TWI354123B - Near-infrared radiation absorption film - Google Patents

Description

1354123 修正本 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種吸收近紅外線之光學薄膜’詳言之’ 關於一種高溫時之色調變化爲少的、耐久性優異的近紅# 線吸收薄膜。 •【先前技術】 具有近紅外線吸收能力之光學薄膜係具有遮斷近纟工# 線、使可見光得以通過之性質，可使用於各種用途。 φ 近年來，電漿顯示器作爲薄型大畫面顯示器受到矚目， 根據從電漿顯示器所放射出之近紅外線，將有使用近紅外 線遙控之電子機器引起誤動作的問題，於電漿顯示器前面 具有該近紅外線吸收能力之薄膜將被使用。 具有近紅外線吸收能力之薄膜，有提案：（1 )於磷酸 系玻璃中，含有銅或鐵等金屬離子；（2)藉由積層折射率 不同的層以使透過光干涉，而使特定波長得以透過之干涉 濾光片；（3)於共聚物中含有銅離子之丙烯酸系樹脂薄膜； •( 4)積層已將色素分散或溶解於樹脂中之薄膜。 此等薄膜之中’（4 )之薄膜的加工性、生產性良好， 光學設計之自由度較大，已有人提案各種方法（參照專利 文獻1〜9 ) » 專利文獻1:日本專利特開2002-82219號公報 專利文獻2:日本專利特開2002-138203號公報 專利文獻3:日本專利特開2002-214427號公報 專利文獻4:日本專利特開2002-264278號公報 專利文獻5:日本專利特開2002-303720號公報 1354123 修正本 專利文獻6:日本專利特開2002-333517號公報 專利文獻7:日本專利特開2003-82302號公報 專利文獻8:日本專利特開2003-96040號公報 專利文獻9:日本專利特開2003-114323號公報 於此等方法之中，具有充分遮斷從電漿顯示器所放射出 '之近紅外線的能力，並且，具備即使長時間使用下經時變 化少的薄膜。 另一方面，爲了顯示器之輕量化或高畫質化，有人提案 種不使用玻璃而使含有近紅外線吸收薄膜之光學濾光片 貼合於電漿顯示器面板之方式。於此方式中，要求顯示器 之熱容易傳導至近紅外線吸收薄膜，耐濕熱性或耐熱性優 異的近紅外線吸收薄膜。 【發明內容】 發明所欲解決之技術問題 本發明之目的係爲了解決該習用技術之課題所進行 的，提供一種近紅外線吸收薄膜，其擴大近紅外領域，並 廣範圍加以吸收的同時，耐久性、特別是耐濕熱性或耐 熱性高度優異。 解決問題之技術手段 能夠解決該課題的本發明之近紅外線吸收薄膜係由下 列構造而成的： 第1項發明係一種近紅外線吸收薄膜，其係於透明基 材上，設置主要由近紅外線吸收色素、樹脂構成之組成物 而成的近紅外線吸收層之近紅外線吸收薄膜，其中該近紅 外線吸收色素不包含選自下列通式（I)〜（III)所示化合物組 成之群之陽離子及抑制劑陰離子所構成的安定化花青 1354123 修正本1354123 MODIFICATION OF THE INVENTION EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to an optical film that absorbs near-infrared rays, which is described in detail as a near-red line of excellent durability with little change in color tone at high temperatures. Absorbing film. • [Prior Art] An optical film having near-infrared absorbing ability has a property of blocking the near-line and allowing visible light to pass, and can be used for various purposes. φ In recent years, the plasma display has attracted attention as a thin large-screen display. According to the near-infrared rays emitted from the plasma display, there is a problem that the electronic device using the near-infrared remote control causes a malfunction, and the near-infrared light is provided in front of the plasma display. A film of absorbency will be used. A film having a near-infrared absorbing ability has been proposed: (1) containing a metal ion such as copper or iron in a phosphoric acid glass, and (2) a specific wavelength by allowing a layer having a different refractive index to interfere with transmitted light. An interference filter that passes through; (3) an acrylic resin film containing copper ions in the copolymer; (4) a film that has been dispersed or dissolved in the resin. Among these films, the film of '(4) has good processability and productivity, and the degree of freedom in optical design is large. Various methods have been proposed (see Patent Documents 1 to 9) » Patent Document 1: Japanese Patent Laid-Open 2002 Japanese Patent Laid-Open Publication No. JP-A-2002-138427 (Patent Document No. JP-A-2002-214427) Patent Document 4: JP-A-2002-264278 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the above-mentioned methods, it has the ability to sufficiently block the near-infrared rays emitted from the plasma display, and has a film which changes little with time when used for a long period of time. . On the other hand, in order to reduce the weight of the display or to improve the image quality, it has been proposed to bond the optical filter containing the near-infrared absorbing film to the plasma display panel without using glass. In this embodiment, it is required that the heat of the display is easily conducted to the near-infrared absorbing film, and the near-infrared absorbing film excellent in moist heat resistance or heat resistance. DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a near-infrared absorbing film which expands the near-infrared field and absorbs it in a wide range while maintaining the object of the prior art. In particular, it is highly resistant to moist heat or heat resistance. Means for Solving the Problem The near-infrared absorbing film of the present invention which can solve the problem is constructed as follows: The first invention is a near-infrared absorbing film which is attached to a transparent substrate and is mainly provided by near-infrared absorption. a near-infrared absorbing film of a near-infrared absorbing layer formed of a composition of a dye or a resin, wherein the near-infrared absorbing dye does not contain a cation and a suppression of a group selected from the group consisting of compounds represented by the following general formulae (I) to (III) Stabilized flower blue 1354123 composed of agent anions

[式中’環A及環A’各自獨立代表苯環、萘環 '或吡啶 環’R1及R1’各自獨立代表鹵素原子、硝基；氰基、碳數 6~30之芳基 '碳數1~8之烷基或碳數1〜8之烷氧基，R2、 R3及R4各自獨立代表氫原子、鹵素原子、氰基、碳數6〜30 之芳基、二苯基胺基或碳數1〜8之烷基，X及X’各自獨立 代表氧原子、硫原子、硒原子、丙烷-2,2 -二基、丁烷-2,2-基、碳數3〜6之環院-1，1-二基、-NH -或- NY!-，Y、Y，及 Y!各自獨立代表碳數1〜3 0之有機基，r及r，各自獨立代表 0〜2之整數];其特徵爲： 於該組成物中，含有三氟甲烷磺酸化合物或雙（三氟甲 烷磺醯基）醯亞胺酸化合物作爲相對離子的花青色素作爲 近紅外線吸收色素。 第2項發明係如揭示於第1項發明之近紅外線吸收薄 膜’其中近紅外線吸收色素含有—亞胺鑰（diimonium)鹽化 合物。 第3項發明係如揭示於第2項發明之近紅外線吸收薄 1354123 修正本 膜’其中二亞胺鎗鹽化合物係一種將雙（三氟甲烷磺醯基） 醯亞胺酸化合物作成相對離子的二亞胺鑰鹽化合物。 第4項發明係如揭示於第1至3項發明中任一項之近紅 外線吸收薄膜，其中近紅外線吸收色素係一種將三氟甲烷 磺酸化合物或雙（三氟甲烷磺醯基）醯亞胺酸化合物作成 ‘相對離子的花青（cyanine)色素，其係於近紅外線吸收層中 含有0.1質量％以上、10.0質量％以下。 第5項發明係如揭示於第4項發明之近紅外線吸收薄 •I ’其中近紅外線吸收色素包含將雙（三氟甲烷磺醯基） 醯亞胺酸化合物作成相對離子的二亞胺鎰鹽化合物及將三 氟甲烷磺酸化合物或雙（三氟甲烷磺醯基）醯亞胺酸化合 物作成相對離子的花青色素。 第6項發明係如揭示於第1至5項發明中任一項之近紅 外線吸收薄膜，其中構成近紅外線吸收層之樹脂爲丙烯酸 系樹脂。 [發明之效果] φ 將本發明之近紅外線吸收薄膜作爲近紅外線吸收濾光 片而設置於電漿顯示器之前面的情形，相同於習知之近紅 外線吸收濾光片，不僅盡可能吸收從顯示器所放射出的不 要之近紅外線，也防止精密機器之誤動作，由於能夠大幅 減低因熱所造成之色調變化，具有能夠有助於電漿顯示器 之高畫質化的同時，提高光學薄膜設計自由度的優點。 【實施方式】 以下，詳細說明本發明。 (透明基材） 1354123 修正本 於本發明中，透明基材並未予以特別限定，全部光線透 過率較宜爲80%以上’並且霧度較宜爲5%以下。基材於 透明性變差之情形下，不僅使顯示器之亮度降低，影像之 清晰性也變得不良。 如此之透明基材，例如，可列舉：聚酯系、丙烯酸系、 •纖維素系、聚乙烯系、聚丙烯系、聚烯烴系、聚氯乙烯系、 聚碳酸酯系 '酚系、胺基甲酸酯系等之塑膠薄膜或片材、 玻璃及貼合此等任意二種以上之基材。較宜爲耐熱性、柔 •^性之均衡性良好之聚酯系薄膜，更佳爲聚對苯二甲酸乙 二醇酯薄膜。 所謂適合作爲本發明使用之透明基材的聚酯系薄膜，其 係藉由進行作爲二羧酸成分之對苯二甲酸、間苯二甲酸、 萘二甲酸等芳香族二羧酸或其酯，與作爲二醇成分之乙二 醇、二乙二醇、1，4-丁二醇、新戊二醇等之酯化反應或酯 交換反應，接著，將聚縮合反應而得到的聚酯碎片予以乾 燥後，利用擠壓機進行熔融，將從T模頭擠壓成片狀而得 的未拉伸片，至少沿著單軸方向進行拉伸，接著，進行 熱固定處理、緩和處理所製造的薄膜。 基於強度等之觀點，該薄膜尤以雙軸拉伸薄膜特別理 想。拉伸方法可列舉：管式拉伸法、同時雙軸拉伸法、逐 次雙軸拉伸法等，但是基於平面性、尺寸安定性、厚度不 均勻等，較宜爲逐次雙軸拉伸法。例如，逐次雙軸拉伸薄 膜係於長軸方向、聚酯之玻璃轉移溫度（Tg)〜（Tg +3 0 °C )下，沿著長軸方向，進行2.0〜5.0倍之滾筒拉伸，接 著，利用拉幅器，於預熱後1 20〜1 5 0°C，沿著寬度方向進 1354123 修正本 行1.2〜5.0倍之拉伸。再者，能夠於雙軸拉伸後，於22〇 °C以上、熔點-1 (TC以下之溫度進行熱固定處理，接著，沿 著寬度方向予以3〜8%緩和而加以製造。另外，爲了進一 步改善薄膜長軸方向之尺寸安定性，也可以倂用縱向弛緩 處理。 ' 於薄膜中，爲了賦與作業性（例如，積層後之捲取性）， 較宜含有粒子而於薄膜表面形成突起。於薄膜中所含之粒 子’可列舉：二氧化矽、高嶺土、滑石、碳酸鈣、沸石、 化鋁等之無機粒子；丙烯酸、PMMA、耐綸、聚苯乙烯、 聚酯、苯并三聚氰二胺-甲醛縮合物等耐熱性高分子粒子。 基於透明性之觀點，薄膜中之粒子的含量較宜爲少的，例 如.’較宜爲1 pp m以上、1 0 0 0 p p m以下。再者，基於透明性 之觀點’較宜選擇所用之樹脂與折射率接近的粒子。另外， 必要的話’將各種機能賦與薄膜，也可以含有耐光劑（抗 紫外線劑）、色素、抗靜電劑等。 於本發明中，將抗反射層設置於積層近紅外線吸收層面 #相反面之情形，由於根據從外部射入之紫外線而容易導 致近紅外線吸收色素之劣化，較宜於透明基材內含有紫外 線吸收劑。 紫外線吸收劑大致區分爲有機系紫外線吸收劑與無機 系紫外線吸收劑，基於確保透明性之觀點，期望使用有機 系紫外線吸收劑（低分子型、高分子型）。有機系紫外線 吸收劑（低分子型），並未予以特別限定，例如，可列舉： 苯并***系、二苯甲酮系、環狀醯亞胺基酯系等，及此等 之組合。基於耐久性之觀點，此等紫外線吸收劑之中，較 -10- 1354123 修正本 宜爲苯并***系、環狀醯亞胺基酯系，再者，爲了承受基 材製造時之溫度，分解溫度較宜使用2 9〇°C以上之紫外線 吸收劑。 紫外線吸收劑之含量較宜使近紅外線吸收層的光劣化 能控制之方式，並使380nm以下波長之透過率成爲1〇%以 '下之方式來調整。具體而言，於透明基材中，紫外線吸收 劑之含量較宜爲〇.1〜4質量％，更佳爲0.3〜2質量％。 若紫外線吸收劑量過小時，因爲紫外線吸收能力將變小， #過多時，將有薄膜變黃之情形或薄膜製膜性降低之情形 而不佳。 本發明所用之透明基材可以爲單層薄膜，也可以爲已積 層表層與中心層之二層以上的複合薄膜。複合薄膜之情 形，具有能夠獨立設計表層與中心層機能之優點。例如， 藉由僅於厚度薄之表層含有粒子而於表面形成凹凸，維持 作業性的同時，藉由實質上於厚度厚的中心層中不含有粒 子，整體複合薄膜能夠進一步使透明性得以提高。另外， 與紫外線吸收能力之情形，藉由僅於中心層含有紫外線 吸收劑，由於能夠減低薄膜製造時或經時之紫外線吸收劑 朝表面之析出’能抑制對近紅外線吸收層之耐熱性劣化等 之不良影響。該複合薄膜之製法，並未予以特別限定，但 是若考慮生產性時，尤其從個別擠壓機擠出表層與中心層 之原料，導入一模頭而得到未拉伸片材後，至少使其配向 於單軸方向’利用所謂的共擠出法進行積層特別理想。 透明基材之厚度係視原材料而有所不同，使用聚酯薄膜 之情形下’下限較宜爲35μιη以上，更佳爲50μιη以上。另 -11 - 1354123 修正本 —方面’厚度之上限較宜爲26〇μπι以下，更佳爲200μιη以 下。厚度爲薄的情形下，不僅使作業性變得不良，或是使 近紅外線吸收層之殘留溶劑變少之方式來於乾燥時加熱之 情形下，於薄膜中發生熱皺摺，平面性容易變得不良。另 一方面’厚度厚的情形下，不僅成本面有問題，捲取成滾 筒狀後保存的情形下，因捲取彎曲而造成的平面性不良也 變得容易發生。 (中間層） •雖然本發明之近紅外線吸收濾光片係於透明基材上積 層近紅外線吸收層之構造所構成的，以透明基材與近紅外 線吸收層之緊貼性提高或透明基材之透明性提高爲目的， 較宜設置中間層。還有，於薄膜中不含粒子之情形，藉由 於薄膜製造時同時設置含有粒子之中間層，維持作業性的 同時’也能夠得到高度之透明性。 構成該中間層之樹脂’可列舉：聚酯系樹脂、聚胺基甲 酸醋樹脂、聚酯胺基甲酸酯樹脂、丙烯酸系樹脂、三聚氰 fe：樹脂等’使基材與近紅外線吸收層之緊貼性得以良好 之方式來加以選擇爲重要的，具體而言，構成基材與紅外 線吸收層之樹脂只要爲丙烯酸系的話，較宜選定丙烯酸 系、共聚合聚酯系、聚酯胺基甲酸酯系。 於該中間層中’以緊貼性與耐水性之提高爲目的，也可 以含有交聯劑而形成交聯構造。交聯劑可列舉：尿素系、 環氧系、三聚氰二胺系、異氰酸酯系。尤其，樹脂於高溫 與闻濕度下之白化或強度降低之情形下，因交聯劑而得到 的效果爲顯著的。還有，不使用交聯劑，樹脂也可以使用 -12- 1354123 修正本 具有自我交聯性之接枝共聚合樹脂。 於中間層中，基於使凹凸得以形成於表面而改善平滑性 之目的’也可以含有各種粒子。於中間層中所含之粒子， 例如’可列舉：二氧化矽、高嶺土、滑石、碳酸鈣、沸石、 氧化鋁等之無機粒子；丙烯酸、PMMA、耐綸、聚苯乙烯、 聚酯、苯并三聚氰二胺-甲醛縮合物等有機粒子。還有，基 於透明性之觀點，較宜選擇與所用之樹脂的折射率接近之 粒子。 φ再者’爲了將各種機能賦與中間層，也可以含有界面活 性劑、抗靜電劑、色素、紫外線吸收劑等。 中間層具有目的機能的情形，可以爲單層，必要的話， 也可以積層二層以上。 中間層之厚度只要具有目的機能的話，並未予以特別限 定，較宜爲Ο.ΟΙμηι以上、5μηι以下。厚度薄的情形下，作 爲中間層之機能變得難以表現，相反的，厚的情形下，透 明性則容易變得不良。 φ 設置中間層的方法較宜爲塗布法》塗布法能夠使用凹版 塗布方式、輕拂塗布方式、浸漬方式、噴霧塗布方式、淋 幕塗布方式、氣刀塗布方式、刀片塗布方式、逆輥塗布方 式等習知之塗布法，於薄膜之製程中設置塗布層之聯線塗 布方式、於薄膜製造後設置塗布層之離線塗布方式而加以 設置。此等方式之中，聯線塗布方式不僅於塗布面優異， 也藉由在塗布層中含有粒子，由於透明基材中變得沒有必 要含有粒子，因而能夠高度改善透明性。 (近紅外線吸收層） -13- 1354123 修正本 本發明之近紅外線吸收濾光片係直接地或使中間層介 於中間而將由主要含有近紅外線吸收色素與樹脂之組成物 而成的近紅外線吸收層設置於透明基材上。所謂該「主要 含有近紅外線吸收色素與樹脂」意指於該組成物中含有80 質量％以上之近紅外線吸收色素與樹脂。 ' 所謂近紅外線吸收色素係於波長800〜1 200nm之近紅 外線領域具有極大吸收的色素，可列舉：二亞胺鑰系、酞 菁系、二硫醇金屬錯鹽系、蔡酞菁（Naphthalocyanine)系、 @氮系、聚亞甲基系、蒽醌系、萘醌系、吡喃鑰系、噻喃 鑰系、方酸內鏺（Squarilium)系、克羅可鎗（Croconium) 系、四氫可林（Tetradehydookorine)系、三苯基甲院系、花 青系、偶氮系、胺鑰系等化合物。此等化合物可以單獨使 用或混合二種以上後使用，較宜含有近紅外線吸收領域之 吸收爲大的，並且吸收領域爲廣的，進而可見光領域之透 過率也爲高的下式（1)所示之二亞胺鑰鹽化合物：[In the formula, 'ring A and ring A' each independently represent a benzene ring, a naphthalene ring' or a pyridine ring 'R1 and R1' each independently represent a halogen atom, a nitro group; a cyano group, an aryl group having a carbon number of 6 to 30 carbon number An alkyl group of 1 to 8 or an alkoxy group having 1 to 8 carbon atoms, and R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, a cyano group, an aryl group having 6 to 30 carbon atoms, a diphenylamino group or a carbon. a number of 1 to 8 alkyl groups, X and X' each independently represent an oxygen atom, a sulfur atom, a selenium atom, a propane-2,2-diyl group, a butane-2,2-yl group, and a carbon number of 3 to 6 -1,1-diyl, -NH- or - NY!-, Y, Y, and Y! each independently represent an organic group having a carbon number of 1 to 30, and r and r each independently represent an integer of 0 to 2] The composition is characterized in that: a cyanine dye containing a trifluoromethanesulfonic acid compound or a bis(trifluoromethanesulfonyl)phosphinic acid compound as a relative ion in the composition is used as a near-infrared absorbing dye. The second invention is the near-infrared absorbing film of the first invention, wherein the near-infrared absorbing pigment contains a diimonium salt compound. The third invention is as disclosed in the second invention of the near-infrared absorption thin 1354123. The film of the invention wherein the diimine salt compound is a bis(trifluoromethanesulfonyl) ruthenium compound as a relative ion Diimine salt compound. The invention is the near-infrared absorbing film according to any one of the first to third invention, wherein the near-infrared absorbing pigment is a trifluoromethanesulfonic acid compound or a bis(trifluoromethanesulfonyl) fluorene. The amino acid compound is a cyanine dye which is a relative ion, and is contained in the near-infrared ray absorbing layer in an amount of 0.1% by mass or more and 10.0% by mass or less. The fifth invention is disclosed in the fourth aspect of the invention, wherein the near-infrared absorbing pigment comprises a bis(trifluoromethanesulfonyl) ruthenium amide compound as a relative ion diimine sulfonium salt. A compound and a cyanine dye which is a relative ion of a trifluoromethanesulfonic acid compound or a bis(trifluoromethanesulfonyl) liminium compound. The invention relates to a near-infrared absorbing film according to any one of the first to fifth aspects, wherein the resin constituting the near-infrared absorbing layer is an acrylic resin. [Effect of the Invention] φ When the near-infrared ray absorbing film of the present invention is provided as a near-infrared absorbing filter in front of the plasma display, it is the same as the conventional near-infrared absorbing filter, and is not only absorbed as much as possible from the display. The near-infrared rays that are emitted are also prevented from malfunctioning by the precision machine, and the color tone change due to heat can be greatly reduced, which contributes to the high image quality of the plasma display and improves the degree of freedom in designing the optical film. advantage. [Embodiment] Hereinafter, the present invention will be described in detail. (Transparent substrate) 1354123 In the present invention, the transparent substrate is not particularly limited, and the total light transmittance is preferably 80% or more and the haze is preferably 5% or less. In the case where the substrate is deteriorated in transparency, not only the brightness of the display is lowered, but also the sharpness of the image is deteriorated. Examples of such a transparent substrate include polyester, acrylic, cellulose, polyethylene, polypropylene, polyolefin, polyvinyl chloride, polycarbonate, phenol, and amine. A plastic film or sheet such as a formate or a glass, and a substrate of any two or more of these. The polyester film which is preferably a combination of heat resistance and flexibility is more preferably a polyethylene terephthalate film. The polyester-based film which is suitable as the transparent substrate used in the present invention is an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid or an ester thereof, which is a dicarboxylic acid component. An esterification reaction or a transesterification reaction with ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol or the like as a diol component, followed by a polyester condensation obtained by a polycondensation reaction After drying, it is melted by an extruder, and the unstretched sheet obtained by extruding the sheet from the T die is stretched at least along the uniaxial direction, followed by heat setting treatment and relaxation treatment. film. The film is particularly desirable as a biaxially stretched film, from the viewpoint of strength and the like. Examples of the stretching method include a tubular stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, and the like, but it is preferably a sequential biaxial stretching method based on planarity, dimensional stability, thickness unevenness, and the like. . For example, the sequential biaxially stretched film is stretched in the long axis direction, the glass transition temperature (Tg) of the polyester (Tg + 30 ° C), and is stretched by 2.0 to 5.0 times along the long axis direction. Next, using a tenter, after preheating, 1 20 to 150 ° C, and 1354123 in the width direction, the stretching of the line is corrected by 1.2 to 5.0 times. Further, after biaxial stretching, it can be thermally cured at a temperature of 22 ° C or higher and a melting point of -1 (TC or less, and then 3 to 8% in the width direction, and then produced. Further, the dimensional stability of the film in the long-axis direction can be further improved, and longitudinal relaxation treatment can also be used. In the film, in order to impart workability (for example, winding property after lamination), particles are preferably contained to form protrusions on the surface of the film. Examples of the particles contained in the film include inorganic particles such as cerium oxide, kaolin, talc, calcium carbonate, zeolite, and aluminum; acrylic acid, PMMA, nylon, polystyrene, polyester, and benzotrimer. The heat-resistant polymer particles such as a cyanodiamine-formaldehyde condensate are preferably contained in the film in view of transparency, and are preferably, for example, 1 pp m or more and 1 000 ppm or less. Furthermore, based on the viewpoint of transparency, it is preferable to select the resin to be used and the particle having a refractive index close to it. In addition, if necessary, various functions can be imparted to the film, and light stabilizer (anti-UV agent), pigment, antistatic can also be contained. In the present invention, when the antireflection layer is disposed on the opposite side of the near-infrared absorbing layer #, it is easy to cause deterioration of the near-infrared absorbing pigment according to ultraviolet rays incident from the outside, and is preferable to a transparent substrate. The ultraviolet absorber is contained in the organic ultraviolet absorber and the inorganic ultraviolet absorber. From the viewpoint of ensuring transparency, it is desirable to use an organic ultraviolet absorber (low molecular type, high molecular type). The ultraviolet absorber (low molecular type) is not particularly limited, and examples thereof include a benzotriazole system, a benzophenone system, a cyclic quinone imido ester system, and the like, and a combination thereof. From the point of view of the nature, it is preferable that the UV absorber is a benzotriazole-based or cyclic quinone-imido ester system, and further, in order to withstand the temperature at the time of substrate production, the decomposition temperature is higher than that of -10- 1354123. It is preferable to use a UV absorber of 2 9 ° C or higher. The content of the UV absorber is preferably such that the photo-degradation of the near-infrared absorbing layer can be controlled, and the 380 nm can be controlled. The transmittance of the wavelength is adjusted to 1% by weight. Specifically, in the transparent substrate, the content of the ultraviolet absorber is preferably 11 to 4% by mass, more preferably 0.3 to 2% by mass. If the ultraviolet absorbing dose is too small, the ultraviolet absorbing ability will become small, and when it is too large, the film may be yellowed or the film forming property may be lowered. The transparent substrate used in the present invention may be a single layer. The film may also be a composite film having two or more laminated layers and a central layer. In the case of a composite film, it has the advantage of being able to independently design the surface layer and the center layer function, for example, by containing particles only in a thin surface layer. When the surface is formed with irregularities and the workability is maintained, the entire composite film can further improve the transparency by substantially eliminating the inclusion of particles in the center layer having a large thickness. In addition, in the case of the ultraviolet