10 N / mm2 are regarded as "X." (3) Evaluation of damage resistance The heat-insulating sheets of the examples and comparative examples were attached to a glass substrate having a thickness of 2 mm through an adhesive layer, and were placed thereon. Lower the blue quartz needle with a radius of 0.1 mm and a tip angle of 60 °. Next, put a weight on the blue quartz needle, and move the heat-insulating sheet at a speed of 2600 mm / min, and confirm the weight of 5 yards at the time of damage at 25 times the lens g parity. An evaluation of 600 gram without damage is considered as "◦", and a damage of 300 grams or less is considered as "x". (4) Evaluation of adhesion
將實施例之隔熱性薄片，切成寬25mm、長度1 50mm 的大小，並且貼附至SUS 3 04鋼板，且於23 °C，50%R.H 之環境氣體中放置5分鐘，並以剝離強度3 00mm/分鐘， 角度1 8 0 °剝離，且測定黏著力。黏著力爲超過8 0 0克 /25mm者視爲「◦」，800克/25mm以下者視爲「△」。 -22- (20) 200403288 表1 隔熱性 貼附性 防損傷性 黏著性 實 施 例 1 〇 〇 〇 Δ 實 施 例 2 〇 〇 〇 Δ 實 施 例 3 〇 〇 〇 〇 比 較 例 1 〇 Δ X 一 比 較 例 2 〇 X X — 比 較 例 3 〇 X X — 如表1所闡明般，實施例之隔熱性薄片爲較比較例1、 2之隔熱性薄片之拉伸屈服強度更小，且較比較例1、2之 隔熱性薄片，可以較弱之力量開始延伸，其結果，對於具 有彎曲面之被黏體等亦顯示優良的貼附性。又，實施例之 隔熱層僅管較比較例1、2之隔熱層含有更高密度之成爲延 伸障礙的隔熱性顏料，但仍可以較弱的力量取得可貼附至 被黏體程度的延伸度，可輕鬆追從樹脂層的延伸，且於隔 熱層不會發生龜裂。 另一方面，使用丙烯酸系樹脂代替胺基甲酸乙酯系樹 脂做爲樹脂層，並且使用丙烯酸系樹脂做爲隔熱層之黏合 成分之比較例3的隔熱性薄片於延伸上需要較大的力量， 並且於延伸時於隔熱層發生龜裂。 又，實施例之隔熱性薄片除了上述效果，加上於防損 傷性上亦取得較比較例之隔熱性薄片更爲優良的評價結果 ，顯示適於做爲貼附至被黏體外側的材料。 -23· (21) (21)200403288 更且，實施例3之隔熱性薄片因爲設置防止溶劑滲透 層，故可防止形成隔熱層時之隔熱層塗佈液之溶劑及隔熱 層中殘留的溶劑滲透至樹脂層，並且移行至黏著層，故可 維持高黏著性。 由以上之實施例所闡明般，若根據本發明，經由將含 有胺基甲酸乙酯系樹脂及隔熱性顏料的隔熱層，與胺基甲 酸乙酯所構成的樹脂層予以層合，則可取得即使於被黏體 爲彎曲面等之情況亦可良好貼附的隔熱性薄片。又，因爲 未使用添加可塑劑的氯乙烯系樹脂，故可取得於焚燒處理 時不會發生有毒氣體，又，即使長期使用亦不會於隔熱層 發生龜裂等的隔熱性薄片。 【圖式簡單說明】 圖1爲示出本發明之隔熱性薄片之實施形態的截面圖 ，11爲表示隔熱層，12爲表示樹脂層，13爲表示黏著層， 1 4爲表示防止溶劑滲透層。圖2爲隔熱性評價用試驗裝置 之截面圖。 符號說明】 11 隔熱層 12 樹脂層 13 黏著層 14 防止溶劑滲透層 15 間隔件 -24- (22) (22)200403288 21 S式驗片 22 白熱燈 23 溫度感應器 2 4 試驗箱 2 5 試驗裝置 -25-The heat-insulating sheet of the example was cut into a size of 25 mm in width and 150 mm in length, attached to a SUS 3 04 steel plate, and left in an ambient gas at 23 ° C, 50% RH for 5 minutes, with a peel strength It was peeled at 300 mm / min at an angle of 180 °, and the adhesion was measured. Those with an adhesive force exceeding 800 g / 25mm are regarded as "◦", and those with an adhesion force of 800 g / 25mm or less are regarded as "△". -22- (20) 200403288 Table 1 Insulation, adhesion, anti-damage, adhesiveness, Example 1 〇00Δ Example 2 〇〇Δ Example 3 〇〇〇〇 Comparative Example 1 〇Δ X A Comparative Example 2 XX — Comparative Example 3 XX — As explained in Table 1, the heat-insulating sheet of the example has a lower tensile yield strength than the heat-insulating sheet of Comparative Examples 1 and 2, and is smaller than Comparative Example 1 The heat-insulating sheet of 2 can start to extend with a weaker force. As a result, it also exhibits excellent adhesion to adherends having curved surfaces. In addition, the heat-insulating layer of the example only contains a higher-density heat-insulating pigment that is an obstacle to elongation than the heat-insulating layer of Comparative Examples 1 and 2, but can still obtain a degree of adhesion to the adherend with a weaker force. The degree of extension can easily follow the extension of the resin layer without cracking in the heat insulation layer. On the other hand, the insulation sheet of Comparative Example 3, which uses an acrylic resin in place of the urethane resin as the resin layer, and uses an acrylic resin as the heat insulation layer, requires a large extension. Strength, and cracks in the insulation during extension. In addition, in addition to the above-mentioned effects of the heat-insulating sheet of the example, in addition to the damage prevention property, a better evaluation result than that of the heat-insulating sheet of the comparative example was obtained, and it was shown that the heat-resistant sheet was suitable for being attached to the outside of the adherend. material. -23 · (21) (21) 200403288 Furthermore, since the heat-shielding sheet of Example 3 is provided with a solvent-permeation prevention layer, it can prevent the solvent and heat-shielding layer of the heat-shielding layer coating liquid from forming a heat-shielding layer. The remaining solvent penetrates into the resin layer and migrates to the adhesive layer, so that high adhesiveness can be maintained. As explained in the above examples, according to the present invention, if a heat-shielding layer containing a urethane-based resin and a heat-shielding pigment is laminated with a resin layer made of urethane, A heat-insulating sheet that can be attached well even when the adherend is a curved surface can be obtained. In addition, since a vinyl chloride-based resin containing a plasticizer is not used, it is possible to obtain a heat-insulating sheet that does not generate toxic gases during incineration and does not cause cracks in the heat-insulating layer even after long-term use. [Brief description of the drawings] FIG. 1 is a cross-sectional view showing an embodiment of the heat-insulating sheet of the present invention, 11 is a heat-insulating layer, 12 is a resin layer, 13 is an adhesive layer, and 14 is a solvent-proof layer. Permeable layer. Fig. 2 is a cross-sectional view of a test apparatus for evaluating heat insulation properties. Explanation of symbols] 11 Insulation layer 12 Resin layer 13 Adhesive layer 14 Solvent permeation prevention layer 15 Spacer -24- (22) (22) 200403288 21 S-type test piece 22 Incandescent lamp 23 Temperature sensor 2 4 Test box 2 5 Test Device-25-