absorbing ability, the ultraviolet absorbing agent is contained only in the center layer, and the precipitation of the ultraviolet absorbing agent toward the surface at the time of film production or over time can be reduced, and deterioration of heat resistance to the near-infrared absorbing layer can be suppressed. Bad influence. The method for producing the composite film is not particularly limited. However, when productivity is considered, in particular, the raw materials of the surface layer and the center layer are extruded from individual extruders, and a die is introduced to obtain an unstretched sheet, at least It is particularly desirable to align the uniaxial direction to laminate by the so-called co-extrusion method. The thickness of the transparent substrate varies depending on the material. In the case of using a polyester film, the lower limit is preferably 35 μm or more, more preferably 50 μm or more. -11 - 1354123 The upper limit of the thickness of the present invention is preferably 26 〇 μπι or less, more preferably 200 μηη or less. When the thickness is small, not only the workability is deteriorated, but also the residual solvent of the near-infrared ray absorbing layer is reduced. In the case of heating during drying, heat wrinkles occur in the film, and the planarity is liable to change. Bad. On the other hand, in the case where the thickness is thick, not only the cost surface is problematic, but also when it is taken up in a roll shape and stored, the flatness defect caused by the winding and bending is also likely to occur. (Intermediate layer) • Although the near-infrared ray absorbing filter of the present invention is constituted by a structure in which a near-infrared absorbing layer is laminated on a transparent substrate, the adhesion between the transparent substrate and the near-infrared absorbing layer is improved or the transparent substrate is formed. For the purpose of improving transparency, it is preferable to provide an intermediate layer. Further, in the case where the film does not contain particles, it is possible to obtain a high degree of transparency while maintaining the workability while providing an intermediate layer containing particles at the time of film production. The resin constituting the intermediate layer is exemplified by a polyester resin, a polyurethane urethane resin, a polyester urethane resin, an acrylic resin, a melamine resin: a resin, etc. It is important that the adhesion of the layer is selected in a good manner. Specifically, the resin constituting the substrate and the infrared absorbing layer is preferably an acrylic type, a copolymerized polyester type, or a polyester amine as long as it is an acrylic type. Carbamate system. In the intermediate layer, for the purpose of improving the adhesion and the water resistance, a crosslinking agent may be formed to form a crosslinked structure. Examples of the crosslinking agent include urea-based, epoxy-based, melamine-diamine-based, and isocyanate-based. In particular, in the case where the whitening or strength of the resin is lowered under high temperature and humidity, the effect obtained by the crosslinking agent is remarkable. Further, the resin may also be modified to have a self-crosslinking graft copolymer resin by using -12-1354123 without using a crosslinking agent. In the intermediate layer, the purpose of improving the smoothness based on the formation of the unevenness on the surface may also contain various particles. The particles contained in the intermediate layer, for example, may be exemplified by inorganic particles such as cerium oxide, kaolin, talc, calcium carbonate, zeolite, alumina, etc.; acrylic acid, PMMA, nylon, polystyrene, polyester, benzo Organic particles such as melamine-formaldehyde condensate. Further, from the viewpoint of transparency, it is preferred to select particles which are close to the refractive index of the resin to be used. Further, in order to impart various functions to the intermediate layer, an interface activator, an antistatic agent, a dye, an ultraviolet absorber, or the like may be contained. The intermediate layer has a function of the purpose, and may be a single layer or, if necessary, a layer of two or more layers. The thickness of the intermediate layer is not particularly limited as long as it has the intended function, and is preferably Ο.ΟΙμηι or more and 5μηι or less. In the case where the thickness is thin, the function as an intermediate layer becomes difficult to express, and conversely, in the case of a thick case, transparency is liable to become poor. φ The method of setting the intermediate layer is preferably a coating method. The coating method can use a gravure coating method, a light coating method, a dipping method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, and a reverse roll coating method. A conventional coating method is provided by providing an in-line coating method of a coating layer in a film process, and an off-line coating method in which a coating layer is provided after film production. Among these, the in-line coating method is excellent not only in the coated surface but also in the coating layer, and since the transparent substrate does not necessarily contain particles, the transparency can be highly improved. (Near-infrared absorbing layer) -13- 1354123 The near-infrared absorbing filter of the present invention is modified by a near-infrared absorbing layer mainly composed of a composition containing a near-infrared absorbing pigment and a resin, directly or with an intermediate layer interposed therebetween. Set on a transparent substrate. The term "mainly contains a near-infrared absorbing pigment and a resin" means that the composition contains 80% by mass or more of a near-infrared absorbing pigment and a resin. The near-infrared absorbing pigment is a dye having a maximum absorption in the near-infrared region having a wavelength of 800 to 1 200 nm, and examples thereof include a diimine key system, a phthalocyanine system, a dithiol metal salt system, and a Naphthalocyanine system. @Nitrogen, polymethylene, lanthanide, naphthoquinone, pyranyl, thiopyran, Squarilium, Croconium, tetrahydrocolin (Tetradehydookorine), a compound such as a triphenylmethine system, a cyanine system, an azo system, or an amine key system. These compounds may be used singly or in combination of two or more kinds, preferably containing a large absorption in the field of near-infrared absorption, and having a wide absorption field, and the transmittance in the visible light region is also high (1). Diimide salt compound:

-14- 1354123 修正本-14- 1354123 Revision

該式（1 )中之R1〜R8之具體例可列舉：（a )甲基、 乙基、正-丙基、異-丙基、正-丁基、異-丁基、第三-丁基、 正-戊基、正-己基、正-辛基、2 -羥乙基、2-氰乙基、3-羥 丙基、3-氰丙基、甲氧乙基、乙氧乙基、丁氧乙基等之烷 基；（b)苯基、氟苯基、氯苯基、甲苯基、二乙胺基苯基、 萘基等之芳基；（c)乙烯基、丙烯基、丁烯基、戊烯基等 #烯基：（d)苄基、對-氟苄基、對-氯苄基、苯丙基、萘 乙基等之芳烷基。 另外，R9〜R12可列舉：氫、氟、氯、溴、二乙胺基、 二甲胺基、氰基、硝基、甲基、乙基、丙基、三氟甲基、 甲氧基、乙氧基、丙氧基等。 另外，X_可列舉：氟離子、氯離子、溴離子、碘離子、 過氯酸鹽離子、六氟銻酸離子、六氟磷酸離子、四氟硼酸 離子、雙（三氟甲烷磺醯基）醯亞胺酸離子等。 此二亞胺鐺鹽化合物係市售品可取得的，例如，適宜 -15- 1354123 修正本 爲：日本化藥製之 Kayasorb IRG-022、IRG-023、IRG-024 ' IRG-068;日本 Carlit 製之 CIR- 1 080、CIR-108 卜 CIR- 1 08 3、 CIR-1085、 CIR-1085F 、 CIR-RL 等。 於此等化合物之中，藉由使近紅外線吸收層中含有三氟 甲烷磺酸化合物或雙（三氟甲烷磺醯基）醯亞胺酸化合物 '而提高耐濕熱性或耐熱性之觀點，較宜爲將雙（三氟甲烷 磺醯基）醯亞胺酸離子作成相對離子之二亞胺鑰鹽化合物。 將雙（三氟甲烷磺醯基）醯亞胺酸離子作成相對離子之 亞胺鑰鹽化合物，於該市售之二亞胺鑰鹽化合物之中， 可列舉：曰本化藥製之Kayasorb IRG-068;日本Carlit製 之 CIR-1085 、 CIR-1085F ' CIR-RL 等。 除了該式（1 )所示之二亞胺鑰鹽化合物以外，以近紅 外線領域吸收領域之擴大、色調之調整爲目的，本發明之 近紅外線吸收薄膜也可以添加其他之近紅外線吸收色素。 可以倂用該二亞胺鎗鹽系化合物之其他近紅外線吸收 色素可列舉：酞菁系化合物、二硫醇金屬錯鹽系化合物、 #青系化合物、萘酞菁系化合物、方酸內鑰系化合物、吡 喃鐵系化合物、噻喃鑰系化合物、克羅可鑰系化合物、靛 苯胺鉗合物系色素、茚醇系色素、偶氮系色素、偶氮鉗合 物系色素、鋁鹽系色素、醌系色素、蒽醌系色素、聚亞甲 基系色素、三苯基甲烷系色素等。此等色素之中，較宜爲 高溫高濕度下色素本身劣化少的酞菁系化合物、二硫醇金 屬錯鹽系化合物。使用容易劣化之色素的情形下，近紅外 領域透過率之經時安定性不僅成爲不良的，二亞胺鍚鹽系 化合物也發揮作爲淬滅劑（q u e n c h e r)作用而劣化，近紅外線 • 16 - 1354123 修正本 吸收薄膜將變黃。 此等色素之一部分係市售品可取得的，例如，可列舉： 日本觸媒製之酞菁系色素（IR-l、IR-2、IR-3、IR-4、IR-10、 IR-10A、IR-12、IR-14)、日本旭電化製之花青系色素 (TZ-111、114、119、121、123)、日本 Midori 化學製之 鎳錯鹽系色素（' MIR-111、MIR-121、MIR-102、 MIR-1011'MIR-1021)、日本山田化學製之花青系色素 (IR-301)、日本山本化成製之花青系色素（YKR-2900)、 •菁系色素（YKR-3 07 0、YKR- 3 08 1 ) » 另外，基於耐濕熱性或耐熱性提高之觀點，於該近紅外 線吸收色素之中，將三氟甲烷磺酸化合物或雙（三氟甲烷 磺醯基）醯亞胺酸化合物作成相對離子的花青色素。例如， 市售品可列舉：曰本化藥製之 CY-40MC(F) 、CYP4646 (F)或日本旭電化工業製之TZ-109D。 於本發明中，爲了控制設爲目的之近紅外線領域的吸 收、於可見光領域之透過率，於近紅外線吸收層厚度方向 g任意面上，較宜使近紅外線吸收色素之量存在於 0.0 lg/m2以上、1.0 g/m2以下之方式來調整。近紅外線吸收 色素之量少的情形下，於近紅外線領域的吸收能力將不足 的，相反的，多的情形下，於可見光領域的透過性將不足 而發生顯示器亮度降低的問題。 於本發明中，將近紅外線吸收層積層於透明基材之方法 可列舉：爲利用加熱近紅外線吸收色素與樹脂予以熔融而 設置於透明基材上的方法；先將近紅外線吸收色素與樹脂 溶於有機溶劑中，再於透明基材上進行塗布 '乾燥而積層 •17- 1354123 修正本 的塗布法。較宜爲容易得到近紅外線吸收層之寬度方向及 流動方向均勻性之塗布法。 於本發明中，用於近紅外線吸收層之樹脂，只要爲能使 近紅外線吸收色素得以均勻溶解或分散的話，並未予以特 別限定，能夠適合使用聚酯系、丙烯酸系、聚醯胺系 '聚 1安基甲酸酯系、聚烯烴系、聚碳酸酯系樹脂。其中，較宜 爲耐熱性優異的丙燒酸系樹脂。再者，樹脂之玻璃轉移溫 度較宜爲所用機器的保證使用溫度以上。 φ若玻璃轉移溫度爲機器使用溫度以下時，樹脂中所分散 的彼此色素將反應’或是樹脂吸收外部空氣中之水份等， 色素或黏著劑樹脂之劣化將變大。另外，於本發明中，只 要樹脂之玻璃轉移溫度爲機器使用溫度以上的話，並未予 以特別限定，尤以8 5 °C以上、1 6 0 °C以下特別理想。 還有，玻璃轉移溫度係遵循JIS K7121，利用微分掃描 熱量法（DSC )進行測定，玻璃轉移溫度係使用外插之玻 璃轉移開始溫度。測定之順序係進行如下之方式： φ 將約5mg之試料，密封於測定用鋁製鍋中之後，裝設於 微分掃描熱量計（MACScienceDSC3100S)內，於氮氣環 境中，以l〇°C/分鐘之速度，從30°C升溫至200°C，到達 2 00 °C後取出試料，立即進行急冷。再次.將此鍋裝設於微分 掃描熱量計內，以1 〇°C /分鐘之速度，從3 0°C起升溫，測 定玻璃轉移溫度（Tg : °C )。 用於近紅外線吸收層之樹脂的玻璃轉移溫度低於8 5 °C 之情形，引起色素與樹脂之相互作用、色素間之相互作用 等，色素之改性變得容易發生。另外，玻璃轉移溫度超過 -18- 1354123 修正本 160 °C之情形，若使該樹脂溶於溶劑中，於塗布於透明基材 上時予以充分乾燥的話，必須加熱至高溫，發生因基材之 熱皺摺所造成之平面性不佳，甚至色素劣化。另外，於低 溫進行乾燥之情形，乾燥時間變長、生產性變差，生產性 變得不良。另外，也有無法充分乾燥之可能性，溶劑將殘 •留於塗膜中，如上所述，樹脂外觀之玻璃轉移溫度將降低， 同樣的，色素之改性將變得容易發生。 另外，玻璃轉移溫度高的丙烯酸系樹脂將有缺乏柔軟 #、近紅外線吸收層因衝擊或彎曲而容易發生裂痕之問 題。如後所述，藉由於近紅外線吸收層中含有離子性液體， 賦與柔軟性變得可能。 相對於樹脂，近紅外線吸收層中之近紅外線吸收色素的 量較宜爲1質量％以上、10質量％以下。樹脂中之近紅外 線吸收色素之量少的情形下，爲了達成設爲目的之近紅外 線吸收能力，必須增加近紅外線吸收層之塗布量，若欲進 行充分乾燥的話，必須設爲高溫及/或長時間，變得容易引 f色素之劣化或基材之平面性不佳等。相反的，樹脂中之 近紅外線吸收色素之量多的情形下，色素間之相互作用變 強，即使減少近紅外線吸收層中之殘留溶劑量，也容易引 起色素之經時性變化。 於本發明中，近紅外線吸收層係於透明基材上，進行含 有近紅外線吸收色素、樹脂、及有機溶劑之塗布液的塗布、 乾燥所形成的。此時，使界面活性劑含於該塗布液中爲重 要的。藉由含有界面活性劑而改善近紅外線吸收層之塗布 外觀，尤其改善因微小氣泡所造成之脫落、由於污染物等 -19- 1354123 修正本 附著所造成之凹陷與乾燥步驟中之偏異。再者’界面活性 劑係藉由塗布乾燥而導致表面溶劑完全揮發而予以定域 化，一旦添加HLB低的界面活性劑時，不僅耐久性將提高， 也賦與平滑性，於近紅外線吸收層或/及相反面不形成表面 凹凸，作業性也變得良好，捲取成滾筒狀變得容易。 ' 雖然界面活性劑能夠適合使用陽離子系、陰離子系、非 離子系之習知界面活性劑，但是基於與近紅外線吸收色素 之劣化等問題，較宜爲無極性基之非離子系，再者，較宜 •I界面活性能力優異的矽系或氟系界面活性劑。 矽系界面活性劑可列舉：二甲基矽酮、胺基矽烷'丙烯 基矽烷、乙烯基苄基矽烷、乙烯基苄基胺基矽烷' 縮水甘 油基矽烷、锍基矽烷、二甲基矽烷 '聚二甲基矽氧烷、聚 烷氧基矽氧烷、氫化二烯改性矽氧烷、乙烯基改性矽氧烷、 羥基改性矽氧烷、胺基改性矽氧烷、羧基改性矽氧烷、鹵 化改性矽氧烷、環氧基改性矽氧烷、甲基丙烯醯氧基改性 矽氧院、毓基改性矽氧烷、氟改性矽氧烷、烷基改性矽氧 、苯基改性矽氧烷、環氧烷基改性矽氧院等。 氟系界面活性劑可列舉：四氟化乙烯、過氟烷基銨鹽、 過氟院基擴酸醯胺、過氟院基擴酸鈉鹽、過氟院基擴酸紳 鹽、過氣院基竣酸鹽、過贏院基擴酸鹽、過氟院基環氧乙 烷加成物、過氟烷基三甲基銨鹽、過氟烷基胺基擴酸鹽、 過氟院基碟酸醋、過氟烷基烷基化合物、過氟烷基烷基甜 菜鹼、過氟烷基鹵化物等。 相對於構成近紅外線吸收層之樹脂，界面活性劑之含量 較宜爲0.01質量％以上、2.00質量％以下。界面活性劑之 -20- 1354123 含量少的情形下，塗布外觀之改善或平滑性賦與之 不足，相反的，大多之情形下，具有近紅外線吸收 容易吸收水份且色素之劣化被加速之情形。 於本發明中，界面活性劑之HLB較宜爲2以上 下。HLB之下限値較宜爲3，尤以4特別理想。另一 • HLB之上限値較宜爲1 1，尤以10特別理想^ HLB 形下，表面予以防水化，能夠抑制因耐濕熱所造成 劣化，並且，容易賦與易滑性：過低之情形下，將 @活性能力之不足而造成平坦性變得不足之傾向 的，H LB高的情形下，不僅平滑性將不足，近紅外 層也變得容易吸收水份，色素之經時安定性容易變爲 還有，所謂 HLB係美國 Atlas Powder公司之 Griffin 命名爲 Hydorophil Lyophile Balance (親水 基均衡性），其係將界面活性劑分子中所含之親水 油基的均衡性作爲特性値而予以指標化之値，此値 油性變得越高，相反的，此値越高親水性變得越高 φ 對近紅外線吸收層表面之界面活性劑的定域化， 之種類或溶劑而有所不同，HLB之値於7附近，最 生，並且，初期乾燥緩慢者較容易發生。定域化之 夠藉由對照使用E S C A測得之近紅外線吸收層表面 面活性劑的量，與利用化學分析法測得之近紅外線 中界面活性劑的量而進行評估。 於本發明中，於近紅外線吸收層中含有三氟甲烷 合物或雙（三氟甲烷磺醯基）醯亞胺酸化合物中任 重要的。藉由含有該化合物，減低因近紅外線吸收 修正本 效果將 層變得 、12以 方面， 低的情 之色素 有因界 。相反 線吸收 丨不佳。 W. C. 基親油 基與親 越低親 〇 因樹脂 容易發 程度能 附近界 吸收層 磺酸化 一種爲 色素， -21 - 1354123 修正本 二亞胺鏺鹽化合物之熱所造成之劣化成爲可能的。 雖然作用機構尙未明確，推定於塗布液中或乾燥後，該化 合物j與二亞胺鏺鹽化合物之相對離子進行離子交換而使二 亞胺鎗鹽化合物予以安定化。二亞胺鎗鹽化合物之相對離 子爲三氟甲烷磺酸化合物或雙（三氟甲烷磺醯基）醯亞胺 •酸化合物之情形，認爲由於抑制其他色素或樹脂中所含之 低分子量相對離子與二亞胺鑰鹽化合物相對離子進行離子 交換’耐濕熱性或耐熱性將提高。 •於本發明中’使用習知之三氟甲烷磺酸化合物爲可能 的’可列舉：三氟甲烷磺酸鋰、三氟甲烷磺酸鉀、三氟甲 烷磺酸銀、三氟甲烷磺酸酐、三氟甲烷磺酸錫、三氟甲烷 磺酸銨、三氟甲烷磺酸釔、三氟甲烷磺酸鎘、三氟甲烷磺 酸-3,5-二氯-1-氟吡啶鏺、三氟甲烷磺酸2，2,2_三氟乙基 酯、三氟甲烷磺酸三甲基甲矽烷基酯、三氟甲烷磺酸鈉。 雙（三氟甲烷磺醯基）醯亞胺酸化合物可列舉：雙（三氟 甲烷磺醯基）醯亞胺酸鋰、雙（三氟甲烷磺醯基）醯亞胺 #銀、雙（三氟甲烷磺醯基）醯亞胺酸鈉、雙（三氟甲烷 磺醯基）醯亞胺酸鉀、雙（三氟甲烷磺醯基）醯亞胺酸鉋、 雙（三氟甲烷磺醯基）醯亞胺酸四甲基銨、雙（三氟甲院 磺醯基）醯亞胺酸乙基三甲基銨 '雙（三氟甲烷磺醯基） 醯亞胺酸二乙基二甲基銨、雙（三氟甲烷磺醯基）醯亞胺 酸三乙基甲基銨、雙（三氟甲院擴醯基）酿亞胺酸四乙基 銨、雙（三氟甲烷磺醯基）醯亞胺酸四丁基銨、雙（三氟 甲院擴醯基）醯亞胺酸N，N -二甲基吡咯院鐵、雙（三氟甲 烷磺醯基）醯亞胺酸N-乙基-N-甲基吡咯烷鑰、雙（三氟 -22- 1354123 甲院磺醯基）醯亞胺酸N，N_二甲基哌啶鎗、雙（ 擴醒基）醯亞胺酸乙基-N -甲基哌啶鎗、雙（ 擴醋基）酿亞胺酸四甲基鎸根、雙（三氟甲烷磺 亞胺酸四乙基鳞根、雙（三氟甲烷磺醯基）醯亞 基-2-甲基咪挫鑰、雙（三氟甲烷磺醯基）醯亞胺 • -2,3-二甲基咪嗤鎗、雙（三氟甲烷磺醯基）醯亞胺g 四甲基咪唑鑰。 於本發明中’只要雙（三氟甲烷磺醯基）醯亞 g (全氟烷磺醯基）甲基化物類爲工業上能取得 似於·雙（三氟甲烷磺醯基）醯亞胺酸化合物之構 可能的。 於本發明中，二亞胺鑰鹽化合物以外之近紅外 素也可以將三氟甲烷磺酸化合物或雙（三氟甲烷 醯亞胺酸中任一種作成相對離子而成的。於此情 然根據光學特性而限制含量，必要時，只要其他 別的三氟甲烷磺酸化合物或雙（三氟甲烷磺醯基 gp化合物中任一種的話即可。 於本發明中，於近紅外線吸收層中，較宜使三 酸化合物或雙（三氟甲烷磺醯基）醯亞胺酸化合 種含有0.1質量％以上、10.0質量％以下。若該 於0.1質量％的話，便難以得到耐熱性提高之效 的，若該化合物超過10質量％之情形下，發生因 良而使霧度變高的問題。 另外，三氟甲烷磺酸化合物或雙（三氟甲烷磺 亞胺酸化合物爲離子性液體之情形，藉由使近紅 修正本 三氟甲烷 三氟甲烷 醯基）醯 胺酸1-乙 酸1-乙基 ^ 1,2,3,4- !胺酸類、 的話，類 造爲使用 線吸收色 磺醯基） 形下，雖 途徑含有 )醯亞胺 氟甲烷磺 物中任一 化合物少 果。相反 溶解性不 醯基）醯 外線吸收 -23- 1354123 修正本 層中含有離子性液體，不僅近紅外線吸收層之柔軟性將提 高，便也可能減低因近紅外線吸收色素，尤其是二亞胺鑰 鹽化合物之熱所造成之劣化。藉由於近紅外線吸收層中含 有大量之離子，發揮作爲可塑劑作用而能賦與柔軟性，進 一步與二亞胺_鹽化合物之相對離子進行交換而得以安定 •化。二亞胺鎗鹽化合物之相對離子與離子性液體爲相同的 情形下，妨礙其他色素或樹脂中所含之低分子量相對離子 與二亞胺鑰鹽化合物相對離子的離子交換，耐熱性將提高》 φ 該離子性液體爲一種僅由陰離子、陽離子之離子所構成 的液體狀鹽。 構成離子性液體之陰離子種，例如，可列舉：Cr、Br·、 Γ、A1 C 1 4、A12 C 17 —、B F 4 —、P F 6、C 1 Ο 4 —、Ν Ο 3 -、C Η 3 C Ο CT、 CFsCOO' ' CH3SO3 ' CF3SO3 ' (CF3S02)2N·、( CF3SO2 ) 3 C ' ' A s F 6' ' SbF6·、NbF6.、TaF6.、F( HF) n-、( C N ) 2 N" ' C4F9S03-、（ C2F5S02 ) 2N·、C3F7CO〇-、（ CF3S02 ) ( CF3CO ) 化等。於此等離子種之中，包含含有氟原子之陰離子成分 #易得到低熔點之離子性化合物，便容易賦與近紅外線吸 收層之柔軟性。再者，二亞胺鑰鹽化合物之相對離子爲雙 (三氟甲烷磺醯基）醯亞胺酸之情形下，藉由使用相同的 相對離子，可以得到耐濕熱性或耐熱性之提高效果。 陽離子種具體可列舉：咪唑鑰、吡啶鑰。藉由使用由含 氮鑰、含硫鑰、含磷鑰而成的陽離子種，較宜將抗靜電效 果賦與近紅外線吸收層成爲可能的。 雖然如該離子性液體可以使用市售品，進行如下方式進 行合成也爲可能的。離子性液體之合成方法，只要能得到 •24- 1354123 修正本 目的之離子性液體的話，並未予以特別限定，一般而言， 可以使用如文獻”離子性液體-開發之最前線與未來〔（股 份）CMC出版發行〕所揭示之鹵化物法、氫酸化合物法、 酸酯法、錯鹽形成法與中和法等。 離子性化合物之含量較宜於近紅外線吸收層中含有0.1 •質量％以上、10.0質量％以下。若少於0.1質量％的話， 因含有離子性液體所造成之耐熱性提高或柔軟性賦與之效 果變得難以發現。相反的，超過10質量％之情形下，於近 0：外線吸收層表面將析出，與黏著劑之緊貼性將變得容易 降低。 於本發明中，近紅外線吸收層較宜藉由將含有樹脂、近 紅外線吸收色素、界面活性劑之塗布液，於透明基材上進 行塗布與乾燥後予以積層。基於塗布性，該塗布液必須藉 由有機溶劑加以稀釋。 該有機溶劑可列舉：（1)甲醇、乙醇、正-丙醇、異丙 醇、正-丁醇、十三烷醇、環己醇、2-甲基環己醇等醇類； 2)乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙二醇、 二丙二醇、甘油等二醇類；（3)乙二醇一甲基醚、乙二醇 一乙基醚、乙二醇一丁基醚、二乙二醇一甲基醚、二乙二 醇一乙基醚、二乙二醇丁基醚、乙二醇一甲基醚醋酸酯、 乙二醇一乙基醋酸酯、乙二醇一丁基醋酸酯、二乙二醇— 甲基醋酸酯、二乙二醇一乙基醚酸酯、二乙二醇一 丁基醋 酸酯等二醇醚類；（4)醋酸乙酯、醋酸異戊酯、醋酸_正_ 丁酯等酯類；（5)丙酮、甲基乙基酮、甲基異丁基酮、環 己酮、環戊酮、異佛爾酮、二丙酮醇等酮類；此等有機溶 -25- 1354123 修正本 劑能夠單獨使其或混合二種以上後使用。 相對使用於塗布液之全部有機溶劑，較宜含有3〇質量 %以上、80質量％以下之色素溶解性優異的酮類。其他之 有機溶劑較宜考量平坦性、乾燥性後加以選定。另外，有 機溶劑之沸點較宜爲6 0 °C以上、1 8 0 °C以下。沸點低的情 •形下’塗布時之塗布液的固形成分濃度將改變，塗布厚度 難以安定化。相反的，沸點高的情形下，殘存於塗膜中之 有機溶劑量將增加，經時安定性變得不良。 φ將近紅外線吸收色素與樹脂溶解或分散於有機溶劑中 的方法’可列舉：加熱下之攪拌、分散與粉碎的方法。藉 由加熱而能夠提高色素與樹脂之溶解性，防範因未溶解物 等所造成之塗布外觀的不良。另外，藉由進行分散及粉碎 而於0·3μπι以下之微粒狀態下將樹脂與色素分散於塗布液 中’形成透明性優異的層將成爲可能的。能夠使用習知之 分散機與粉碎機’具體而言，可列舉：球磨機、混砂機、 硏磨機、輥磨機、攪拌機 '乳化機、超音波均質機、均勻 f合機、珠磨機、濕式噴射磨機、塗料搖動機、蝶形混合 機、行星式混合機、亨舍爾（Henschel)混合機等。 於塗布液中存在污染物或Ιμιη以上未溶解物之情形，由 於塗布後之外觀變得不良，於進行塗布之前，必須利用過 濾器等進行去除。能夠使用合適之各種過濾器，較宜使用 去除99%以上之Ιμπι大小的污染物或未溶解物之過濾器。 進行含有Ιμιη以上污染物或未溶解物之塗布液的塗布、乾 燥之情形下，於其周圍發生凹陷等，將有成爲100〜1 000 μηι 大小缺陷之情形。 -26- 1354123 修正本 於塗布液中所含之樹脂與色素等固形成分濃度較宜爲 10質量％以上、30質量％以下。固形成分濃度低的情形 下，塗布後之乾燥費時，不僅生產性變差，或是殘存於塗 膜中之溶劑量增加，經時安定性也將變得不佳。相反的， 固形成分濃度高的情形下，塗布液之黏度變高，或平坦性 •不足，塗布外觀將變得不良。基於塗布外觀方面，塗布液 之黏度較宜爲l〇cps以上、300cps以下，較宜成爲此範圍 之方式來調整固形成分濃度、有機溶劑等。 鲁於本發明中’利用塗布法而將近紅外線吸收層積層於透 明基材上之方法，可採用凹版塗布方式、輕拂塗布方式、 浸漬方式、噴霧塗布方式、淋幕塗布方式、氣刀塗布方式、 刀片塗布方式、逆輥塗布方式、桿式塗布方式、邊緣塗布 方式等通常所用之方法。此等方法之中，較宜爲能夠進行 均勻塗布之凹版塗布方式，尤其逆凹版塗布方式特別理 想。另外，凹版之直徑較宜爲8 0 m m以下。直徑大的情形 下，於流動方向上，起棱條紋發生的頻率增加。 φ 近紅外線吸收層之乾燥後的塗布量並未予以特別限 定’下限較宜爲lg/m2,更佳爲3g/m2;上限較宜爲5〇g/m2, 更佳爲3 Og/m2。乾燥後之塗布量少的情形下，近紅外線之 吸收力容易變得不足。因此，一旦增加樹脂中之近紅外線 吸收色素的存在量時，由於色素間之距離變短，色素間之 相互作用變強。其結果，便容易引起色素之劣化等，經時 安定性將變得不良。相反的，乾燥後之塗布量多的情形下， 雖然近紅外線吸收能力足夠，但是於可見光領域之透明性 將降低’顯示器之亮度將降低。因此，一旦減低樹脂中之 -27- 1354123 修正本 近紅外線吸收色素的存在量時，雖然光學特性能夠加以調 節，但是乾燥容易變得不足。其結果，因塗膜中之殘留溶 劑而使得色素之經時安定性變得不良。另一方面，充分予 以乾燥之情形下，基材之平面性變得不良。 於透明基材上進行塗布液之塗布、乾燥的方法，可列 ‘舉：習知之熱風乾燥、紅外線加熱等，乾燥速度快的熱風 乾燥較佳。 於塗布後之初期等速乾燥階段中，較宜於2(TC以上、80 m 以下，使用 2m/秒以上、30m/秒以下之熱風進行乾燥。 加速進行初期乾燥（熱風溫度爲高的，熱風之風量爲大的） 之情形下，不僅界面活性劑於表面之定域化將難以發生， 耐久性提高或平滑性賦與之效果也將難以顯現，來自氣泡 之微小的塗布脫落、微小的逬開、裂痕等塗膜之微小缺陷 也將變得容易發生。相反的，減弱初期乾燥（熱風溫·度爲 低的，熱風之風量爲小的）之情形下，雖然外觀變得良好， 不僅耗費乾燥時間，成本面上將發生問題，急遽蒸發等問 #也將發生。不將界面活性劑添加於塗布液中之情形下， 該微小缺陷將容易發生，必須明顯減弱初期乾燥。 於減速乾燥之步驟中，具有較減弱初期乾燥更爲高溫， 使塗膜中的溶劑得以減少之必要，較佳之溫度爲1 2 0 °C以 上、180°C以下。尤以下限値爲140°C，上限値爲170°C特 別理想。溫度低的情形下，塗膜中之溶劑變得難以減少， 成爲殘留溶劑而使得色素之經時安定性變得不足。相反 的’高溫之情形下，不僅因熱雛摺而造成基材平面性不良， 近紅外線吸收色素也將因熱而劣化。另外，通過時間較宜 -28- 1354123 修正本 爲5秒以上、1 8 0秒以下。時間短的情形下，塗膜中之所 殘留的溶劑將變多，經時安定性將變得不良，相反的，時 間長的情形下，不僅生產性變得不良，基材上發生熱皺摺 而使得平面性也變得不良。基於生產性與平面性之觀點， 尤以通過時間之上限設爲3 0秒鐘特別理想。 ' 於乾燥之最後，較宜將熱風溫度設爲樹脂之玻璃轉移溫 度以下，平坦狀態下，較宜使基材之實際溫度設爲樹脂之 玻璃轉移溫度以下。依然維持高溫之狀態下，具有塗布面 0觸於滾筒表面時，平滑性變得不良，不僅缺陷等將發生， 也將發生卷縮等之情形。 (近紅外線吸收薄膜） 於本發明中，所謂近紅外線吸收薄膜係指8 00〜1 200nm 之近紅外線吸收領域的透過率爲低的、400nm〜800nm之可 見光吸收領域的透過率爲高的薄膜。近紅外線領域之透過 率越低越好，具體而言，較宜爲40%以下，更佳爲30%以 下。透過率高的情形下，從電漿顯示器所放射出的近紅外 #吸收將不足，無法防止使用近紅外線遙控之電子機器的 誤動作。 ^ 透過率之調整能夠根據該近紅外線吸收色素之種類、每 單位面積之近紅外線吸收色素的存在量而改變。 近紅外線吸收薄膜之色調，若以Lab表色系顯現時，a 値較宜爲-10.0〜+1〇.〇、b値較宜爲·10·0〜+10.0。若爲此 範圍的話，設置於電漿顯示器前面之情形下，較宜成爲天 然色。 調整色調之方法係藉由該近紅外線吸收色素之種類、每 -29- 1354123 修正本 單位面積之近紅外線吸收色素的存在量，再者，根據其他 色素之混合而能夠達成。還有’使用已著色於後述近紅外 線吸收薄膜之前面或裏面的黏著層而與抗電磁波薄膜、抗 反射薄膜、玻璃等其他構件相貼合之情形下，光學薄膜較 宜成爲天然色之方式來調整色調。 * 近紅外線吸收層之塗布外觀必須不存在直徑300μιη以 上缺陷，更佳爲不存在100 μπι尺寸缺陷之方式來進行。若 3 ΟΟμπι以上之缺陷設置於電漿顯示器前面時將成爲如亮點 #，缺陷將被顯著化。藉由黏著加工等貼合ΙΟΟμηι以上、 低於3 00 μιη之缺陷，將有利用透鏡效果等加以強調之情 形，必須盡可能不存在之方式來進行。另外，於塗布層之 淺條紋、不均勻等顯示器前面將被顯著化而成爲問題。 近紅外線吸收薄膜即使於高溫、高濕下予以長期放置， 近紅外線之透過率、可見光之透過率較宜不改變。高溫、 高濕下之經時安定性爲不良之情形下，不僅顯示器影像之 色調改變’也將有使用近紅外線遙控之電子機器誤動作的 f發明效果消失之情形。 針對使經時安定性得以良好化，雖然根據色素或樹脂的 種.類、添加劑而改變，能夠藉由控制於塗布液中所用之有 機溶劑的種類、塗布層的厚度、乾燥條件等而減低近紅外 線吸收層中之殘留溶劑量，或是藉由調整樹脂中色素之含 量而得以良好化。還有，雖然近紅外線吸收層之殘留溶劑 量越少越好，較宜成爲3質量％以下。若成爲3質量％以 下的話，實質上使經時安定性之差異得以消除。然而，爲 了進一步使殘留溶劑量得以降低，例如，一旦將乾燥設爲 -30- 1354123 修正本 過苛之條件時，使過濾器之平面性成爲不良等之弊病將發 生，利用如減壓乾燥之方法，生產性將降低。 於本發明中，也可以將其他機能賦與未設置近紅外線吸 收層之表面。具體而言，可列舉：抗靜電層、易接著層、 易滑層、抗反射層、抗電磁波層。藉由設置抗反射層、抗 •電磁波層，能夠減少光學濾光片之構件，不僅盡可能地廉 價，也能夠減少干涉光之表面而使電漿顯示器的畫質提 高。抗靜電層能夠減低近紅外線吸收層之形成時、後段步 #之污染物附著，使微小缺陷之減低或製造時之良率提高 成爲可能的。易接著層係利用黏著層而提高與其他構件相 貼合時之緊貼力，易滑層係使提高作業性成爲可能的。 能夠使用習知用於抗靜電層之抗靜電劑，於近紅外線吸 收薄膜製造時，捲取於滚筒上之際，由於抗靜電層與近紅 外線吸收層接觸，近紅外線吸收色素，尤其二亞胺鎗鹽化 合物將劣化，不宜使用陰離子系或陽離子系之界面活性劑 型、或4級銨鹽之陽離子系樹脂，必須含有π共軛系導電 g生高分子。π共軛系導電性高分子不會加速近紅外線吸收 色素，尤其是二亞胺鑰鹽之劣化，相反的，具有經時安定 性成爲良好之情形。π共軛系導電性高分子可列舉：苯胺 及/或其之衍生物、吡咯及/或其之衍生物、異硫茚及/或其 之衍生物、乙炔及/或其之衍生物、噻吩及/或其之衍生物 等。其中’較宜爲著色少的噻吩及/或其之衍生物。 於本發明中，基於遮斷從顯示器所放射出的有害電磁波 之目的下，可以與紅外線吸收層相同面，或是也可以於相 反面上直接設置導電層或藉由黏著劑而設置導電層。該導 •31 · 1354123 修正本 電層可以使用金屬篩網與導電薄膜中任一種，使用金屬飾 網之情形，必須具有開口率爲50%以上之金屬篩網導電 層。金屬篩網之開口率低的話，雖然電磁波屏蔽性變得良 好，具有光線透過率降低之問題，因此，爲了得到良好之 光線透過率，開口率必須爲50%以上。使用於本發明之金 •屬篩網’可以使用對導電性高的金屬箔進行蝕刻處理而作 成篩網狀的金屬篩網’也可以使用金屬纖維之織物狀篩 網，或是使用電鍍等手法而將金屬附著於高分子纖維表面 #纖維。雖然使用於該電磁波吸收層之金屬，其導電性爲 高的，只要安定性良好的話，任何金屬均可，並未予以特 別限定’基於加工性、成本等之觀點，較宜爲銅、鎳、鎢 等。 另外，使用導電薄膜之情形，透明導電層可以爲任一種 導電膜，較宜爲金屬氧化物。藉此，能夠得到更高的可見 光線透過率。另外，於本發明中，欲使透明導電層之導電 率提高之情形，較宜爲金屬氧化物/金屬/金屬氧化物之三 #以上重複構造。藉由將金屬予以多層化，除了維持高的 可見光透過率之同時，能夠得到導電性。可用於本發明。 只要金屬氧化物具有導電性與可見光透過性的話，任一種 金屬氧化物均可。例如，可列舉：氧化錫、銦氧化物、銦 錫氧化物、氧化錫、氧化鈦、氧化鉍等。以上係一例，並 未予以特別限定。另外，基於導電性之觀點，可用於本發 明之金屬層較宜爲含有金、銀及該等化合物。 再者，將導電層予以多層化之情形，例如重複層數爲三 層之情形，銀層之厚度較宜爲5〇〜200A，更佳爲50〜 -32- 1354123 修正本 ΙΟΟΑ。膜厚較其爲厚的情形，光線透過率將降低，薄的情 形’電阻値將上升。另外，金屬氧化物層之厚度較宜爲100 〜1000A，更佳爲100〜500A。較此厚度爲厚的情形下，著 色後色調將改變，薄的情形下，電阻値將上升。再者，予 以三層以上多層化之情形，例如，作成如金屬氧化物/銀/ •金屬氧化物/銀/金屬氧化物五層之情形，中心之金屬氧化 物厚度較宜較此外之金屬氧化物層的厚度爲厚。藉由進行 如此方式，整個多層膜之光線透過率將提高。 Φ 所謂抗反射層係指具有防止表面反射、防止螢光燈等映 入之機能。賦與該抗反射機能之方法雖然並未予以限定， 可以任意選擇，例如，可列舉：將折射率不同之層積層於 基材表面，利用該層界面上之反射光干涉而減低的方法； 及將凹凸賦與表面之方法。形成該方法之抗反射膜的方 法，大致上可列舉下列二種方法：一種方法係利用蒸鍍法 或濺鍍法，於基材表面形成抗反射膜之方法；另一種方法 係藉由將抗反射用塗布液塗布於基材表面、使其乾燥，形 f抗反射膜之方法。一般而言，認爲抗反射特性爲前者較 佳，經濟性則爲後者較佳，於本發明中，可以使用任一種 方法。 (光學濾光片） 於本發明中，所謂光學濾光片係設置於電漿顯示器前 面，其具有切斷從顯示器所發生的近紅外線、電磁波之同 時，具有爲了顯示器辨識性提高之抗反射、顏色再現性提 高等之機能，進一步具有顯示器保護之機能。 光學濾光片可列舉：利用黏著劑貼合抗反射薄膜、玻 -33- 1354123 璃、抗電磁波薄膜、近紅外線吸收薄膜的構造爲一 宜將紫外線吸收能力、顏色校正機能、顏色再現性 機能賦與黏著劑。另外，藉由使用將各個機能賦與 一面或相反面之複合薄膜，由於能夠進行構件數之 輕量化，基於成本降低之觀點，該複合薄膜係較佳 •形態。再者，爲了輕量化、高畫質化，不使用玻璃 貼合於電漿顯示器面板之直接貼合式濾光片也爲較 施形態。 φ藉由不使用玻璃而直接將光學濾光片貼合於電 器面板’雖然畫質提高及輕量化成爲可能的，由於 熱變得容易傳導，要求具有高度之耐熱性。然而， 發明之近紅外線吸收薄膜具有高度優異，直接貼合 片用也爲適合的。 實施例 接著，顯示本發明之實施例與比較例。另外，本 用的特性値之測定方法及效果之評估方法係如下所 y塗布液黏度> 將塗布液調節至20 °C，使用Β型黏度計（日本 器製之BL) ’利用轉子旋轉數60rpm進行測定。 <透過率〉 使用分光光度計（日立U-3500型），於波長1100〜 之範圍’使光照射於近紅外線吸收層側之方式來進 室內之空氣作爲對照透過率而進行測定。 <色調> 使用色差計（日本電色工業製之ZE-2000)，使 修正本 例，較 提高之 薄膜同 減低、 之實施 而直接 佳之實 漿顯示 面板之 由於本 式濾光 發明使 不： 東京計 2 0 0 n m 行，將 光照射 -34- 1354123 修正本 於近紅外線吸收層側之方式來進行’利用D65光源、10度 視野角進行測定。 <耐濕熱性> 測定於溫度60°C、濕度95%之氣體環境中放置500小 時後之色調，求出處理前後之色調變化量Δχ、ΔΥ。 • <耐熱性> 測定於溫度90 °C之氣體環境中放置5 00小時後之色 調，求出處理前後之色調變化量Ax' Ay。 φ：柔軟性> 將薄膜切斷成寬度1 〇mm，使近紅外線吸收層朝向外側 而捲繞於金屬棒，確認近紅外線吸收層有無裂痕。使用直 徑爲1〜20mm、間隔1mm之20根金屬棒，將裂痕不發生 之最小直徑設爲柔軟性之評估値。 參考例1 1 .透明基材之製造 (1 )含有紫外線吸收劑之母煉膠（mastorbatch)的調整 0 混合1 〇質量份之已乾燥的紫外線吸收劑（CYTEC公司 製之 CYASORB UV-3638; 2,2’-( 1，4 -伸苯基）雙（4H-3,1-苯并曙阱-4-酮））、90質量份之不含粒子的聚對苯二甲酸 乙二醇酯（PET )樹脂（日本東洋紡績製之ME 5 5 3 )，使 用混攪擠壓機，製作母煉膠。此時之擠壓溫度爲285 1， 擠壓時間爲7分鐘。 (2)易接著層形成用塗布液之調整 遵循下列方法而調製易接著層形成用塗布液。將95質 量份之對苯二甲酸二甲酯、95質量份之間苯二甲酸二甲 -35- 1354123 修正本 酯、35質量份之乙二醇、145質量份之新戊二醇、0.1質量 份之醋酸鋅與0.1質量份之三氧化銻進料於反應容器內， 於180°C耗時3小時進行酯交換反應。接著，添加6.〇質量 份之5 -磺基間苯二甲酸-5_鈉，於240 °C耗時1小時進行酯 交換反應後’進行聚縮合反應，得到聚酯樹脂。 ' 分別混合6 · 7質量份之所得到的3 0質量％聚酯樹脂水 分散液、40質量份之含有被亞硫酸碳酸氫鈉所封端基的異 氰酸酯之自我交聯型聚胺基甲酸酯樹脂的20質量％水溶 # (日本第一工業製藥製之Elastron H-3) 、0.5質量份之Specific examples of R1 to R8 in the formula (1) include (a) methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, and tert-butyl group. , n-pentyl, n-hexyl, n-octyl, 2-hydroxyethyl, 2-cyanoethyl, 3-hydroxypropyl, 3-cyanopropyl, methoxyethyl, ethoxyethyl, butyl An alkyl group such as oxyethyl; (b) an aryl group such as a phenyl group, a fluorophenyl group, a chlorophenyl group, a tolyl group, a diethylaminophenyl group or a naphthyl group; (c) a vinyl group, a propylene group, and a butene group; Base, pentenyl, etc. #alkenyl: (d) an aralkyl group such as benzyl, p-fluorobenzyl, p-chlorobenzyl, phenylpropyl or naphthylethyl. Further, examples of R9 to R12 include hydrogen, fluorine, chlorine, bromine, diethylamino, dimethylamino, cyano, nitro, methyl, ethyl, propyl, trifluoromethyl, methoxy, Ethoxy, propoxy, and the like. Further, X_ may be exemplified by fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hexafluoroantimonate ion, hexafluorophosphate ion, tetrafluoroborate ion, bis(trifluoromethanesulfonate) Indole acid ions and the like. The diimine sulfonium salt compound is commercially available, for example, the appropriate -15-1354123 amendment is: Kayasorb IRG-022, IRG-023, IRG-024 'IGG-068, manufactured by Nippon Kasei Co., Ltd.; Japan Carlit CIR- 1 080, CIR-108, CIR- 1 08 3, CIR-1085, CIR-1085F, CIR-RL, etc. Among these compounds, a viewpoint of improving moist heat resistance or heat resistance by including a trifluoromethanesulfonic acid compound or a bis(trifluoromethanesulfonyl) ruthenium amide compound in the near-infrared ray absorbing layer It is preferred to use a bis(trifluoromethanesulfonyl) ruthenium ion as a relatively ionic diimine salt compound. The bis(trifluoromethanesulfonyl) ruthenium ion is used as a relative ion imide salt salt compound. Among the commercially available diimine salt compounds, Kayasorb IRG manufactured by Sakamoto Chemical Co., Ltd. -068; CIR-1085, CIR-1085F 'CIR-RL, etc. made by Carlit, Japan. In addition to the diimine salt compound represented by the formula (1), the near-infrared absorbing film of the present invention may be added with other near-infrared absorbing dyes for the purpose of expanding the field of absorption in the near-infrared field and adjusting the color tone. Other near-infrared absorbing pigments which can be used for the diimide gun salt-based compound include a phthalocyanine-based compound, a dithiol metal-salt-based compound, a #cyanoid compound, a naphthalocyanine-based compound, and a squaraine internal key system. a compound, a pyrithione compound, a thiopyranyl compound, a Crocodyl compound, an indoleamine-based dye, a sterol-based dye, an azo dye, an azo-based dye, or an aluminum salt A pigment, an anthraquinone dye, an anthraquinone dye, a polymethylene dye, a triphenylmethane dye, or the like. Among these pigments, a phthalocyanine-based compound or a dithiol metal-missing salt-based compound which is less deteriorated by the pigment itself under high temperature and high humidity is more preferable. In the case of using a pigment which is easily deteriorated, the stability with respect to the transmittance in the near-infrared region is not only poor, but the diimine sulfonium salt compound also functions as a quencher and deteriorates, and near infrared rays • 16 - 1354123 Correct the absorbing film will turn yellow. Some of these pigments are commercially available, and examples thereof include phthalocyanine dyes (IR-l, IR-2, IR-3, IR-4, IR-10, IR- by Japanese catalyst). 10A, IR-12, IR-14), Cyanine pigments (TZ-111, 114, 119, 121, 123) made by Japan Asahi Chemical Co., Ltd., and Nickel's salt-based pigments (MIR-111, manufactured by Japan Midori Chemical Co., Ltd.) MIR-121, MIR-102, MIR-1011 'MIR-1021), Cyanine pigment (IR-301) manufactured by Yamada Chemical Co., Ltd., and Cyanine pigment (YKR-2900) manufactured by Yamamoto Chemical Co., Ltd., Japan Pigment (YKR-3 07 0, YKR- 3 08 1 ) » In addition, based on the improvement of heat and humidity resistance or heat resistance, a trifluoromethanesulfonic acid compound or bis(trifluoromethane) is used among the near-infrared absorbing pigments. The sulfonyl) ruthenium amide compound is used as a relative ionic cyanine pigment. For example, commercially available products include CY-40MC (F) manufactured by Sakamoto Chemical Co., Ltd., CYP4646 (F), or TZ-109D manufactured by Asahi Chemical Co., Ltd., Japan. In the present invention, in order to control the absorption in the near-infrared field and the transmittance in the visible light region, it is preferable to make the amount of the near-infrared absorbing pigment present on any surface of the near-infrared absorbing layer in the thickness direction g. 0 lg/m2 or more, 1. Adjust by 0 g/m2 or less. When the amount of the near-infrared absorption pigment is small, the absorption capacity in the near-infrared region will be insufficient. On the contrary, in many cases, the permeability in the visible light region will be insufficient, and the display brightness will be lowered. In the present invention, a method in which a near-infrared ray absorbing layer is laminated on a transparent substrate is a method in which a near-infrared absorbing pigment and a resin are melted and provided on a transparent substrate, and a near-infrared absorbing pigment and a resin are dissolved in an organic solvent. In the solvent, apply a coating on the transparent substrate to dry and laminate. 17- 1354123 Correct the coating method. It is preferred to apply a coating method in which the width direction of the near-infrared absorbing layer and the uniformity of the flow direction are easily obtained. In the present invention, the resin used for the near-infrared ray absorbing layer is not particularly limited as long as it can uniformly dissolve or disperse the near-infrared absorbing pigment, and a polyester-based, acrylic-based or polyamidiamine-based compound can be suitably used. A poly-l-based resin, a polyolefin-based or a polycarbonate-based resin. Among them, a propionic acid resin which is excellent in heat resistance is preferred. Further, the glass transition temperature of the resin is preferably higher than the guaranteed use temperature of the machine used. φ If the glass transition temperature is equal to or lower than the machine use temperature, the mutually dispersed pigment in the resin will react. Or the resin absorbs moisture in the outside air, and the deterioration of the dye or the adhesive resin will become large. Further, in the present invention, the glass transition temperature of the resin is not particularly limited as long as it is at least the machine use temperature, and particularly preferably 85 ° C or higher and 160 ° C or lower. Further, the glass transition temperature was measured in accordance with JIS K7121 by differential scanning calorimetry (DSC), and the glass transition temperature was an external glass transition starting temperature. The order of measurement was as follows: φ A sample of about 5 mg was sealed in a measuring aluminum pot, and then placed in a differential scanning calorimeter (MACScience DSC3100S) in a nitrogen atmosphere at 10 ° C/min. The speed was raised from 30 ° C to 200 ° C. After reaching 200 ° C, the sample was taken out and immediately quenched. once again. The pot was placed in a differential scanning calorimeter and the temperature was raised from 30 °C at a rate of 1 〇 ° C / minute to measure the glass transition temperature (Tg : ° C ). When the glass transition temperature of the resin used for the near-infrared absorbing layer is lower than 85 ° C, the interaction between the dye and the resin, the interaction between the dyes, and the like are caused, and the modification of the dye is likely to occur. In addition, the glass transition temperature exceeds -18-1354123. If the resin is dissolved in a solvent and is sufficiently dried when applied to a transparent substrate, it must be heated to a high temperature. The flatness caused by hot wrinkles is poor, and even the pigment is degraded. Further, in the case of drying at a low temperature, the drying time becomes long, the productivity is deteriorated, and the productivity is deteriorated. Further, there is a possibility that the solvent may not be sufficiently dried, and the solvent remains in the coating film. As described above, the glass transition temperature of the resin appearance is lowered, and similarly, the modification of the pigment is likely to occur. Further, the acrylic resin having a high glass transition temperature has a problem that the softness of the near-infrared absorbing layer is likely to be cracked due to impact or bending. As will be described later, by providing an ionic liquid in the near-infrared ray absorbing layer, flexibility can be imparted. The amount of the near-infrared absorbing pigment in the near-infrared ray absorbing layer is preferably 1% by mass or more and 10% by mass or less based on the resin. When the amount of the near-infrared absorbing pigment in the resin is small, it is necessary to increase the coating amount of the near-infrared ray absorbing layer in order to achieve the near-infrared absorbing ability for the purpose, and it is necessary to set the high-temperature and/or long-term to be sufficiently dried. The time becomes easy to cause deterioration of the pigment of the f or poor planarity of the substrate. On the other hand, in the case where the amount of the near-infrared absorbing pigment in the resin is large, the interaction between the dyes becomes strong, and even if the amount of residual solvent in the near-infrared ray absorbing layer is reduced, the temporal change of the pigment tends to occur. In the present invention, the near-infrared ray absorbing layer is formed on a transparent substrate, and is coated and dried by a coating liquid containing a near-infrared absorbing dye, a resin, and an organic solvent. At this time, it is important to include the surfactant in the coating liquid. The coating appearance of the near-infrared absorbing layer is improved by the inclusion of the surfactant, and in particular, the detachment caused by the microbubbles and the variation in the sag and drying steps caused by the adhesion of the contaminants, etc., -19-35442, are improved. Furthermore, the surfactant is localized by completely drying the surface solvent by coating drying. When a surfactant having a low HLB is added, not only the durability but also the smoothness is imparted to the near infrared absorbing layer. On the other hand, the surface unevenness is not formed on the opposite side, and the workability is also good, and it is easy to wind up into a roll shape. ' Although the surfactant can be suitably used as a conventional surfactant such as a cationic, anionic or nonionic surfactant, it is preferably a non-polar nonionic system based on problems such as deterioration of the near-infrared absorbing pigment. A suitable lanthanide or fluorine-based surfactant with excellent interfacial activity. Examples of the lanthanide surfactant include dimethyl fluorenone, amino decane 'propenyl decane, vinyl benzyl decane, vinyl benzyl amine decane 'glycidyl decane, decyl decane, dimethyl decane' Polydimethyloxane, polyalkoxydecane, hydrogenated diene modified alkane, vinyl modified alkane, hydroxyl modified alkane, amine modified alkane, carboxyl modified Alkoxysilane, halogenated modified alkane, epoxy modified alkane, methacryloxy modified alkoxy, thiol modified alkane, fluorine modified alkane, alkyl Modified oxime, phenyl modified decane, epoxy alkyl modified oxime, etc. Examples of the fluorine-based surfactant include tetrafluoroethylene, perfluoroalkylammonium salt, perfluoric acid-based extended acid amide, sodium fluoride-based sodium salt, and fluoride-based acid-expanded strontium salt. Sulfate, over-winning compound, acid fluoride, fluoride-based ethylene oxide adduct, perfluoroalkyltrimethylammonium salt, perfluoroalkylamine-based acid salt, perfluorinated base disk A vinegar, a perfluoroalkylalkyl compound, a perfluoroalkylalkylbetaine, a perfluoroalkyl halide, and the like. The content of the surfactant is preferably 0. 重量 relative to the resin constituting the near-infrared absorbing layer. 01% by mass or more, 2. 00% by mass or less. When the content of the surfactant -20- 1354123 is small, the improvement of the coating appearance or the smoothness of the coating is insufficient. On the contrary, in many cases, the near-infrared absorption absorbs water easily and the deterioration of the pigment is accelerated. . In the present invention, the HLB of the surfactant is preferably 2 or more. The lower limit of HLB is preferably 3, especially 4 is particularly desirable. The other • HLB upper limit 値 is preferably 1 1, especially 10 is particularly ideal ^ HLB shape, the surface is waterproof, can inhibit the deterioration caused by heat and humidity resistance, and easy to impart slippery: too low In the case where the H LB is high, not only the smoothness will be insufficient, but also the near-infrared layer will easily absorb water, and the stability of the pigment will be easy. In addition, the so-called HLB system of Griffin of Atlas Powder Company of the United States is named Hydorophil Lyophile Balance, which is characterized by the balance of the hydrophilic oil groups contained in the surfactant molecules as characteristics. Then, the slickability becomes higher, and conversely, the higher the hydrazine becomes, the higher the hydrophilicity is. φ The localization of the surfactant on the surface of the near-infrared absorbing layer differs depending on the kind or solvent, HLB It is near the 7th, the most raw, and the initial dryness is more likely to occur. The localization was evaluated by comparing the amount of the near-infrared absorbing layer surface active agent measured by using E S C A with the amount of the surfactant in the near-infrared ray measured by chemical analysis. In the present invention, it is important that the near-infrared ray absorbing layer contains a trifluoromethane compound or a bis(trifluoromethanesulfonyl) ruthenium amide compound. By containing this compound, the effect of correcting the effect by the near-infrared absorption is reduced, and the layer is low in color. On the contrary, the absorption of the line is not good. W.  C.  The base-lipophilic group and the pro-lower affinity are due to the proneness of the resin. The vicinity of the absorption layer is sulfonated. One is a pigment, -21 - 1354123 It is possible to correct the deterioration caused by the heat of the diimine salt compound. Although the mechanism of action is not clear, it is presumed that the compound j is ion-exchanged with the counter ion of the diimine sulfonium salt compound after the coating liquid or after drying, and the diimine gun salt compound is stabilized. The relative ion of the diimine gun salt compound is a trifluoromethanesulfonic acid compound or a bis(trifluoromethanesulfonyl) quinone imine acid compound, and it is considered that the low molecular weight relative to other pigments or resins is inhibited. The ions and the diimine salt compound are ion-exchanged with respect to ions, and the heat resistance or heat resistance is improved. • In the present invention, 'use of a conventional trifluoromethanesulfonic acid compound is possible', and examples thereof include lithium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, silver trifluoromethanesulfonate, trifluoromethanesulfonic anhydride, and the like. Sodium fluoromethanesulfonate, ammonium trifluoromethanesulfonate, cesium trifluoromethanesulfonate, cadmium trifluoromethanesulfonate, 3,5-dichloro-1-fluoropyridinium trifluoromethanesulfonate, trifluoromethanesulfonate Acid 2,2,2-trifluoroethyl ester, trimethylmethanesulfonyl trifluoromethanesulfonate, sodium trifluoromethanesulfonate. The bis(trifluoromethanesulfonyl) ruthenium amide compound may be exemplified by lithium bis(trifluoromethanesulfonyl) ruthenate, bis(trifluoromethanesulfonyl) quinone imine #银,双(三Sodium fluoromethanesulfonyl) sulphonate, potassium bis(trifluoromethanesulfonyl) phthalimidate, bis(trifluoromethanesulfonyl) phthalic acid, bis(trifluoromethanesulfonyl) Tetramethylammonium imidate, bis(trifluoromethyl sulfonyl) phthalimidoethyl trimethylammonium bis(trifluoromethanesulfonyl) phthalimide diethyl dimethyl Ammonium, bis(trifluoromethanesulfonyl) ruthenium imidate, triethylmethylammonium, bis(trifluoromethyl), tetraethylammonium imidate, bis(trifluoromethanesulfonyl) Tetrabutylammonium imidate, bis(trifluoromethyl) ruthenium imidate N,N-dimethylpyrrole iron, bis(trifluoromethanesulfonyl) ruthenic acid N-B --N-methylpyrrolidine, bis(trifluoro-22- 1354123 sulfonyl) ruthenium N,N-dimethylpiperidine gun, double (opening) ruthenium imidate Base-N-methyl piperidine gun, double (expanded vinegar) Alfalfa root, bis(trifluoromethanesulfonate tetraethyl sulphate, bis(trifluoromethanesulfonyl) fluorenylene-2-methylidene, bis(trifluoromethanesulfonyl)pyrene Amine-2,3-dimethylimidazole gun, bis(trifluoromethanesulfonyl) quinone imine g tetramethylimidazole key. In the present invention, as long as bis(trifluoromethanesulfonyl)pyrene g (perfluoroalkylsulfonyl) methide is industrially possible to obtain a structure similar to that of bis(trifluoromethanesulfonyl) ruthenium amide. In the present invention, diimine salt The near-infrared fluoresin other than the compound may be formed by using any one of a trifluoromethanesulfonic acid compound or bis(trifluoromethane sulfilimine) as a relative ion. The content is limited according to optical characteristics, and if necessary, as long as necessary Any other trifluoromethanesulfonic acid compound or bis(trifluoromethanesulfonyl gp compound) may be used. In the present invention, in the near infrared absorbing layer, it is preferred to use a triacid compound or bis(trifluoro). Methanesulfonyl) ruthenium amide contains 0. 1% by mass or more, 10. 0% by mass or less. If it should be 0. When the amount is 1% by mass, it is difficult to obtain an effect of improving heat resistance. When the compound exceeds 10% by mass, the problem of high haze is caused. In addition, in the case of a trifluoromethanesulfonic acid compound or a bis(trifluoromethanesulfonimide compound as an ionic liquid, the trifluoromethane trifluoromethanesulfonyl group is modified by making a near red) lysine 1-acetic acid 1- Ethyl ^ 1,2,3,4-! Aminic acid, if it is used in the form of a line-absorbing sulfonyl group, although the route contains a compound of quinone imine fluoromethane sulfonate. On the contrary, the solubility is not fluorenyl) 醯 external absorption -23- 1354123 Correction This layer contains ionic liquid, not only the softness of the near-infrared absorbing layer will be improved, but also the absorption of pigment by near-infrared rays, especially the diimine key Deterioration caused by the heat of the salt compound. Since the near-infrared ray absorbing layer contains a large amount of ions, it functions as a plasticizer to impart flexibility, and is further stabilized by exchange with the opposite ions of the diimine-salt compound. When the relative ion of the diimine gun salt compound is the same as that of the ionic liquid, the ion exchange of the low molecular weight relative ion contained in the other dye or resin and the ion of the diimine salt compound is hindered, and the heat resistance is improved. φ The ionic liquid is a liquid salt composed only of anions and cation ions. Examples of the anionic species constituting the ionic liquid include Cr, Br·, hydrazine, A1 C 1 4, A12 C 17 —, BF 4 —, PF 6 , C 1 Ο 4 —, Ν Ο 3 −, C Η . 3 C Ο CT, CFsCOO' 'CH3SO3 'CF3SO3 ' (CF3S02)2N·, ( CF3SO2 ) 3 C ' ' A s F 6' ' SbF6·, NbF6. , TaF6. , F( HF) n-, (C N ) 2 N" 'C4F9S03-, (C2F5S02) 2N·, C3F7CO〇-, (CF3S02) (CF3CO). Among the plasma species, an anionic component containing a fluorine atom, an ionic compound having a low melting point, is easily obtained, and the flexibility of the near-infrared absorbing layer is easily imparted. Further, in the case where the relative ion of the diimine salt compound is bis(trifluoromethanesulfonyl) ruthenium, the effect of improving moist heat resistance or heat resistance can be obtained by using the same counter ion. Specific examples of the cationic species include an imidazole key and a pyridyl key. By using a cationic species consisting of a nitrogen-containing key, a sulfur-containing key, and a phosphorus-containing key, it is preferable to impart an antistatic effect to the near-infrared absorbing layer. Although a commercially available product can be used as the ionic liquid, it is also possible to carry out the synthesis as follows. The method for synthesizing the ionic liquid is not particularly limited as long as it can obtain the ionic liquid of the purpose of the modification of the object. In general, it can be used as the front line and the future of the literature "ionic liquid-development" ( The shares are disclosed in the CMC publication, the halide method, the hydrogen acid compound method, the acid ester method, the salt formation method, the neutralization method, etc. The content of the ionic compound is preferably in the near-infrared absorbing layer. 1 • More than mass%, 10. 0% by mass or less. If less than 0. When the amount is 1% by mass, the heat resistance due to the ionic liquid is increased or the effect of the softness is difficult to find. On the other hand, in the case of more than 10% by mass, at about 0: the surface of the outer absorbent layer will precipitate, and the adhesion to the adhesive will be easily lowered. In the present invention, the near-infrared ray absorbing layer is preferably applied by coating and drying a coating liquid containing a resin, a near-infrared absorbing dye, and a surfactant on a transparent substrate. The coating liquid must be diluted by an organic solvent based on the coating property. The organic solvent may, for example, be: (1) an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tridecyl alcohol, cyclohexanol or 2-methylcyclohexanol; Glycols such as diol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin; (3) ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Alcohol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate , glycol ethers such as ethylene glycol monobutyl acetate, diethylene glycol methyl acetate, diethylene glycol monoethyl ether ester, diethylene glycol monobutyl acetate; (4) acetic acid Ethyl ester, isoamyl acetate, esters such as _-n-butyl acetate; (5) acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, isophorone, two Ketones such as acetol; these organic solvents -25-1354123. This agent can be used alone or in combination of two or more. The ketone which is excellent in the dye solubility of 3 〇% by mass or more and 80% by mass or less is preferably contained in the total amount of the organic solvent to be used in the coating liquid. Other organic solvents are preferably selected after considering flatness and dryness. Further, the boiling point of the organic solvent is preferably 60 ° C or more and 180 ° C or less. When the boiling point is low, the solid concentration of the coating liquid at the time of coating is changed, and the coating thickness is difficult to stabilize. On the other hand, in the case where the boiling point is high, the amount of the organic solvent remaining in the coating film is increased, and the stability over time becomes poor. The method of dissolving or dispersing the near-infrared absorbing dye and the resin in an organic solvent is exemplified by a method of stirring, dispersing, and pulverizing under heating. By heating, the solubility of the dye and the resin can be improved, and the coating appearance due to undissolved matter or the like can be prevented. In addition, by dispersing and pulverizing, the resin and the dye are dispersed in the coating liquid in a state of fine particles of 0.3 μm or less, and it is possible to form a layer having excellent transparency. The conventional dispersing machine and the pulverizer can be used. Specifically, a ball mill, a sand mixer, a honing machine, a roll mill, a mixer emulsifier, an ultrasonic homogenizer, a uniform f-joint, a bead mill, and the like can be cited. Wet jet mills, paint shakers, butterfly mixers, planetary mixers, Henschel mixers, and the like. In the case where a contaminant or an undissolved substance of Ιμηη or more is present in the coating liquid, the appearance after coating becomes poor, and it is necessary to remove it by a filter or the like before coating. It is possible to use a filter which is more than 99% of Ιμπι size or undissolved by using a suitable filter. When coating or drying of a coating liquid containing a contaminant or an undissolved material of Ιμηη or more is carried out, a depression or the like is formed around the coating liquid, and a defect of a size of 100 to 1 000 μm may be obtained. -26- 1354123 The concentration of the solid component such as the resin and the pigment contained in the coating liquid is preferably 10% by mass or more and 30% by mass or less. When the solid content concentration is low, drying after coating is time-consuming, and not only the productivity is deteriorated, but also the amount of the solvent remaining in the coating film is increased, and the stability over time is also poor. On the other hand, in the case where the solid content concentration is high, the viscosity of the coating liquid becomes high, or the flatness is insufficient, and the coating appearance becomes poor. The viscosity of the coating liquid is preferably 1 〇 cps or more and 300 cps or less, and the solid content concentration, the organic solvent, and the like are preferably adjusted in such a range. In the present invention, the method of coating the near-infrared absorbing layer on the transparent substrate by the coating method may be a gravure coating method, a light smear coating method, a dipping method, a spray coating method, a curtain coating method, or an air knife coating method. The method generally used, such as a blade coating method, a reverse roll coating method, a rod coating method, and an edge coating method. Among these methods, a gravure coating method capable of uniform coating is preferable, and in particular, a reverse gravure coating method is particularly desirable. Further, the diameter of the intaglio is preferably 80 mm or less. In the case of a large diameter, the frequency at which the rib stripes occur increases in the flow direction. The coating amount after drying of the φ near-infrared absorbing layer is not particularly limited. The lower limit is preferably lg/m2, more preferably 3 g/m2; the upper limit is preferably 5 〇g/m2, more preferably 3 Og/m2. When the amount of coating after drying is small, the absorption of near-infrared rays tends to be insufficient. Therefore, when the amount of the near-infrared absorbing pigment in the resin is increased, the distance between the pigments becomes shorter, and the interaction between the pigments becomes stronger. As a result, deterioration of the dye or the like is likely to occur, and stability over time is deteriorated. On the contrary, in the case where the amount of coating after drying is large, although the near-infrared absorbing ability is sufficient, the transparency in the visible light field is lowered, and the brightness of the display is lowered. Therefore, when the amount of the near-infrared absorbing pigment is corrected in the resin, the optical properties can be adjusted, but the drying tends to be insufficient. As a result, the stability of the dye over time is deteriorated due to the residual solvent in the coating film. On the other hand, in the case where it is sufficiently dried, the planarity of the substrate becomes poor. The method of applying and drying the coating liquid on a transparent substrate can be exemplified by conventional hot air drying, infrared heating, etc., and hot air drying with a high drying speed is preferred. In the initial constant-speed drying stage after coating, it is more preferable to use 2 (TC or more, 80 m or less, and to use hot air of 2 m/sec or more and 30 m/sec or less to dry. Accelerate initial drying (hot air temperature is high, hot air) In the case where the amount of the air is large, not only the localization of the surfactant on the surface is difficult to occur, but also the effect of improving durability or smoothness is hard to be revealed, and the coating from the bubbles is slightly peeled off, and the flaws are small. In the case of a small defect such as a crack or a crack, it is likely to occur. On the contrary, when the initial drying is weakened (the hot air temperature is low and the amount of hot air is small), the appearance is good, and it is not only expensive. Drying time, problems will occur on the cost side, and rapid evaporation will also occur. If the surfactant is not added to the coating liquid, the micro defects will easily occur, and the initial drying must be significantly weakened. In the step, it is necessary to reduce the drying temperature at a higher temperature to reduce the solvent in the coating film, and the temperature is preferably 120 ° C or more and 180 ° C or less. It is particularly preferable that the temperature is limited to 140 ° C and the upper limit 値 is 170 ° C. When the temperature is low, the solvent in the coating film becomes difficult to be reduced, and the solvent becomes a residual solvent, so that the stability of the pigment is insufficient. In the case of high temperature, not only the flatness of the substrate is caused by heat shrinkage, but also the near-infrared absorbing pigment is also deteriorated by heat. In addition, the time is better than -28-1354123, and the correction is 5 seconds or more and 1880 seconds. In the case where the time is short, the amount of solvent remaining in the coating film will increase, and the stability will become poor over time. On the contrary, in the case of a long time, not only the productivity becomes poor, but heat is generated on the substrate. Wrinkles make the flatness also poor. From the viewpoint of productivity and flatness, it is particularly preferable to set the upper limit of the passage time to 30 seconds. 'At the end of drying, it is preferable to set the hot air temperature to resin. When the glass transition temperature is lower than the glass transition temperature, it is preferable to set the actual temperature of the substrate to be lower than the glass transition temperature of the resin. When the coated surface 0 is in contact with the surface of the drum, the smoothness is deteriorated while maintaining the high temperature. In the present invention, the near-infrared absorbing film means a low transmittance in the field of near-infrared absorption of 800 to 1 200 nm. A film having a high transmittance in the visible light absorption field of 400 nm to 800 nm. The lower the transmittance in the near-infrared field, the better, specifically, it is preferably 40% or less, more preferably 30% or less. Next, the near-infrared # absorption from the plasma display will be insufficient, and it is impossible to prevent malfunction of the electronic device using the near-infrared remote control. ^ The transmittance can be adjusted according to the type of the near-infrared absorbing pigment, and the near-infrared per unit area. The amount of absorption of the pigment changes. The color of the near-infrared absorbing film, if expressed in the Lab color system, a 値 is preferably -10. 0~+1〇. 〇, b値 is preferably ·10·0~+10. 0. If it is in this range, it should be a natural color when it is placed in front of the plasma display. The method of adjusting the color tone is based on the type of the near-infrared absorbing pigment, and the amount of the near-infrared absorbing pigment per unit area is corrected per -29 to 1354123, and further, it can be achieved by mixing other pigments. Further, in the case where an adhesive layer which has been colored on the front surface or the inside of the near-infrared ray absorbing film described later is bonded to other members such as an electromagnetic wave preventing film, an antireflection film, and glass, the optical film is preferably a natural color. Adjust the color tone. * The coating appearance of the near-infrared absorbing layer must be such that there is no defect of 300 μm or more in diameter, and more preferably, there is no dimensional defect of 100 μm. If a defect of 3 ΟΟμπι or more is set in front of the plasma display, it will become a bright spot #, and the defect will be noticed. When a defect of ΙΟΟμηι or more and less than 300 μm is bonded by adhesion processing or the like, it is emphasized that the lens effect or the like is emphasized, and it is necessary to carry out the method as much as possible. In addition, the front side of the display such as light streaks and unevenness of the coating layer is noticeable and becomes a problem. The near-infrared absorbing film is placed for a long period of time even under high temperature and high humidity, and the transmittance of near-infrared rays and the transmittance of visible light are preferably not changed. In the case where the stability over time under high temperature and high humidity is bad, not only the color tone of the display image is changed, but also the effect of the invention in which the electronic device using the near-infrared remote control malfunctions disappears. In order to improve the stability over time, although depending on the pigment or resin species. The amount of the residual solvent in the near-infrared absorbing layer can be reduced by controlling the type of the organic solvent used in the coating liquid, the thickness of the coating layer, the drying conditions, etc., or by adjusting the coloring matter in the resin. The content is improved. In addition, the amount of residual solvent in the near-infrared ray absorbing layer is preferably as small as possible, and is preferably 3% by mass or less. If it is 3% by mass or less, the difference in stability over time is substantially eliminated. However, in order to further reduce the amount of the residual solvent, for example, when the drying is set to -30 - 1354123 to correct the excessively severe conditions, the planarity of the filter is deteriorated, etc., and the drying is performed by, for example, drying under reduced pressure. Method, productivity will be reduced. In the present invention, other functions may be imparted to the surface on which the near-infrared absorbing layer is not provided. Specifically, an antistatic layer, an easy-adhesion layer, an easy-slip layer, an antireflection layer, and an anti-electromagnetic wave layer are mentioned. By providing the antireflection layer and the anti-electromagnetic wave layer, the members of the optical filter can be reduced, and the surface of the interference light can be reduced as much as possible, and the image quality of the plasma display can be improved. The antistatic layer can reduce the adhesion of contaminants in the formation of the near-infrared absorbing layer and the subsequent step, and it is possible to reduce the micro defects or improve the yield at the time of manufacture. The easy-adhesion layer utilizes an adhesive layer to improve the adhesion to other members, and the easy-to-slip layer makes it possible to improve workability. It is possible to use an antistatic agent conventionally used for an antistatic layer. When the near infrared ray absorbing film is produced, it is wound on the drum, and the near infrared absorbing pigment, especially the diimine, is contacted by the antistatic layer and the near infrared absorbing layer. The gun salt compound is deteriorated, and it is not preferable to use an anionic or cationic surfactant type or a fourth-order ammonium salt cationic resin, and it is necessary to contain a π-conjugated conductive g-polymer. The π-conjugated conductive polymer does not accelerate the deterioration of the near-infrared absorbing pigment, especially the diimine-based salt, and conversely, it has a good stability over time. Examples of the π-conjugated conductive polymer include aniline and/or a derivative thereof, pyrrole and/or a derivative thereof, isothiopurine and/or a derivative thereof, acetylene and/or a derivative thereof, and thiophene And / or its derivatives. Among them, thiophene and/or a derivative thereof which is less colored is preferable. In the present invention, the conductive layer may be provided directly on the opposite side of the infrared absorbing layer or the conductive layer may be provided on the opposite side based on the purpose of blocking the harmful electromagnetic waves emitted from the display. This guide • 31 · 1354123 Correction This electrical layer can use either a metal mesh or a conductive film. In the case of a metal mesh, it must have a metal mesh conductive layer with an aperture ratio of 50% or more. When the opening ratio of the metal mesh is low, the electromagnetic wave shielding property is good and the light transmittance is lowered. Therefore, in order to obtain a good light transmittance, the aperture ratio must be 50% or more. The gold-based screen used in the present invention can be formed by etching a highly conductive metal foil to form a mesh-shaped metal screen. It is also possible to use a metal-like fabric-like screen or a plating method. The metal is attached to the surface of the polymer fiber #fiber. The metal used in the electromagnetic wave absorbing layer has high conductivity, and any metal may be used as long as the stability is good, and is not particularly limited. From the viewpoints of workability, cost, etc., it is preferably copper or nickel. Tungsten, etc. Further, in the case of using a conductive film, the transparent conductive layer may be any conductive film, and is preferably a metal oxide. Thereby, a higher visible light transmittance can be obtained. Further, in the present invention, in order to increase the conductivity of the transparent conductive layer, it is preferable to repeat the structure of three or more metal oxide/metal/metal oxide. By multilayering the metal, conductivity can be obtained while maintaining high visible light transmittance. It can be used in the present invention. Any metal oxide may be used as long as the metal oxide has conductivity and visible light transmittance. For example, tin oxide, indium oxide, indium tin oxide, tin oxide, titanium oxide, cerium oxide, or the like can be given. The above is an example and is not particularly limited. Further, from the viewpoint of electrical conductivity, the metal layer which can be used in the present invention preferably contains gold, silver and the like. Further, in the case where the conductive layer is multi-layered, for example, in the case where the number of layers is three, the thickness of the silver layer is preferably from 5 〇 to 200 Å, more preferably from 50 。 to 32 。 。 。 。 。. When the film thickness is thicker than this, the light transmittance will decrease, and the thin shape 'resistance 値 will rise. Further, the thickness of the metal oxide layer is preferably from 100 to 1,000 A, more preferably from 100 to 500 Å. In the case where the thickness is thicker, the color tone will change after coloring, and in the case of thinness, the resistance 値 will rise. Furthermore, in the case where three or more layers are multilayered, for example, in the case of five layers of metal oxide/silver/metal oxide/silver/metal oxide, the thickness of the metal oxide in the center is more preferable than the metal oxidation. The thickness of the layer is thick. By doing so, the light transmittance of the entire multilayer film will increase. Φ The anti-reflection layer refers to a function that prevents surface reflection and prevents reflection of fluorescent lamps. The method for imparting the anti-reflection function is not limited, and may be arbitrarily selected. For example, a method in which a layer having a different refractive index is laminated on a surface of a substrate and the reflection light at the interface of the layer is reduced is used; The method of assigning bumps to the surface. The method for forming the antireflection film of the method is generally exemplified by the following two methods: one is a method of forming an antireflection film on the surface of a substrate by an evaporation method or a sputtering method; and the other method is by using an anti-reflection film. A method in which a coating liquid for reflection is applied to a surface of a substrate and dried to form an anti-reflection film. In general, the antireflection property is considered to be superior to the former, and the economy is preferred to the latter, and in the present invention, either method can be used. (Optical Filter) In the present invention, the optical filter is provided in front of the plasma display, and has an anti-reflection for improving the visibility of the display while cutting off near-infrared rays and electromagnetic waves generated from the display. The function of improving color reproducibility and the like further has the function of display protection. The optical filter can be exemplified by a structure in which an antireflection film, a glass-33- 1354123 glass, an anti-electromagnetic wave film, and a near-infrared absorbing film are bonded by an adhesive, and the ultraviolet absorbing ability, the color correcting function, and the color reproducibility function are suitable. With an adhesive. Further, by using a composite film in which each function is imparted to one surface or the opposite surface, the number of components can be reduced, and the composite film is preferable in terms of cost reduction. Further, in order to reduce the weight and high image quality, a direct-bonding filter that does not use a glass bonded to a plasma display panel is also a preferred embodiment. φ directly bonds the optical filter to the electric panel by using no glass. Although the image quality is improved and the weight is reduced, heat is easily transmitted, and high heat resistance is required. However, the near-infrared absorbing film of the invention is highly excellent, and is also suitable for direct bonding. EXAMPLES Next, examples and comparative examples of the present invention are shown. In addition, the measurement method and the effect evaluation method of the present invention are as follows: y coating liquid viscosity> Adjusting the coating liquid to 20 ° C, using a Β type viscosity meter (BL manufactured by Nippon Instruments) 'Using the number of rotations of the rotor The measurement was carried out at 60 rpm. <Transmittance> Using a spectrophotometer (Hitachi U-3500 type), the air entering the room was irradiated on the near-infrared ray absorbing layer side in a wavelength range of 1100 〜, and the air was measured as a control transmittance. <Hue> Using a color difference meter (ZE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) to correct this example, the film is improved, and the film is directly improved. : Tokyo calculates the 0 0 nm line, and the light irradiation -34 - 1354123 is corrected on the side of the near-infrared absorbing layer to perform measurement using a D65 light source and a 10 degree viewing angle. <Heat-and-moisture resistance> The color tone after standing for 500 hours in a gas atmosphere having a temperature of 60 ° C and a humidity of 95% was measured, and the amount of change in color tone Δ χ and Δ 前后 before and after the treatment was determined. • <Heat resistance> The color tone after leaving for 500 hours in a gas atmosphere at a temperature of 90 ° C was measured, and the amount of change in color tone Ax' Ay before and after the treatment was determined. φ: Softness> The film was cut into a width of 1 mm, and the near-infrared absorbing layer was wound outward on the metal bar to confirm whether or not the near-infrared ray absorbing layer was cracked. Using 20 metal rods having a diameter of 1 to 20 mm and a spacing of 1 mm, the minimum diameter at which cracks did not occur was evaluated as softness. Reference Example 1 1. Production of Transparent Substrate (1) Adjustment of Mastorbatch Containing Ultraviolet Absorber 0 Mixing 1 part by mass of dried ultraviolet absorber (CYASORB UV-3638 manufactured by CYTEC Co., Ltd.; 2 , 2'-(1,4-phenylene)bis(4H-3,1-benzoxanthene-4-one)), 90 parts by mass of polyethylene terephthalate containing no particles ( PET) Resin (ME 5 5 3, manufactured by Toyobo, Japan), using a mixing and agitating extruder to produce a masterbatch. The extrusion temperature at this time was 285 1, and the extrusion time was 7 minutes. (2) Adjustment of coating liquid for easy adhesion layer formation The coating liquid for easy adhesion layer formation was prepared by the following method. 95 parts by mass of dimethyl terephthalate, 95 parts by mass of dimethyl phthalate-35-1354123 modified ester, 35 parts by mass of ethylene glycol, 145 parts by mass of neopentyl glycol, 0.1 mass A portion of zinc acetate and 0.1 part by mass of antimony trioxide were fed into a reaction vessel, and a transesterification reaction was carried out at 180 ° C for 3 hours. Next, a mass fraction of 5-sulfoisophthalic acid-5-sodium was added thereto, and after undergoing a transesterification reaction at 240 ° C for 1 hour, a polycondensation reaction was carried out to obtain a polyester resin. ' Mixing 6 · 7 parts by mass of the obtained 30% by mass aqueous polyester resin dispersion, and 40 parts by mass of self-crosslinking polyaminocarboxylic acid containing isocyanate terminated by sodium hydrogen sulfite 20% by mass of ester resin, water soluble # (Elastron H-3, manufactured by Japan Daiichi Pharmaceutical Co., Ltd.), 0.5 parts by mass

Elastron用觸媒（Cat64) 、47.8質量份之水及5質量份之 異丙醇’進一步添加相對於塗布液爲1質量％之陰離子性 界面活性劑’及添加相對於塗布液之固形成分爲5質量％ 之二氧化矽膠體粒子（日本日產化學工業公司製之 SNOWTEX 0L )而作成塗布液。 (3 )基材薄膜之製膜Elastron uses a catalyst (Cat64), 47.8 parts by mass of water, and 5 parts by mass of isopropyl alcohol to further add 1% by mass of an anionic surfactant with respect to the coating liquid' and the solid addition to the coating liquid is divided into 5 A mass% of cerium oxide colloidal particles (SNOWTEX 0L, manufactured by Nissan Chemical Industries, Ltd.) was used as a coating liquid. (3) Film formation of substrate film

於135 °C，將90質量份之固有黏度爲0.62 dl/g且不含 #子之PET樹脂九粒（日本東洋紡績製之ME553)與10 質量份之該含有紫外線吸收劑的母煉膠予以6小時減壓乾 燥（ITorr)後’供應至擠壓機。擠壓機之熔融部、混攪部、 聚合物管、齒輪泵、過濾器爲止之樹脂溫度設爲28 (TC， 其後的聚合物管設爲27 5 °C，從噴嘴形成片狀後進行擠壓。 此等聚合物係分別使用不銹鋼燒結物之濾材（標稱過濾精 確度：將95%之ΙΟμηι以上粒子予以濾除）後進行過濾。 另外，平口模頭係使樹脂溫度成爲275 °C之方式來進行。 利用靜電施加澆鑄法，將擠壓的樹脂捲繞於表面溫度3 (TC -36- 1354123 修正本 之澆鑄轉筒（筒徑400φ、Ra〇.ipm以下）後加以冷卻固化， 製作未拉伸薄膜。此時之噴出量爲48kg/hr，所得到的未拉 伸片係寬度300mm、厚度14〇〇μ!η。 接著’使用加熱該澆鑄膜之滾筒群與紅外線加熱器而加 熱至100 °C，其後利用具有圓周速度差之滾筒群，沿著長 •軸方向（移動方向）拉伸3.5倍而得到單軸配向薄膜。有 關用於該薄膜製造時之所有滾筒，使滾筒之表面粗糙度Ra 控制於Ο.ίμιη以下，於縱向拉伸步驟之預熱入口與冷卻滾 #設置滾筒清潔器。縱向拉伸步驟之滾筒直徑爲15〇πιιη， 採用吸氣滚筒、靜電緊貼、緊貼裝置、部分壓軋之緊貼裝 置而使薄膜緊貼於滾筒。 其後’利用過濾粒子大小（初期過濾效率：9 5 % ) 2 5 μ m 之毯型聚丙烯製濾材進行精密過濾，利用逆輥法，進行兩 面塗布、乾燥。塗布後，接著利用壓板夾住薄膜之端部而 導入已加熱至130 °C之熱風區，沿著乾燥後寬度方向拉伸 4.0倍，於23 0°C進行5秒鐘熱處理，於此熱處理步驟中， #著寬度方向進行3%之弛緩處理，得到基材薄膜（B)。 該薄膜之厚度爲ΙΟΟμιη，此時之易接著層塗布量爲 0.01g/m2。所得到的薄膜之波長3 80nm的透過率爲4%， 具有優異的紫外線吸收特性。另外，全部光線透過率爲91 %，霧度爲0.6%，透明性優異。 2 .近紅外線吸收層之積層 於該中間塗布層上，使乾燥下列塗布液A(黏度：23 cps ) 後之950nm的透過率成爲4.3%之方式來利用直徑6〇Cm的 斜線凹版進行逆向塗布’分別使其通過以40 °C、5m/秒之 -37- 1354123 修正本 熱風乾燥20秒鐘，以150°C、20m/秒之熱風乾燥20秒鐘， 進一步以90 °C、20m /秒之熱風乾燥10秒鐘後，作成近紅 外線吸收濾光片。 (近紅外線吸收層用之塗布液A) 利用下列之質量比混合塗布液材料，攪拌3 0分鐘以上。 接著’利用標稱過濾精確度Ιμηι之過濾器，去除未溶解物 來調整塗布液Α。 甲苯 甲基乙基酮 丙烯酸系樹脂 22.193 質量 ％ 23.083 質量 ％ 52.762 質量 ％ (日本總硏化學製之GS-1030、固形成分濃度：3〇質量％、 Tg : 1 15t：) *二亞胺鐵鹽化合物（色素A) 〇_937質量％ (日本Car lit製之CIR 1085、相對離子：雙（三氟甲烷磺 醯基）醯亞胺酸） *花青系色素 〇·〇76質量％ 日本旭電化工業製之ΤΖ-123 ) *矽系界面活性劑 0.059質量％ (Dow Corning 製之 PaintAd 57、HLB ： 6.7) *三氟甲烷磺酸鋰（化合物C) 0.890質量％ 於表1，顯示於近紅外線吸收層中所含之近紅外線吸收 色素（二亞胺鑰鹽化合物）之種類、三氟甲烷磺酸化合物 之種類與含量。如表2所示，所得到的近紅外線吸收薄膜， 不僅近紅外線領域之吸收爲強的，於可見光領域之透過率 爲高的’耐濕熱性或耐熱性也爲良好的。 -38- 1354123 修正本 參考例2 除了使用下列塗布液B以外，進行相同於參考例1之方 式而得到近紅外線吸收薄膜。 (近紅外線吸收層用之塗布液B) ' 利用下列之質量比混合塗布液材料，攪捽3 0分鐘以上。 •接著，利用標稱過濾精確度Ιμπι之過濾器，去除未溶解物 來調整塗布液Β。 •甲苯 22.998質量％ |甲基乙基酮 2 3.0 8 3質量％ *丙烯酸系樹脂 52.762質量％ (日本總硏化學製之GS-1030、固形成分濃度：30質量％、 T g : 1 1 5 °C ) 鲁二亞胺鑰鹽化合物（色素A) 0.937質量％ (日本Car lit製之CIR 1085、相對離子：雙（三氟甲烷磺 醯基）醯亞胺酸） ♦花青系色素 0.076質量％ _(日本旭電化工業製之TZ-123) *矽系界面活性劑 0.059質量％ (Dow Corning 製之 PaintAd 57、HLB: 6.7) *三氟甲烷磺酸鋰（化合物C) 0.085質量％ 於表1，顯示於近紅外線吸收層中所含之近紅外線吸收 色素（二亞胺纖鹽化合物）之種類、三氟甲烷磺酸化合物 之種類與含量。如表2所示，所得到的近紅外線吸收薄膜， 不僅近紅外線領域之吸收爲強的，於可見光領域之透過率 爲高的，耐濕熱性或耐熱性也爲良好的。 -39- 1354123 修正本 參考例3 除了使用下列塗布液C以外’進行相同於參考例1之方 式而得到近紅外線吸收薄膜。 (近紅外線吸收層用之塗布液C) ' 利用下列之質量比混合塗布液材料，攪拌30分鐘以上。 -接著，利用標稱過濾精確度Ιμηι之過濾器，去除未溶解物 來調整塗布液C。 •甲苯 21.411質量％ #甲基乙基酮 23.08 3質量％ *丙烯酸系樹脂 52.762質量％ (日本總硏化學製之GS-1030、固形成分濃度：3〇質量％、90 parts by mass of a PET resin having an intrinsic viscosity of 0.62 dl/g and containing no ## of the PET resin (ME553, manufactured by Toyobo Co., Ltd.) and 10 parts by mass of the masterbatch containing the ultraviolet absorber at 135 °C After 6 hours of drying under reduced pressure (ITorr), it was supplied to the extruder. The resin temperature of the melted portion, the mixing portion, the polymer tube, the gear pump, and the filter of the extruder was 28 (TC, and the subsequent polymer tube was set at 27 5 ° C, and the sheet was formed into a sheet shape from the nozzle. Extrusion. These polymers are separately filtered using a filter material of stainless steel sinter (nominal filtration accuracy: 95% of the particles above ημηι are filtered). In addition, the flat die is such that the resin temperature becomes 275 °C. By electrostatic application casting method, the extruded resin is wound on a surface temperature of 3 (TC -36-1354123 modified casting drum (bottle diameter 400 φ, Ra 〇.ipm or less), and then cooled and solidified. The unstretched film was produced, and the discharge amount at this time was 48 kg/hr, and the obtained unstretched sheet was 300 mm in width and 14 μm in thickness η. Next, 'the roller group and the infrared heater which heated the cast film were used. After heating to 100 ° C, a uniaxial alignment film was obtained by stretching a drum group having a peripheral speed difference by 3.5 times in the longitudinal direction (moving direction). Roller surface roughness Ra is controlled below Ο.ίμιη, in the longitudinal stretching step of the preheating inlet and cooling roller # set the roller cleaner. The longitudinal stretching step of the drum diameter is 15〇πιηη, using suction cylinder, electrostatic close, close device The part of the nip is placed in close contact with the film to adhere the film to the drum. Thereafter, the substrate is filtered by a blanket type polypropylene filter material having a filter particle size (initial filtration efficiency: 9.5 %) 2 5 μm, using a reverse roll. The method is applied to both sides and dried. After coating, the end portion of the film is sandwiched by a press plate to introduce a hot air zone heated to 130 ° C, and stretched 4.0 times in the width direction after drying, and carried out at 23 0 ° C. In the heat treatment step, a 3% relaxation treatment was carried out in the width direction to obtain a base film (B). The thickness of the film was ΙΟΟμηη, and the easy-adhesion layer coating amount was 0.01 g/m 2 at this time. The obtained film had a transmittance of 3% at a wavelength of 3 to 80 nm and had excellent ultraviolet absorbing properties. The total light transmittance was 91%, the haze was 0.6%, and the transparency was excellent. 2. The near-infrared absorbing layer was laminated. In this On the intermediate coating layer, the transmittance of 950 nm after drying the following coating liquid A (viscosity: 23 cps) was 4.3%, and the reverse coating was performed by a slanting gravure of 6 〇 Cm, respectively, and passed at 40 ° C, respectively. 5m/sec -37- 1354123 Correct the hot air drying for 20 seconds, dry at 150 ° C, 20 m / sec for 20 seconds, and further dry at 90 ° C, 20 m / s for 10 seconds, then make a near Infrared absorption filter (Coating liquid A for near-infrared absorbing layer) The coating liquid material was mixed by the following mass ratio, and stirred for 30 minutes or more. Then, the coating liquid was adjusted by using a filter having a nominal filtration accuracy of ημηι to remove undissolved matter. Toluene methyl ethyl ketone acrylic resin 22.193% by mass 23.083% by mass 52.762% by mass (GS-1030, manufactured by Nippon Scientific Co., Ltd., solid content concentration: 3% by mass, Tg: 1 15t:) * Diimine iron salt Compound (Pigment A) 〇 9373% by mass (CIR 1085, Japan car lit, relative ion: bis(trifluoromethanesulfonyl) ruthenium imidate) *Cyanine pigment 〇·〇76% by mass Industrial ΤΖ-123 ) *矽 surfactant is 0.059% by mass (PaintAd 57 by Dow Corning, HLB: 6.7) * Lithium trifluoromethane sulfonate (Compound C) 0.890% by mass is shown in Table 1. The type of near-infrared absorbing pigment (diimine salt compound) contained in the absorbing layer, and the kind and content of the trifluoromethane sulfonic acid compound. As shown in Table 2, the obtained near-infrared ray absorbing film is excellent not only in the near-infrared field but also in the visible light region, which is high in heat resistance and heat resistance. -38- 1354123 MODIFICATION Reference Example 2 A near-infrared absorbing film was obtained in the same manner as in Reference Example 1 except that the following coating liquid B was used. (Coating liquid B for the near-infrared absorbing layer) ' Mix the coating liquid material with the following mass ratio, and stir for more than 30 minutes. • Next, adjust the coating solution by using a filter with a nominal filtration accuracy of Ιμπι to remove undissolved material. • Toluene 22.998% by mass | Methyl ethyl ketone 2 3.0 8 3 % by mass * Acrylic resin 52.762% by mass (GS-1030, manufactured by Nippon Scientific Co., Ltd., solid content concentration: 30% by mass, T g : 1 1 5 ° C) Ludiimide salt compound (Pigment A) 0.937% by mass (CIR 1085, Japan car lit, relative ion: bis(trifluoromethanesulfonyl) phthalic acid) ♦ Cyanine pigment 0.076% by mass _(TZ-123, manufactured by Asahi Kasei Kogyo Co., Ltd.) * 矽-based surfactant 0.059 mass% (PaintAd 57 by Dow Corning, HLB: 6.7) * Lithium trifluoromethane sulfonate (Compound C) 0.085 mass% The type of near-infrared absorbing pigment (diimine fiber salt compound) contained in the near-infrared ray absorbing layer, and the kind and content of the trifluoromethanesulfonic acid compound. As shown in Table 2, the obtained near-infrared ray absorbing film has high absorption in the near-infrared field, high transmittance in the visible light region, and good moist heat resistance and heat resistance. -39- 1354123 MODIFICATION Reference Example 3 A near-infrared absorbing film was obtained in the same manner as in Reference Example 1 except that the following coating liquid C was used. (Coating liquid C for the near-infrared absorbing layer) 'The mixture was mixed for 30 minutes or more by using the following mass ratio to mix the coating liquid material. - Next, the coating liquid C is adjusted by using a filter having a nominal filtration accuracy of ημηι to remove undissolved matter. • Toluene 21.411% by mass #methyl ethyl ketone 23.08 3% by mass * Acrylic resin 52.762 mass% (GS-1030, manufactured by Nippon Scientific Co., Ltd., solid content concentration: 3% by mass,

Tg : 1 1 5°C ) *二亞胺鑰鹽化合物（色素Α) 〇·93 7質量％ (曰本Car lit製之CIR 1085、相對離子：雙（三氟甲烷磺 醯基）醯亞胺酸） *花青系色素 0.076質量％ 日本旭電化工業製之TZ-123) *矽系界面活性劑 〇 . 〇 5 9質量％ (Dow Corning 製之 PaintAd 57、HLB : 6.7 ) ♦三氟甲烷磺酸鋰（化合物C) 1.671質量％ 於表1，顯示於近紅外線吸收層中所含之近紅外線吸收 色素（二亞胺鑰鹽化合物）之種類、三氟甲烷磺酸化合物 之種類與含量。如表2所示，所得到的近紅外線吸收薄膜， 不僅近紅外線領域之吸收爲強的，於可見光領域之透過率 爲高的，耐濕熱性或耐熱性也爲良好的。 -40- 1354123 修正本 比較例1 除了使用下列塗布液D以外，進行相同於參考例1之方 式而得到近紅外線吸收薄膜。本比較例1係於近紅外線吸 收層中不含三氟甲烷磺酸化合物或雙（磺醯基）醯亞胺酸 化合物之例子。 (近紅外線吸收層用之塗布液D) 利用下列之質量比混合塗布液材料，攪拌3 0分鐘以上。 接著，利用標稱過濾精確度Ιμηι之過濾器，去除未溶解物 #調整塗布液D。 春甲苯 23.083質量％ *甲基乙基酮 23.083質量％ *丙烯酸系樹脂 52.762質量％ (日本總硏化學製之GS-1030、固形成分濃度：30質量％、 T g ： 1 1 5 °C ) *二亞胺鑰鹽化合物（色素A) 0.937質量％ (日本Carlit製之CIR1085、相對離子：雙（三氟甲烷磺 基）醯亞胺酸） 0.076質量％ 0.059質量％ HLB ： 6.7 ) 花青系色素 曰本旭電化工業製之TZ-123 ) 矽系界面活性劑 (Tg : 1 1 5 ° C ) * Diimine salt compound (pigment Α) 〇 · 93 7 mass % (CIR 1085, relative ion: bis(trifluoromethanesulfonyl) quinone imine Acid) * Cyanine pigment 0.076 mass% TZ-123 manufactured by Asahi Kasei Co., Ltd. * 矽 surfactant 〇. 〇 5 9 mass% (PaintAd 57 by Dow Corning, HLB: 6.7) ♦ Trifluoromethane sulfonate Lithium acid (Compound C) 1.671% by mass Table 1 shows the types of near-infrared absorbing pigments (diimine salt-salt compounds) contained in the near-infrared ray absorbing layer, and the types and contents of trifluoromethanesulfonic acid compounds. As shown in Table 2, the obtained near-infrared ray absorbing film has high absorption in the near-infrared field, high transmittance in the visible light region, and good moist heat resistance and heat resistance. -40- 1354123 MODIFICATION EXAMPLE 1 A near-infrared absorbing film was obtained in the same manner as in Reference Example 1 except that the following coating liquid D was used. This Comparative Example 1 is an example in which a trifluoromethanesulfonic acid compound or a bis(sulfonyl)phosphinic acid compound is not contained in the near-infrared absorbing layer. (Coating liquid D for the near-infrared absorbing layer) The coating liquid material was mixed by the following mass ratio, and stirred for 30 minutes or more. Next, the undissolved material is removed by using a filter having a nominal filtration accuracy of ημηι # adjusting the coating liquid D. Spring toluene 23.083% by mass *Methyl ethyl ketone 23.083% by mass *Acrylic resin 52.762% by mass (GS-1030, manufactured by Nippon Scientific Co., Ltd., solid content concentration: 30% by mass, Tg: 1 15 °C) * Diimine salt compound (Pigment A) 0.937% by mass (CIR1085, manufactured by Carlit, Japan, relative ion: bis(trifluoromethanesulfonyl) phthalic acid) 0.076% by mass 0.059% by mass HLB: 6.7) Cyanine pigment TZ-123 manufactured by Sakamoto Asahi Chemical Co., Ltd.) lanthanide surfactant (

Dow Corning 製之 PaintAd 57、 於表1，顯示於近紅外線吸收層中所含之近紅外線吸收 色素（二亞胺鑰鹽化合物）之種類。如表2所示，所得到 的近紅外線吸收薄膜，其近紅外線領域之吸收爲強的。然 而’相較於近紅外線吸收層中含有三氟甲烷磺酸化合物（化 -41 - 1354123 修正本 合物C)之參考例1〜3,於可見光領域之透過率稍微降低， 耐熱性不佳。 參考例4 於參考例1，除了將近紅外線吸收層中所含之三氟甲烷 '磺酸鋰（化合物C)變更爲雙（三氟甲烷磺醯基）醯亞胺 •酸化合物（化合物D )以外，進行相同於參考例1之方式 而得到近紅外線吸收薄膜。 於表1，顯示於近紅外線吸收層中所含之近紅外線吸收 @素（二亞胺鑰鹽化合物）之種類、三氟甲烷磺酸化合物 之種類與含量。如表2所示，所得到的近紅外線吸收薄膜’ 不僅近紅外線領域之吸收爲強的，於可見光領域之透過率 爲高的，耐濕熱性或耐熱性也爲良好的。 參考例5 除了使用下列塗布液E以外，進行相同於參考例1之方 式而得到近紅外線吸收薄膜。 (近紅外線吸收層用之塗布液E ) g 利用下列之質量比混合塗布液材料，攪拌3 0分鐘以上° 接著，利用標稱過濾精確度Ιμιη之過濾器，去除未溶解物 來調整塗布液Ε。 籲甲苯 22.193質量％ *甲基乙基酮 23.08 3質量％ *丙烯酸系樹脂 52.762質量％ (日本總硏化學製之GS-l〇3〇、固形成分濃度：30質量％、 T g : 1 1 5 °C ) *二亞胺鑰鹽化合物（色素B) 0.937質量％ -42- 1354123 修正本 (曰本Carl it製之CIR 1081、相對離子：六氟化銻） *化青系色素 0.076質量％ (曰本旭電化工業製之TZ-123 ) *矽系界面活性劑 〇〇59質量％ (Dow Corning 製之 PaintAd 57、HLB: 6.7) 二氟甲院擴酸鋰（化合物C) 0.890質量％ 於表1，顯示於近紅外線吸收層中所含之近紅外線吸收 色素（二亞胺鑰鹽化合物）之種類、三氟甲烷磺酸化合物 種類與含量。如表2所示，所得到的近紅外線吸收薄膜， 不僅近紅外線領域之吸收爲強的，於可見光領域之透過率 爲高的，耐濕熱性或耐熱性也爲良好的。 比較例2 除了使用下列塗布液F以外，進行相同於參考例1之方 式而得到近紅外線吸收薄膜。本比較例2係於近紅外線吸 收層中不含三氟甲烷磺酸化合物或雙（磺醯基）醯亞胺酸 化合物之例子。 近紅外線吸收層用之塗布液F ) 利用下列之質量比混合塗布液材料，攪拌3 0分鐘以上。 接著，利用標稱過濾精確度ΐμηι之過濾器，去除未溶解物 來調整塗布液F。 •甲苯 2 3.0 8 3質量％ ♦甲基乙基酮 23.08 3質量％ *丙烯酸系樹脂 52.762質量％ (日本總硏化學製之GS-1030、固形成分濃度：3〇質量％、 Tg ： 1 15°c ) -43- 1354123 修正本 ♦二亞胺鎗鹽化合物（色素B ) 0.93 7質量％ (日本Carlit製之CIR1 08 1、相對離子：六氟化銻） *花青系色素 0 076質量％ (日本旭電化工業製之TZ-123) 矽系界面活性劑 0.059質量％ • ( Dow Corning 製之 PaintAd 57、HLB : 6.7) 於表1，顯示於近紅外線吸收層中所含之近紅外線吸收 色素（二亞胺鑰鹽化合物）之種類。如表2所示，所得到 #近紅外線吸收薄膜，雖然近紅外線領域之吸收爲強的， 但是耐濕熱性（尤其是Ay)與耐熱性變差。 實施例6 除了使用下列塗布液G以外，進行相同於參考例1之方 式而得到近紅外線吸收薄膜。 (近紅外線吸收層用之塗布液G) 利用下列之質量比混合塗布液材料，攪拌3 0分鐘以上。 接著’利用標稱過濾精確度Ιμπι之過濾器，去除未溶解物 #調整塗布液G。 *甲苯 23.08 3質量％ *甲基乙基酮 23.0 8 3質量％ *丙嫌酸系樹脂 52762質量％ (曰本總硏化學製之GS-1030、固形成分濃度：3〇質量％、 Tg ： 1 1 5 °c ) 0.937質量％ 對離子：雙（三氟甲烷磺 ♦二亞胺鑰鹽化合物（色素A) (曰本Carlit製之CIR1085、相 醯基）醯亞胺酸） -44- 1354123 修正本 參化合物E 0.076質量％ (將雙（三氟甲烷磺醯基）醯亞胺酸作成相對離子的花青 色素；日本旭電化工業製之TZ-109D) *矽系界面活性劑 0.059質量％ (Dow Corning 製之 P a i n t A d 5 7、H L B : 6 · 7 ) • 於表1，顯示於近紅外線吸收層中所含之近紅外線吸收 色素（二亞胺鑰鹽化合物）之種類、三氟甲烷磺酸化合物 之種類與含量。如表2所示，所得到的近紅外線吸收薄膜， f僅近紅外線領域之吸收爲強的，於可見光領域之透過率 爲高的，耐濕熱性或耐熱性也爲良好的。 實施例7 除了使用下列塗布液Η以外，進行相同於參考例1之方 式而得到近紅外線吸收薄膜》 (近紅外線吸收層用之塗布液Η ) 利用下列之質量比混合塗布液材料，攪拌3 0分鐘以上。 接著，利用標稱過濾精確度Ιμιη之過濾器，去除未溶解物 胃$調整塗布液Η。 •甲苯 23.083質量％ ♦甲基乙基酮 23.08 3質量％ •丙烯酸系樹脂 52.762質量％ (曰本總硏化學製之GS-l〇3〇、固形成分濃度：30質量％、 T 8 ： 1 1 5 °C ) *二亞胺鑰鹽化合物（色素A) 0.937質量％ (日本Carlit製之CIR1085、相對離子：雙（三氟甲烷磺 鲧基）醯亞胺酸） -45- 1354123 修正本 •化合物E 0.076質量％ (將雙（三氟甲烷磺醯基）醯亞胺酸作成相對離子的花青 色素：日本化藥製之CY-40MC(F)) *矽系界面活性劑 0.059質量％ (Dow Corning 製之 PaintAd 57、HLB : 6.7) 比較例3 除了使用下列塗布液I以外，進行相同於參考例1之方 式而得到近紅外線吸收薄膜。 近紅外線吸收層用之塗布液I ) 利用下列之質量比混合塗布液材料，攪拌3 0分鐘以上。 接著，利用標稱過濾精確度Ιμιη之過濾器，去除未溶解物 來調整塗布液I。 甲苯 甲基乙基酮 丙烯酸系樹脂 23.083 質量 ％ 23.083 質量 ％ 52.762 質量 ％ (曰本總硏化學製之GS-1030、固形成分濃度：30質量％ Γ g ： 1 1 5 °C ) *二亞胺鎗鹽化合物（色素A) 0.937質量％ (日本Car lit製之CIR1085、相對離子：雙（三氟甲烷磺 醯基）醯亞胺酸） •化合物F 0.076質量％ (將六氟化銻作成相對離子的花青色素；日本化藥製之 C Y-40MC ( S )) *矽系界面活性劑 0.059質量％ (Dow Corning 製之 PaintAd 57、HLB ： 6.7) -46- 1354123 修正本 〔表1〕 近紅外線吸收色素 添加劑 (二亞胺鏺鹽） 種類 含量（質量％ ) 參 考 例 1 A C 5.0 參 考 例 2 A C 0.5 .參 考 例 3 A c 9.0 比 較 例 1 A — 0 參 考 例 4 A D 5.0 考 例 5 B C 5.0 比 較 例 2 B — 0 實 施 例 6 A E 0.45 實 施 例 7 A E 0.45 比 較 例 3 A F 0.45 於 表 1 ， 色素A-B、化合物C-F 意指下 列化合物： (色素A ) 將雙（三氟甲烷磺醯基）醯亞胺酸）作成相對離子之 0ί,Ν,Ν’，Ν’-四（對-二-正-丁胺基苯基）-對-伸苯基二亞胺 鏺鹽 (色素Β ) 將六氟化銻作成相對離子之Ν，Ν，Ν’，Ν’-四（對-二-正-丁胺基苯基）-對-亞苯基二亞胺鐺鹽 (化合物C ) 三氟甲烷磺酸鋰 (化合物D ) 正-丁基-3 -甲基吡啶鑰雙（三氟甲烷磺醯基）醯亞胺 -47- 1354123 修正本 (化合物E ) 將雙（三氟甲烷磺醯基）醯亞胺酸作成相對離子之花青 色素 (化合物F ) 將六氟化銻作成相對離子之花青色素PaintAd 57 manufactured by Dow Corning, shown in Table 1, shows the type of near-infrared absorbing pigment (diimine salt compound) contained in the near-infrared absorbing layer. As shown in Table 2, the obtained near-infrared absorbing film was strongly absorbed in the near-infrared field. However, the transmittances in the visible light region were slightly lowered and the heat resistance was poor as compared with Reference Examples 1 to 3 in which the trifluoromethanesulfonic acid compound (Chemical Formula -41 - 1354123 Modified Compound C) was contained in the near-infrared ray absorbing layer. Reference Example 4 In Reference Example 1, except that the trifluoromethane 'sulfonic acid lithium (Compound C) contained in the near-infrared ray absorbing layer was changed to a bis(trifluoromethanesulfonyl) quinone imine acid compound (Compound D) A near-infrared absorbing film was obtained in the same manner as in Reference Example 1. Table 1 shows the types of near-infrared absorption (diimine salt compound) contained in the near-infrared ray absorbing layer, and the kind and content of the trifluoromethanesulfonic acid compound. As shown in Table 2, the obtained near-infrared absorbing film ′ was not only strongly absorbed in the near-infrared region but also had high transmittance in the visible light region, and was also excellent in moist heat resistance and heat resistance. Reference Example 5 A near-infrared absorbing film was obtained in the same manner as in Reference Example 1 except that the following coating liquid E was used. (The coating liquid E for the near-infrared absorbing layer) g is mixed with the coating liquid material in the following mass ratio, and stirred for 30 minutes or more. Next, the coating liquid is removed by using a filter having a nominal filtration accuracy of Ιμιη to remove undissolved matter. . Toluene 22.193% by mass *Methyl ethyl ketone 23.08 3 % by mass *Acrylic resin 52.762% by mass (GS-l〇3〇, manufactured by Nippon Scientific Co., Ltd., solid component concentration: 30% by mass, T g : 1 1 5 °C) *Diimine salt compound (Pigment B) 0.937% by mass -42- 1354123 Amendment (CIR 1081, relative ion: hexafluoride hexafluoride manufactured by Carl It) * 0.076% by mass of cyanine pigment ( TZ-123 manufactured by Sakamoto Asahi Chemical Co., Ltd. * 矽 59% by mass of surfactant surfactant (PaintAd 57 by Dow Corning, HLB: 6.7) Lithium difluoride (Liquid C) 0.890% by weight 1. The type of the near-infrared absorbing pigment (diimine salt-salt compound) contained in the near-infrared ray absorbing layer, and the type and content of the trifluoromethanesulfonic acid compound. As shown in Table 2, the obtained near-infrared ray absorbing film has high absorption in the near-infrared field, high transmittance in the visible light region, and good moist heat resistance and heat resistance. Comparative Example 2 A near-infrared absorbing film was obtained in the same manner as in Reference Example 1 except that the following coating liquid F was used. This Comparative Example 2 is an example in which a trifluoromethanesulfonic acid compound or a bis(sulfonyl)phosphinic acid compound is not contained in the near-infrared absorbing layer. The coating liquid for the near-infrared absorbing layer F) was mixed with the coating liquid material in the following mass ratio, and stirred for 30 minutes or more. Next, the coating liquid F was adjusted by using a filter having a nominal filtration accuracy of ημηι to remove undissolved matter. • Toluene 2 3.0 8 3 mass% ♦ methyl ethyl ketone 23.08 3 mass% * acrylic resin 52.762 mass% (GS-1030, manufactured by Nippon Scientific Co., Ltd., solid component concentration: 3〇 mass%, Tg: 1 15° c) -43- 1354123 Correction of this ♦ diimine gun salt compound (pigment B) 0.93 7 mass% (CIR1 08, manufactured by Carlit, Japan, 1, relative ion: antimony hexafluoride) * Cyanine pigment 0 076% by mass ( TZ-123 manufactured by Asahi Kasei Co., Ltd.) 矽-based surfactant 0.059 mass% • (PaintAd 57 by Dow Corning, HLB: 6.7) Table 1 shows the near-infrared absorbing pigment contained in the near-infrared absorbing layer ( The type of diimine salt compound). As shown in Table 2, the obtained near-infrared absorbing film had strong absorption in the near-infrared field, but deteriorated in moist heat resistance (especially Ay) and heat resistance. Example 6 A near-infrared absorbing film was obtained in the same manner as in Reference Example 1 except that the following coating liquid G was used. (Coating liquid G for the near-infrared absorbing layer) The coating liquid material was mixed by the following mass ratio, and stirred for 30 minutes or more. Next, the filter solution G was adjusted by using a filter having a nominal filtration accuracy of Ιμπι to remove undissolved matter. *Toluene 23.08 3% by mass *Methyl ethyl ketone 23.0 8 3 % by mass * A total of 52,762% by mass of acrylic acid resin (GS-1030, manufactured by 硏本硏硏, solid content concentration: 3% by mass, Tg: 1 1 5 °c ) 0.937% by mass Opion: bis(trifluoromethanesulfonate ii diimide salt compound (pigment A) (CIR1085, based on Carnit, 醯 醯) 醯 imiline) -44- 1354123 The reference compound E was 0.076 mass% (bis(trifluoromethanesulfonyl) ruthenium imidate was used as a relative ion cyanine dye; TZ-109D manufactured by Asahi Kasei Chemical Co., Ltd.) * lanthanide surfactant 0.059 mass% ( P aint A d 5 7 by Dow Corning, HLB: 6 · 7 ) • In Table 1, the type of near-infrared absorbing pigment (diimine salt compound) contained in the near-infrared absorbing layer, trifluoromethane The type and content of the sulfonic acid compound. As shown in Table 2, the obtained near-infrared ray absorbing film had a strong absorption in the near-infrared only region, a high transmittance in the visible light region, and good moist heat resistance and heat resistance. Example 7 A near-infrared absorbing film (a coating liquid for a near-infrared absorbing layer) was obtained in the same manner as in Reference Example 1 except that the following coating liquid was used. The coating liquid material was mixed by the following mass ratio, and stirred for 3 0. More than a minute. Next, using a filter with a nominal filtration accuracy of Ιμιη, remove the undissolved stomach and adjust the coating solution. • Toluene 23.083% by mass ♦ Methyl ethyl ketone 23.08 3% by mass • Acrylic resin 52.762% by mass GS-l〇3〇, 固 硏 硏 〇, solid component concentration: 30% by mass, T 8 : 1 1 5 °C) *Diimine salt compound (Pigment A) 0.937% by mass (CIR1085, manufactured by Carlit, Japan, relative ion: bis(trifluoromethanesulfonyl) phthalic acid) -45- 1354123 Revision compound E 0.076% by mass (Cyanine pigment which uses bis(trifluoromethanesulfonyl) ruthenium amide as a relative ion: CY-40MC (F) made by Nippon Kasei Co., Ltd. * 矽-type surfactant 0.059 mass% (Dow PaintAd 57, HLB: 6.7) manufactured by Corning Comparative Example 3 A near-infrared absorbing film was obtained in the same manner as in Reference Example 1 except that the following coating liquid I was used. The coating liquid for the near-infrared absorbing layer I) was mixed with the coating liquid material by the following mass ratio, and stirred for 30 minutes or more. Next, the coating liquid I was adjusted by using a filter having a nominal filtration accuracy of Ιμηη to remove undissolved matter. Toluene methyl ethyl ketone acrylic resin 23.083% by mass 23.083% by mass 52.762% by mass (GS-1030, manufactured by 硏 硏 、, solid component concentration: 30% by mass Γ g : 1 1 5 ° C ) * Diimine Gun salt compound (pigment A) 0.937% by mass (CIR1085 made by Car lit, Japan, relative ion: bis(trifluoromethanesulfonyl) ruthenium amide) • Compound F 0.076 mass% (Phosphorus hexafluoride is used as a relative ion) Cyanine pigment; C Y-40MC (S)) made by Nippon Kayaku Co., Ltd. *矽9 surfactant% (PaintAd 57 by Dow Corning, HLB: 6.7) -46- 1354123 Amendment [Table 1] Infrared Absorbing Pigment Additive (Diimine Barium Salt) Species Content (% by mass) Reference Example 1 AC 5.0 Reference Example 2 AC 0.5 . Reference Example 3 A c 9.0 Comparative Example 1 A - 0 Reference Example 4 AD 5.0 Test Example 5 BC 5.0 Comparative Example 2 B - 0 Example 6 AE 0.45 Example 7 AE 0.45 Comparative Example 3 AF 0.45 In Table 1, the pigment AB and the compound CF mean the following compounds: (Pigment A) Bis(trifluoromethanesulfonyl) hydrazine Asian Oxate, Ν, Ν'-tetrakis(p-di-n-butylaminophenyl)-p-phenylene diimine sulfonium salt (pigment) As a relative ion, Ν,Ν',Ν'-tetrakis(p-di-n-butylaminophenyl)-p-phenylene diimine sulfonium salt (Compound C) lithium trifluoromethanesulfonate ( Compound D) n-Butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine-47- 1354123 Amendment (Compound E) Bis(trifluoromethanesulfonyl) rutheine A cyanine pigment (compound F) which is made into a relative ion. Cyanine hexafluoride is used as a relative ion cyanine pigment.

-48- 1354123 修正本 〔表2〕 透過率（％) 色調 耐濕熱性 mf m 950nm 850nm Y X y Δχ △y Δχ △ y 參考例1 4.3 9.4 81.2 0.370 0.340 0.001 0.002 0.001 0.002 參考例2 4.3 9.6 81.7 0.317 0.338 0.001 0.002 0.001 0.001 參考例3 4.3 9.1 80.6 0.318 0.340 0.001 0.003 0.002 0.003 比較例1 4.3 9.0 79.8 0.318 0.342 0.002 0.004 0.003 0.008 參考例4 4.3 9.3 80.9 0.317 0.340 0.001 0.002 0.001 0.002 例 5 4.3 9.7 81.1 0.316 0.339 0.002 0.003 0.002 0.004 比較例2 4.3 9.3 80.8 0.317 0.341 0.002 0.006 0.005 0.012 寊施例6 4.3 9‘4 80.9 0.317 0.341 0.001 0.002 0.002 0.004 資施例7 4.3 8.2 80.9 0.315 0.342 0.001 0.002 0.002 0.003 比較例3 4.3 7.9 80.9 0.315 0.342 0.003 0.005 0.004 0.006 實施例8 1 ·透明基材之製造 (1) 含有紫外線吸收劑之母煉膠的調整 # 混合1 0質量份之已乾燥的紫外線吸收劑（CYTEC公司 製之 CYASORB UV-3638; 2,2’-( 1,4 -伸苯基）雙（4H-3J-苯并噚哄-4-酮））、90質量份之不含粒子的聚對苯二甲酸 乙二醇酯（PET )樹脂（日本東洋紡績製之ME 5 5 3 )，使 用混攪擠壓機，製作母煉膠。此時之擠壓溫度爲285 °C， 擠壓時間爲7分鐘。 (2) 易接著層形成用塗布液之調整 遵循下列方法而調製易接著層形成用塗布液。將95質 量份之對苯二甲酸二甲酯、95質量份之間苯二甲酸二甲 -49- 1354123 修正本 酯、35質量份之乙二醇、145質量份之新戊二醇、〇·1質量 份之醋酸鋅與0.1質量份之三氧化銻進料於反應容器內， 於1 8 0 °c耗時' 3小時進行酯交換反應。接著，添加6.0質量 份之5 -鈉5 -磺基間苯二甲酸，於2 4 0 °C耗時1小時進行酯 交換反應後，進行聚縮合反應，得到聚酯樹脂。 • 分別混合6 · 7質量份之所得到的3 0質量％聚酯樹脂水 分散液、4〇質量份之含有被亞硫酸碳酸氫鈉所封端基的異 氰酸酯之自我交聯型聚胺基甲酸酯樹脂的20質量％水溶 日本第一工業製藥製之ElastronH-3) 、0.5質量份之 Elastro η用觸媒（Cat 64) 、47.8質量份之水及5質量份之 異丙醇，分別混合，進一步添加相對於塗布液爲1質量％ 之陰離子性界面活性劑，及添加相對於塗布液之固形成分 爲5質量％之二氧化矽膠體粒子（日本日產化學工業公司 製之SNOWTEX 0L)而作成塗布液。 (3 )基材薄膜之製膜-48- 1354123 Revision [Table 2] Transmittance (%) Hue heat and humidity resistance mf m 950nm 850nm YX y Δχ Δy Δχ △ y Reference example 1 4.3 9.4 81.2 0.370 0.340 0.001 0.002 0.001 0.002 Reference example 2 4.3 9.6 81.7 0.317 0.338 0.001 0.002 0.001 0.001 Reference Example 3 4.3 9.1 80.6 0.318 0.340 0.001 0.003 0.002 0.003 Comparative Example 1 4.3 9.0 79.8 0.318 0.342 0.002 0.004 0.003 0.008 Reference Example 4 4.3 9.3 80.9 0.317 0.340 0.001 0.002 0.001 0.002 Example 5 4.3 9.7 81.1 0.316 0.339 0.002 0.003 0.002 0.004 Comparative Example 2 4.3 9.3 80.8 0.317 0.341 0.002 0.006 0.005 0.012 寊 Example 6 4.3 9'4 80.9 0.317 0.341 0.001 0.002 0.002 0.004 Example 7 4.3 8.2 80.9 0.315 0.342 0.001 0.002 0.002 0.003 Comparative Example 3 4.3 7.9 80.9 0.315 0.342 0.003 0.005 0.004 0.006 Example 8 1 Production of transparent substrate (1) Adjustment of master batch containing ultraviolet absorber # Mix 10 parts by mass of dried UV absorber (CYASORB UV-3638 manufactured by CYTEC Co., Ltd.; 2,2'-(1,4-phenylene)bis(4H-3J-benzoindole-4-one)), 90 parts by mass of particles-free poly A terephthalic acid ethylene glycol ester (PET) resin (ME 5 5 3 manufactured by Toyobo Co., Ltd.) was used to prepare a master batch using a kneading extruder. The extrusion temperature at this time was 285 ° C and the extrusion time was 7 minutes. (2) Adjustment of coating liquid for easy adhesion layer formation The coating liquid for easy adhesion layer formation was prepared by the following method. 95 parts by mass of dimethyl terephthalate, 95 parts by mass of dimethyl sulfonate-49- 1354123 modified ester, 35 parts by mass of ethylene glycol, 145 parts by mass of neopentyl glycol, hydrazine· 1 part by mass of zinc acetate and 0.1 part by mass of antimony trioxide were fed into the reaction vessel, and the transesterification reaction was carried out at 1 800 ° C for 3 hours. Next, 6.0 parts by mass of 5-sodium 5-sulfoisophthalic acid was added, and after a transesterification reaction was carried out at 240 ° C for 1 hour, a polycondensation reaction was carried out to obtain a polyester resin. • Mixing 6.7 parts by mass of the obtained 30% by mass polyester resin aqueous dispersion and 4 parts by mass of self-crosslinking polyamine group containing isocyanate terminated by sodium hydrogen sulfite 20% by mass of the acid ester resin, Elastron H-3, manufactured by Japan Daiichi Pharmaceutical Co., Ltd., 0.5 parts by mass of Elastro η catalyst (Cat 64), 47.8 parts by mass of water and 5 parts by mass of isopropyl alcohol, respectively. Further, an anionic surfactant is added in an amount of 1% by mass based on the coating liquid, and cerium oxide colloidal particles (SNOWTEX 0L, manufactured by Nissin Chemical Industry Co., Ltd.) having a solid content of 5% by mass with respect to the coating liquid are added. Coating solution. (3) Film formation of substrate film

於135°C，將90質量份之固有黏度爲〇.62dl/g且不含 gp子之PET樹脂九粒（日本東洋紡績製之ME553)與10 質量份之該含有紫外線吸收劑的母煉膠予以6小時減壓乾 燥（ITorr)後，供應至擠壓機。擠壓機之熔融部、混攪部、 聚合物管、齒輪泵、過濾器爲止之樹脂溫度設爲2 8 (TC， 其後的聚合物管設爲27 5 °C，從噴嘴形成片狀後進行擠壓。 此等之聚合物係分別使用不銹鋼燒結物之濾材（標稱過濾 精確度：將95%之ΙΟμπι以上粒子予以濾除）後進行過濾。 另外，平口模頭係使樹脂溫度成爲2 7 5 °C之方式來進行。 利用靜電施加澆鑄法，將擠壓的樹脂捲繞於表面溫度30°C -50- 1354123 修正本 之澆鑄轉筒（筒徑400φ、Ra0.1pm以下）後加以冷卻固化， 製作未拉伸薄膜。此時之噴出量爲48kg/hr，所得到的未拉 伸片係寬度300mm、厚度140 Ομιτι。 接著’使用加熱該澆鑄膜之滾筒群與紅外線加熱器而加 熱至100 °C ’其後利用具有圓周速度差之滾筒群，沿著長 •軸方向（移動方向）拉伸3.5倍而得到單軸配向薄膜。有 關用於該薄膜製造時之所有滾筒，使滾筒之表面粗糙度Ra 控制於Ο.ίμιη以下，於縱向拉伸步驟之預熱入口與冷卻滾 設置滾筒清潔器。縱向拉伸步驟之滾筒直徑爲150mm， 採用吸氣滾筒、靜電緊貼、緊貼裝置、部分壓軋之緊貼裝 置而使薄膜緊貼於滾筒。 其後，利用過濾粒子大小（初期過濾效率：9 5 % ) 2 5 μηι 之毯型聚丙烯製濾材進行易黏著層形成用之塗布液的精密 過濾，利用逆輥法，進行兩面之塗布、乾燥》塗布後，接 著利用壓板夾住薄膜之端部而導入已加熱至130 °C之熱風 區，沿著乾燥後寬度方向拉伸4.0倍，於230°C進行5秒鐘 f處理，於此熱處理步驟中，沿著寬度方向進行3%之弛 緩處理，得到基材薄膜（B)。該薄膜之厚度爲100 μιη，此 時之易接著層塗布量爲 0.01 g/m2。所得到的薄膜之波長 3 8 Onm的透過率爲4%，具有優異的紫外線吸收特性。另 外，全部光線透過率爲91%，霧度爲0.6%，透明性優異。 2 .近紅外線吸收層之積層 於該中間塗布層上，使乾燥下列塗布液J(黏度：23 cps) 後之950nm的透過率成爲4.3%之方式來利用直徑60cm的 斜線凹版進行逆向塗布，分別使其通過以40°C、5m/秒之 -51- 1354123 修正本 熱風乾燥20秒鐘’以150°C、2〇m/秒之熱風乾燥2〇秒鐘， 進一步以90°C、20m/秒之熱風乾燥1〇秒鐘後，作成近紅 外線吸收濾光片。 (近紅外線吸收層用之塗布液J) 利用下列質量比混合塗布液材料，攪拌3 〇分鐘以上。 接著’利用標稱過濾精確度Ιμιη之過濾器，去除未溶解物 來調整塗布液J。 參甲苯 22.193質量％ #甲基乙基酮 23.083質量％ 參丙燃酸系樹脂 52.762質量％ (曰本總硏化學製之GS-1〇3〇、固形成分濃度：3〇質量％、 T g ： 1 1 5 °C ) *二亞胺鑰鹽化合物（色素A) 0.937質量％ (日本Car lit製之CIR 1085、相對離子：雙（三氟甲烷磺 醯基）醯亞胺酸） •花青系.色素 0.076質量％ 曰本旭電化工業製之TZ-123) *矽系界面活性劑 0.0 5 9質量％ (Dow Corning 製之 PaintAd 57、HLB ： 6.7) *離子性液體D 0.890質量％ (正-丁基-3-甲基吡啶銷雙（三氟甲烷磺醯基）醯亞胺） 於表3，顯示近紅外線吸收層中之近紅外線吸收色素（二 亞胺銷鹽化合物）之種類、離子性液體之種類與含量。另 外，於表4顯示所得到的近紅外線吸收薄膜之物性。可以 得到近紅外線領域之吸收爲強的，於可見光領域之透過率 -52- 1354123 修正本 爲高的薄膜。另外，耐熱性、柔軟性也爲良好的。 實施例9 除了使用下列塗布液K以外，進行相同於實施例8之方 式而得到近紅外線吸收薄膜。 (近紅外線吸收層用之塗布液K) 利用下列之質量比混合塗布液材料，攪拌3 0分鐘以上。 接者’利用標稱過據精確度Ιμηι之過爐器，去除未溶解物 來調整塗布液Κ。 _甲苯 22.998質量％ ♦甲基乙基酮 23.083質量％ *丙烯酸系樹脂 52.762質量％ (日本總硏化學製之GS-1030、固形成分濃度：30質量％、 T g ： 1 1 5 °C ) *二亞胺鑰鹽化合物（色素A) 0.937質量％ (日本Car lit製之CIR1085、相對離子：雙（三氟甲烷磺 醯基）醯亞胺酸） 花青系色素 0.076質量％ (曰本旭電化工業製之TZ-123) *砂系界面活性劑 0.059質量％ (Dow Corning 製之 PaintAd 57、HLB: 6.7) 鲁離子性液體D 0.085質量％ (正-丁基-3-甲基吡啶鑰雙（三氟甲烷磺醯基）醯亞胺） 於表3，顯示近紅外線吸收層中之近紅外線吸收色素（二 亞胺鐵鹽化合物）之種類、離子性液體之種類與含量。另 外，於表4顯示所得到的近紅外線吸收薄膜之物性。可以 -53- 1354123 修正本 得到近紅外線領域之吸收爲強的’於可見光領域之透過率 爲高的薄膜。另外’耐熱性、柔軟性也爲良好的。 實施例1 〇 除了使用下列塗布液L以外，進行相同於實施例8之方 式而得到近紅外線吸收薄膜。 ’（近紅外線吸收層用之塗布液L) 利用下列之質量比混合塗布液材料，攪拌30分鐘以上。 接著，利用標稱過濾精確度Ιμπι之過濾器，去除未溶解物 #調整塗布液L。 *甲苯 21.411質量％ *甲基乙基酮 23.083質量％ •丙烯酸系樹脂 52.762質量％ (日本總硏化學製之GS-1030、固形成分濃度：3〇質量％、 T g : 1 1 5 °C ) 籲二亞胺鑰鹽化合物（色素A) 0.937質量％ (日本Car lit製之CIR1085、相對離子：雙（三氟甲烷擴 #基）醯亞胺酸） *花青系色素 〇·〇76質量％ (曰本旭電化工業製之ΤΖ-123 ) *矽系界面活性劑 0.059質量％ (Dow Corning 製之 PaintAd 57 ' HLB : 6.7) 籲離子性液體D 1.671質量％ (正-丁基-3 -甲基吡啶鑰雙（三氟甲烷磺醯基）醯亞胺） 於表3，顯示近紅外線吸收層中之近紅外線吸收色素（二 亞胺鑰鹽化合物）之種類、離子性液體之種類與含量。另 -54- 1354123 修正本 外’於表4顯示所得到的近紅外線吸收薄膜之物性。可以 得到近紅外線領域之吸收爲強的，於可見光領域之透過率 爲高的薄膜。另外，耐熱性、柔軟性也爲良好的。 比較例4 除了使用下列塗布液Μ以外，進行相同於實施例8之方 式而得到近紅外線吸收薄膜。 (近紅外線吸收層用之塗布液Μ) 利用下列之質量比混合塗布液材料，攪拌3 0分鐘以上。 •g著，利用標稱過濾精確度Ιμιη之過濾器，去除未溶解物 來調整塗布液Μ。 *甲苯 23.0 8 3質量％ *甲基乙基酮 23.083質量％ •丙烯酸系樹脂 52.762質量％ (日本總硏化學製之GS-l〇3〇、固形成分濃度：3〇質量％、 T g : 115。。） 鲁二亞胺鐵鹽化合物（色素A) 0.937質量％ _(日本Carlit製之CIR1085、相對離子：雙（三氟甲烷磺 醯基）醯亞胺酸） •花青系色素 0.076質量％ (曰本旭電化工業製之TZ-123 ) *矽系界面活性劑 0.059質量％ (D 〇 w C 〇 r ni n g 製之 P ai n t A d 5 7、H LB ： 6.7) 於表3，顯示近紅外線吸收層中之近紅外線吸收色素（二 亞胺鑰鹽化合物）之種類。另外，於表4顯示所得到的近 紅外線吸收薄膜之物性。可以得到近紅外線領域之吸收爲 -55- 1354123 修正本 強的薄膜。相較於已添加離子性液體之實施例8〜10，可 以得到於可見光領域之透過率稍低的薄膜。耐熱性、柔軟 性爲不良的。 參考例1 於實施例8，除了將離子性液體之種類變更爲下列之離 •子性液體G以外，進行相同於實施例8之方式而得到近紅 外線吸收薄膜。 離子性液體G :正-丁基-3-甲基吡啶鏺四氟硼酸鹽 Φ 於表3,顯示近紅外線吸收層中之近紅外線吸收色素（二 亞胺鑰鹽化合物）之種類、離子性液體之種類與含量。另 外，於表4顯示所得到的近紅外線吸收薄膜之物性。可以 得到近紅外線領域之吸收爲強的，於可見光領域之透過率 爲高的薄膜。另外，耐熱性、柔軟性也爲良好的。 實施例1 1 於實施例8，除了將離子性液體之種類變更爲下列之離 子性液體Η以外，進行相同於實施例8之方式而得到近紅 線吸收薄膜。 離子性液體H : N，N，N-三甲基丙基銨雙（三氟甲烷 磺醯基）醯亞胺 於表3，顯示近紅外線吸收層中之近紅外線吸收色素（二 亞胺鐵鹽化合物）之種類、離子性液體之種類與含量。另 外，於表4顯示所得到的近紅外線吸收薄膜之物性。可以 得到近紅外線領域之吸收爲強的薄膜。雖然耐熱性較實施 例8爲差，但是，較比較例4更爲良好。另外，柔軟性爲 良好的。 -56- 1354123 修正本 實施例1 2 除了使用下列塗布液P以外，進行相同於實施例8之方 式而得到近紅外線吸收薄膜。 (近紅外線吸收層用之塗布液P) 利用下列之質量比混合塗布液材料，攪拌3 〇分鐘以上。 •接著，利用標稱過濾精確度Ιμηι之過濾器，去除未溶解物 來調整塗布液Ρ。 *甲苯 22.1 93質量％ φ甲基乙基酮 23.08 3質量％ 聲丙烯酸系樹脂 52.762質量％ (日本總硏化學製之GS-1030、固形成分濃度：30質量％、 T g : 1 1 5°C ) «二亞胺鑰鹽化合物（色素B) 0.937質量％ (曰本Carlit製之CIR1081、相對離子：六氟化銻） 籲花青系色素 〇·〇76質量％ (曰本旭電化工業製之TZ-123) f矽系界面活性劑 0.059質量％ (Dow Corning 製之 PaintAd 57、HLB : 6.7) ♦離子性液體D 0.890質量％ (正-丁基-3-甲基吡啶鑰雙（三氟甲烷磺醯基）醯亞胺） 於表3,顯示近紅外線吸收層中之近紅外線吸收色素（二 亞胺鑰鹽化合物）之種類、離子性液體之種類與含量。另 外，於表4顯示所得到的近紅外線吸收薄膜之物性。可以 得到近紅外線領域之吸收爲強的，於可見光領域之透過率 爲高的薄膜。另外，耐熱性、柔軟性也爲良好的。 -57- 1354123 修正本 比較例5 除了使用下列塗布液Q以外，進行相同於實施例8之方 式而得到近紅外線吸收薄膜。 (近紅外線吸收層用之塗布液Q) 利用下列之質量比混合塗布液材料，攪拌30分鐘以上。 ‘接著，利用標稱過濾精確度Ιμιη之過濾器，去除未溶解物 來調整塗布液Q。 •甲苯 23.08 3質量％ 0甲基乙基酮 23.08 3質量％ *丙烯酸系樹脂 52.762質量％ (日本總硏化學製之GS-1030、固形成分濃度：30質量％、 T g : 1 1 5 °C ) *二亞胺鑰鹽化合物（色素B ) 0.93 7質量％ (日本Carlit製之CIR1081、相對離子：六氟化銻） 籲花青系色素 0.076質量％ (日本旭電化工業製之TZ-123) #矽系界面活性劑 0.059質量％ (D 〇 w C 〇 r n i ng 製之 P ai n t A d 5 7、H L B : 6.7 ) 於表3,顯示近紅外線吸收層中之近紅外線吸收色素（二 亞胺鑰鹽化合物）之種類、離子性液體之種類與含量。另 外，於表4顯示所得到的近紅外線吸收薄膜之物性。可以 得到近紅外線領域之吸收爲強的’於可見光領域之透過率 爲高的薄膜。另外，耐熱性、柔軟性也爲良好的。 實施例1 3 除了使用反射薄膜（日本油脂製之RealLook 7700S)作 -58 - 1354123 修正本 爲透明基材，將近紅外線吸收層積層於與抗反射層相反之 面以外，進行相同於實施例8之方式而得到近紅外線吸收 薄膜。 於表3,顯示近紅外線吸收層中之近紅外線吸收色素（二 _亞胺鑰鹽化合物）之種類、離子性液體之種類與含量。另 •外，於表4顯示所得到的近紅外線吸收薄膜之物性。可以 得到近紅外線領域之吸收爲強的，於可見光領域之透過率 爲高的薄膜。另外，耐熱性、柔軟性也爲良好的。 •表3〕 近紅外線吸收色素 添加劑 (二亞胺鑰鹽） 種類 含量（質量％ ) 實施例8 A D 5.0 實施例9 A D 0.5 實施例1 〇 A D 9.0 比較例4 A 0 參考例1 A G 5 施例1 1 A H 0 實施例1 2 B D 5.0 比較例5 B _ 0 •實施例13 A D 5.0 於表3，色素A、B、化合物D、G、H意指下列化合物： (色素A ) 將雙（三氟甲烷磺醯基）醯亞胺酸作成相胃_ + = N，N,N，，N，-四（對-二-正-丁胺基苯基）-對-伸苯基二亞胺 鑰鹽 •59- 1354123 修正本 (色素B ) 將六氟化銻作成相對離子之N,N，N’，N’-四（對-二-正-丁胺基苯基）-對-伸苯基二亞胺鎗鹽 (離子性液體D ) 正-丁基-3-甲基吡啶鏺雙（三氟甲烷磺醯基）醯亞胺 ‘（離子性液體G ) 正-丁基-3-甲基吡啶鏺四氟硼酸鹽 (離子性液體Η ) φ Ν，Ν，Ν-三甲基-Ν-丙基銨雙（三氟甲烷磺醯基）醯亞胺 〔表4〕 透過率（％) 色調 耐濕熱性 耐熱性 柔軟性 950nm 850nm Y X y Δχ Ay Δχ Δγ 實施例8 4.3 9.3 80.9 0.317 0.340 0.001 0.002 0.001 0.002 2 實施例9 4.3 9.5 81.5 0.317 0.338 0.001 0.002 0.001 0.⑻1 2 實施例10 4.3 9.1 80.4 0.318 0.341 0.001 0.003 0.001 0.002 3 比較例4 4.3 9.0 79.8 0.318 0.342 0.002 0.004 0.003 0.008 6 •參考例1 4.3 9.3 80.8 0.317 0.340 0.001 0.002 0.001 0.002 2 實施伊J11 4.3 9.0 80.9 0.318 0.341 0.001 0.003 0.002 0.004 2 實施例12 4.3 9.7 81.1 0.316 0.339 0.02 0.003 0.002 0.004 2 比較例5 4.3 9.3 80.8 0.317 0.341 0.002 0.006 0.005 0.012 6 實施例13 4.3 9.3 82.9 0.317 0.342 0.001 0.002 0.001 0.002 2 [產業上利用之可能性] 將本發明之近紅外線吸收薄膜設置於作爲近紅外線吸 收濾光片之電漿顯示器前面的情形，相同於習知之近紅外 線吸收濾光片，不僅能夠吸收從電漿顯示器所放射出之不 -60- 1354123 修正本 要的近紅外線，防止精密機器之誤動作’因而也能夠大幅 減低因熱所造成之色調變化，能夠有助於電漿顯示器之高 畫質化的同時，具有提高光學濾光片設計之自由度的優 點，對產業界之貢獻爲大的。 【圖式簡單說明】 - 無。 【主要元件符號說明】 無。90 parts by mass of 90 parts by weight of PET resin having an intrinsic viscosity of 〇62d/g and containing no gp, (ME553 of Toyobo, Japan) and 10 parts by mass of the masterbatch containing ultraviolet absorber After drying under reduced pressure (ITorr) for 6 hours, it was supplied to an extruder. The resin temperature of the melted portion, the mixing portion, the polymer tube, the gear pump, and the filter of the extruder was set to 2 8 (TC, and the subsequent polymer tube was set to 27 5 ° C, and the sheet was formed into a sheet shape from the nozzle. Extrusion is carried out. These polymers are respectively filtered using a filter material of stainless steel sinter (nominal filtration accuracy: 95% of ΙΟμπι or more particles are filtered out), and then the flat die is used to make the resin temperature 2 7 5 ° C. The electrostatic resin is applied by casting, the extruded resin is wound at a surface temperature of 30 ° C -50 - 1354123. After modifying the casting drum (bottle diameter 400 φ, Ra 0.1 pm or less) The film was cooled and solidified to prepare an unstretched film. At this time, the discharge amount was 48 kg/hr, and the obtained unstretched sheet width was 300 mm and the thickness was 140 Ομιτι. Next, 'heating the roll group and the infrared heater to heat the cast film After that, the roller group of the peripheral speed difference is used to stretch by 3.5 times in the longitudinal direction (moving direction) to obtain a uniaxial alignment film. For all the rollers used in the manufacture of the film, the roller is used. Thick surface The roughness Ra is controlled below Ο. ίμιη, and the roller cleaner is arranged in the preheating inlet and the cooling roller in the longitudinal stretching step. The diameter of the roller in the longitudinal stretching step is 150 mm, using an suction roller, an electrostatic close-fitting, a close fitting device, A part of the nip is placed in close contact with the film to adhere the film to the roller. Thereafter, the coating liquid for forming an easy-adhesion layer is formed by a blanket-type polypropylene filter material having a filter particle size (initial filtration efficiency: 9.5 %) 2 5 μηι. The precision filtration is carried out by applying the two-side coating and drying by the reverse roll method. After coating, the end portion of the film is sandwiched by a press plate to introduce a hot air zone heated to 130 ° C, and stretched 4.0 times in the width direction after drying. The f treatment was carried out at 230 ° C for 5 seconds, and in the heat treatment step, 3% relaxation treatment was carried out along the width direction to obtain a base film (B). The thickness of the film was 100 μm, and the film was easy to follow. The coating amount of the layer was 0.01 g/m 2 , and the obtained film had a transmittance of 3 8 nm at a wavelength of 4%, and had excellent ultraviolet absorbing properties. Further, the total light transmittance was 91%, the haze was 0.6%, and transparency was obtained. Excellent. 2 . The near-infrared absorbing layer was laminated on the intermediate coating layer, and the transmittance of 950 nm after drying the following coating liquid J (viscosity: 23 cps) was 4.3%, and the reverse coating was performed by a slanting gravure having a diameter of 60 cm, respectively. By drying at 40 ° C, 5 m / s -51 - 1354123, the hot air drying for 20 seconds 'drying at 150 ° C, 2 〇 m / sec hot air for 2 〇 seconds, further at 90 ° C, 20 m / sec After hot air drying for 1 second, a near-infrared absorption filter was prepared. (Coating liquid J for the near-infrared absorbing layer) The coating liquid material was mixed by the following mass ratio and stirred for 3 sec or more. Next, the coating liquid J was adjusted by using a filter having a nominal filtration accuracy of Ιμηη to remove undissolved matter. Toluene 22.193% by mass #methyl ethyl ketone 23.083% by mass propylene oxide resin 52.762% by mass (GS-1〇3〇, 形成 硏 〇 〇 〇 〇 〇 〇 〇 〇 〇 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固1 1 5 °C ) *Diimine salt compound (Pigment A) 0.937% by mass (CIR 1085, Japan car lit, relative ion: bis(trifluoromethanesulfonyl) ruthenium) • Cyanine .Pigment 0.076% by mass TZ-123 by Sakamoto Asahi Chemical Co., Ltd. *矽矽 surfactants 0.0 5 9质量% (PaintAd 57 by Dow Corning, HLB: 6.7) *Ionic liquid D 0.890% by mass (positive - Butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imine) is shown in Table 3, showing the type and ionicity of the near-infrared absorbing pigment (diimine salt compound) in the near-infrared absorbing layer. The type and content of the liquid. Further, the physical properties of the obtained near-infrared absorbing film are shown in Table 4. It is possible to obtain a strong absorption in the near-infrared field and a transmittance in the visible light region -52- 1354123. In addition, heat resistance and flexibility are also good. Example 9 A near-infrared absorbing film was obtained in the same manner as in Example 8 except that the following coating liquid K was used. (Coating liquid K for the near-infrared absorbing layer) The coating liquid material was mixed by the following mass ratio, and stirred for 30 minutes or more. The picker's use the nominal accuracy of Ιμηι to remove the undissolved material to adjust the coating liquid. _Toluene 22.998% by mass ♦ Methyl ethyl ketone 23.083% by mass * Acrylic resin 52.762% by mass (GS-1030, manufactured by Nippon Scientific Co., Ltd., solid component concentration: 30% by mass, T g : 1 15 °C) * Diimine salt compound (pigment A) 0.937% by mass (CIR1085, Japan car lit, relative ion: bis(trifluoromethanesulfonyl) phthalic acid), cyanine pigment, 0.076% by mass (曰本旭化Industrial TZ-123) * Sand-based surfactant 0.059 mass% (PaintAd 57 by Dow Corning, HLB: 6.7) Lu ionic liquid D 0.085 mass% (n-butyl-3-methylpyridine double Table 3 shows the types of near-infrared absorbing pigments (diimine iron salt compounds) and the types and contents of ionic liquids in the near-infrared ray absorbing layer. Further, the physical properties of the obtained near-infrared absorbing film are shown in Table 4. Can be -53- 1354123 Correction This film has a high absorption in the near-infrared field and has a high transmittance in the visible light field. In addition, heat resistance and flexibility are also good. Example 1 A near infrared ray absorbing film was obtained in the same manner as in Example 8 except that the following coating liquid L was used. ' (The coating liquid L for the near-infrared absorbing layer) The coating liquid material was mixed by the following mass ratio, and stirred for 30 minutes or more. Next, the undissolved material is removed by using a filter having a nominal filtration accuracy of Ιμπι # adjusting the coating liquid L. *Toluene 21.411% by mass *Methyl ethyl ketone 23.083% by mass •Acrylic resin 52.762% by mass (GS-1030, manufactured by Nippon Scientific Co., Ltd., solid component concentration: 3〇 mass%, T g : 1 15 °C)二 胺 钥 key salt compound (pigment A) 0.937% by mass (CIR1085 made by Japan Car lit, relative ion: bis(trifluoromethane)# imiline) *Cyanine pigment 〇·〇76% by mass (曰本旭化化制制制ΤΖ-123) *矽 surfactant is 0.059% by mass (PaintAd 57 'HLB: 6.7 by Dow Corning) ionic liquid D 1.671% by mass (n-butyl-3 - A) The pyridinium bis(trifluoromethanesulfonyl)imine) is shown in Table 3, showing the type of near-infrared absorbing pigment (diimine salt compound) in the near-infrared absorbing layer, and the kind and content of the ionic liquid. Further, -54- 1354123 modifies the above. The physical properties of the obtained near-infrared absorbing film are shown in Table 4. A film having a high absorption in the near-infrared field and a high transmittance in the visible light region can be obtained. In addition, heat resistance and flexibility are also good. Comparative Example 4 A near-infrared absorbing film was obtained in the same manner as in Example 8 except that the following coating liquid was used. (Coating liquid 近 for the near-infrared absorbing layer) The coating liquid material was mixed by the following mass ratio, and stirred for 30 minutes or more. • Use a filter with a nominal filtration accuracy of Ιμιη to remove undissolved material to adjust the coating solution. *Toluene 23.0 8 3 % by mass *Methyl ethyl ketone 23.083% by mass • Acrylic resin 52.762% by mass (GS-l〇3〇, manufactured by Nippon Scientific Co., Ltd., solid component concentration: 3% by mass, T g : 115 . . . Ludiimine iron salt compound (pigment A) 0.937% by mass _ (CIR1085 made by Carlit, Japan, relative ion: bis(trifluoromethanesulfonyl) phthalic acid) • Cyanine pigment 0.076% by mass (TZ-123 manufactured by Sakamoto Asahi Chemical Co., Ltd.) * The lanthanide surfactant is 0.059 mass% (P ii nt A d 5 7 , H LB : 6.7 by D 〇w C 〇r ni ng). The type of near-infrared absorbing pigment (diimine salt compound) in the near infrared ray absorbing layer. Further, the physical properties of the obtained near-infrared absorbing film are shown in Table 4. It is possible to obtain a film with a strong absorption in the near-infrared field of -55- 1354123. Compared with Examples 8 to 10 to which an ionic liquid has been added, a film having a slightly lower transmittance in the visible light region can be obtained. Heat resistance and flexibility are poor. Reference Example 1 In Example 8, a near-infrared absorbing film was obtained in the same manner as in Example 8 except that the type of the ionic liquid was changed to the following ionic liquid G. Ionic liquid G: n-butyl-3-methylpyridinium tetrafluoroborate Φ In Table 3, the type of near-infrared absorbing pigment (diimine salt compound) in the near-infrared absorbing layer, ionic liquid Type and content. Further, the physical properties of the obtained near-infrared absorbing film are shown in Table 4. A film having a high absorption in the near-infrared field and a high transmittance in the visible light region can be obtained. In addition, heat resistance and flexibility are also good. [Example 1] In the same manner as in Example 8, except that the type of the ionic liquid was changed to the following ionic liquid enthalpy, a near-red absorbing film was obtained. Ionic liquid H: N,N,N-trimethylpropylammonium bis(trifluoromethanesulfonyl) quinone imine in Table 3, showing near-infrared absorbing pigment in the near-infrared absorbing layer (diimine iron salt) The type of compound), the type and content of ionic liquid. Further, the physical properties of the obtained near-infrared absorbing film are shown in Table 4. A film which is strongly absorbed in the near-infrared field can be obtained. Although the heat resistance was inferior to that of Example 8, it was better than Comparative Example 4. In addition, the softness is good. -56- 1354123 MODIFICATION EXAMPLE 1 2 A near-infrared absorbing film was obtained in the same manner as in Example 8 except that the following coating liquid P was used. (Coating liquid P for the near-infrared absorbing layer) The coating liquid material was mixed by the following mass ratio and stirred for 3 sec or more. • Next, adjust the coating solution by using a filter with a nominal filtration accuracy of ημηι to remove undissolved material. *Toluene 22.1 93% by mass φ methyl ethyl ketone 23.08 3% by mass Acrylic resin 52.762% by mass (GS-1030, manufactured by Nippon Scientific Co., Ltd., solid component concentration: 30% by mass, T g : 1 1 5 ° C «Diimine salt compound (pigment B) 0.937% by mass (CIR1081, relative ion: hexafluorene hexafluoride manufactured by Carlit) 吁Cyanine pigment 〇·〇76% by mass (Sakamoto Asahi Chemical Co., Ltd.) TZ-123) f矽-based surfactant 0.059 mass% (PaintAd 57 by Dow Corning, HLB: 6.7) ♦ ionic liquid D 0.890% by mass (n-butyl-3-methylpyridinium bis(trifluoromethane) Sulfhydryl)imine) Table 3 shows the types of near-infrared absorbing pigments (diimine salt compounds) and the types and contents of ionic liquids in the near-infrared ray absorbing layer. Further, the physical properties of the obtained near-infrared absorbing film are shown in Table 4. A film having a high absorption in the near-infrared field and a high transmittance in the visible light region can be obtained. In addition, heat resistance and flexibility are also good. -57- 1354123 Revision Example 5 A near-infrared absorbing film was obtained in the same manner as in Example 8 except that the following coating liquid Q was used. (Coating liquid Q for the near-infrared absorbing layer) The coating liquid material was mixed by the following mass ratio, and stirred for 30 minutes or more. ‘Next, the coating solution Q is adjusted by removing the undissolved material using a filter having a nominal filtration accuracy of Ιμηη. • Toluene 23.08 3 mass% 0 methyl ethyl ketone 23.08 3 mass% * Acrylic resin 52.762 mass% (GS-1030, manufactured by Nippon Scientific Co., Ltd., solid component concentration: 30% by mass, T g : 1 15 °C *Diimide salt compound (Pigment B) 0.93 7 mass% (CIR1081, relative ion: hexafluoride hexafluoride manufactured by Carlit, Japan) 0.076% by mass of cyanine pigment (TZ-123, manufactured by Asahi Kasei Kogyo Co., Ltd.) #矽系 surfactants 0.059% by mass (D 〇w C 〇rni ng made by P ai nt A d 5 7 , HLB : 6.7 ) In Table 3, the near-infrared absorbing pigment (diimine) in the near-infrared absorbing layer is shown. The type of key salt compound, the type and content of the ionic liquid. Further, the physical properties of the obtained near-infrared absorbing film are shown in Table 4. It is possible to obtain a film having a high transmittance in the near-infrared field and having a high transmittance in the visible light region. In addition, heat resistance and flexibility are also good. Example 1 3 The same procedure as in Example 8 was carried out except that a reflective film (RealLook 7700S manufactured by Nippon Oil & Fat Co., Ltd.) was used as -58 - 1354123, and the present invention was a transparent substrate, and the near infrared ray absorbing layer was laminated on the opposite side to the antireflection layer. A near-infrared absorbing film is obtained in a manner. Table 3 shows the types of near-infrared absorbing pigments (diamine-imine salt compounds) and the types and contents of ionic liquids in the near-infrared ray absorbing layer. In addition, the physical properties of the obtained near-infrared absorbing film are shown in Table 4. A film having a high absorption in the near-infrared field and a high transmittance in the visible light region can be obtained. In addition, heat resistance and flexibility are also good. • Table 3] Near-infrared absorbing pigment additive (diimine salt) Content content (% by mass) Example 8 AD 5.0 Example 9 AD 0.5 Example 1 〇AD 9.0 Comparative Example 4 A 0 Reference Example 1 AG 5 Example 1 1 AH 0 Example 1 2 BD 5.0 Comparative Example 5 B _ 0 • Example 13 AD 5.0 In Table 3, the pigments A, B, compounds D, G, H mean the following compounds: (Pigment A) Will double (three Fluoromethanesulfonyl) ruthenium as a phase stomach _ + = N,N,N,,N,-tetrakis(p-di-n-butylaminophenyl)-p-phenylene diimide盐•59- 1354123 Amendment (Pigment B) N,N,N',N'-tetrakis(p-di-n-butylaminophenyl)-p-phenylene hexafluoride as a relative ion Diimide gun salt (ionic liquid D) n-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine '(ionic liquid G) n-butyl-3-methyl Pyridinium tetrafluoroborate (ionic liquid Η) φ Ν, Ν, Ν-trimethyl-Ν-propyl ammonium bis(trifluoromethanesulfonyl) quinone imine (Table 4) Transmittance (%) Moisture resistance Heat resistance Softness 950nm 850nm YX y Δχ Ay Δχ Δγ Example 8 4.3 9.3 80.9 0.317 0.340 0.001 0.002 0.001 0.002 2 Example 9 4.3 9.5 81.5 0.317 0.338 0.001 0.002 0.001 0. (8) 1 2 Example 10 4.3 9.1 80.4 0.318 0.341 0.001 0.003 0.001 0.002 3 Comparative Example 4 4.3 9.0 79.8 0.318 0.342 0.002 0.004 0.003 0.008 6 • Reference Example 1 4.3 9.3 80.8 0.317 0.340 0.001 0.002 0.001 0.002 2 Implementation Yi J11 4.3 9.0 80.9 0.318 0.341 0.001 0.003 0.002 0.004 2 Example 12 4.3 9.7 81.1 0.316 0.339 0.02 0.003 0.002 0.004 2 Comparative Example 5 4.3 9.3 80.8 0.317 0.341 0.002 0.006 0.005 0.012 6 Example 13 4.3 9.3 82.9 0.317 0.342 0.001 0.002 0.001 0.002 2 [Probability of industrial use] The near-infrared absorbing film of the present invention is provided as a near-infrared absorbing filter. The front of the plasma display is the same as the conventional near-infrared absorbing filter, which can absorb not only the near-infrared rays that are emitted from the plasma display, but also prevent the malfunction of the precision machine. Significantly reduce the change in color tone caused by heat, which can help High-quality image of the plasma display while having advantages improve the degree of freedom of design of the optical filter, as the contribution of a large industry. [Simple description of the schema] - None. [Main component symbol description] None.

-61 --61 -

Claims (1)

1354123 修正本1354123 Amendment 第096103279號「近紅外線吸收薄膜」專f (2011年8月 十、申請專利範圍： 1. 一種近紅外線吸收薄膜，其特徵爲其係於透明 設置主要由近紅外線吸收色素、樹脂構成之組 的近紅外線吸收層之近紅外線吸收薄膜’其中 線吸收色素不包含選自下列通式（1)~(11Π所示 成之群之陽離子及抑制劑陰離子所構成的安 案 17曰修正） 基材上， 成物而成 該近紅外 化合物組 定化花青 (cyanine) ;No. 096103279 "Near-infrared absorbing film" special f (August 11, 2011, patent application scope: 1. A near-infrared absorbing film characterized in that it is set in a transparent arrangement mainly composed of a near-infrared absorbing pigment and a resin. The near-infrared absorbing film of the near-infrared absorbing layer' wherein the line absorbing dye does not contain a cation and an inhibitor anion selected from the group consisting of the following general formulas (1) to (11 曰) Forming the near-infrared compound group to define cyanine; [式中，環A及環Α·各自獨立代表苯環、萘環、宜 R1及R1’各自獨立代表鹵素原子、硝基；氰基、 之芳基、碳數1〜8之烷基或碳數1~8之烷氧基 及R4各自獨立代表氫原子、鹵素原子、氰基、 之芳基、二苯基胺基或碳數1~8之烷基，X及 卩比D定環， 碳數6~30 R2、R3 碳數6~30 X’各自獨 1354123 修正本 立代表氧原子、硫原子、硒原子、丙烷-2,2 -二基、丁院 -2,2-二基、碳數3~6之環烷-1，1-二基、-1^-或-1^丫|.，丫、 ¥’及Υ»各自獨立代表碳數1〜30之有機基，r，各自獨 立代表〇〜2之整數]， « 於該組成物中，含有三氟甲烷磺酸化合物或雙（三氣甲 烷磺醯基）醯亞胺酸化合物作爲相對離子的花青·乍 爲近紅外線吸收色素。 如申請專利範圍第1項之近紅外線吸收薄膜，其φ @糸工 外線吸收色素含有二亞胺鑰（diimonium)鹽化合物。 3.如申請專利範圍第2項之近紅外線吸收薄膜，其中二@ 胺鑰鹽化合物係一種將雙（三氟甲烷磺醯基）醯gg @ _ 作成相對離子的二亞胺鑰鹽化合物。 4 ·如申請專利範圍第1項之近紅外線吸收薄膜，其中，近 紅外線吸收色素係一種將三氟甲烷磺酸化合物或雙（三 氟甲烷磺醯基）醯亞胺酸化合物作爲相對離子的花青色 φ素係於近紅外線吸收層中含有0.1質量％以上且1〇.〇質 量％以下。 5 _如申請專利範圍第4項之近紅外線吸收薄膜，其中近紅 外線吸收色素包含將雙（三氟甲烷磺醯基）醯亞胺酸化 合物作成相對離子的二亞胺鑰鹽化合物及將三氟甲烷磺 酸化合物或雙（三氟甲烷磺醯基）醯亞胺酸化合物作成 相對離子的花青色素。 6 .如申請專利範圍第〗至5項中任一項之近紅外線吸收薄 -2- 1354123 修正本 膜，其中構成近紅外線吸收層之樹脂爲丙烯酸系樹脂。 7. 如申請專利範圍第1至5項中任一項之近紅外線吸收薄 膜’其係將近紅外線吸收色素及樹脂於有機溶劑中攪拌 .30分鐘以上而調製的塗布液塗布於透明基材上而獲得。 8. 如申請專利範圍第1至5項中任一項之近紅外線吸收薄 膜’其於近紅外線含有界面活性劑。[wherein, ring A and ring oxime each independently represent a benzene ring, a naphthalene ring, preferably R1 and R1' each independently represent a halogen atom, a nitro group; a cyano group, an aryl group, an alkyl group having 1 to 8 carbon atoms or carbon The alkoxy group of 1 to 8 and R4 each independently represent a hydrogen atom, a halogen atom, a cyano group, an aryl group, a diphenylamino group or an alkyl group having 1 to 8 carbon atoms, X and a phosphonium ratio D ring, carbon Number 6~30 R2, R3 Carbon number 6~30 X' Respective 1354123 Correction stands for oxygen atom, sulfur atom, selenium atom, propane-2,2-diyl, Dingyuan-2,2-diyl, carbon number 3~6 of cycloalkane-1,1-diyl, -1^- or -1^丫|., 丫, ¥' and Υ» each independently represent an organic group having a carbon number of 1 to 30, r, each independently represented整数~2 integer], « In this composition, a trifluoromethanesulfonic acid compound or a bis(trioxanesulfonyl) ruthenium amide compound is used as a relative ion of cyanine and lanthanum as a near-infrared absorbing pigment. For example, in the near-infrared absorbing film of claim 1, the φ @糸 external line absorbing dye contains a diimonium salt compound. 3. The near-infrared absorbing film according to item 2 of the patent application, wherein the bis-amine salt compound is a diimine salt compound which forms bis(trifluoromethanesulfonyl) 醯gg @ _ as a relative ion. 4. The near-infrared absorbing film according to item 1 of the patent application, wherein the near-infrared absorbing pigment is a flower having a trifluoromethanesulfonic acid compound or a bis(trifluoromethanesulfonyl) liminium compound as a relative ion. The cyan φ element is contained in the near-infrared ray absorbing layer in an amount of 0.1% by mass or more and 1% by mass or less. 5 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The methanesulfonic acid compound or the bis(trifluoromethanesulfonyl) quinone acid compound is used as a relative ion cyanine dye. 6. The near-infrared absorbing thin film -2- 1354123 according to any one of claims 1-5 to 5, wherein the resin constituting the near-infrared absorbing layer is an acrylic resin. 7. The near-infrared absorbing film of any one of claims 1 to 5, wherein the near-infrared absorbing pigment and the resin are stirred in an organic solvent. The coating liquid prepared by applying the coating liquid to the transparent substrate for 30 minutes or more is applied. obtain. 8. The near infrared absorbing film of any one of claims 1 to 5, which contains a surfactant in the near infrared ray. -3--3-