201228829 六、發明說明： 【發明所屬之技術領域】 本發明關於一種可使用於各種光學機器的快門或光圈 構件等之光學機器用遮光構件。 【先前技術】 近年來，因爲對高性能單眼反射式相機、小型相機、 攝影機等的各種光學機器要求小型化、輕量化，由金屬材 料所形成的光學機器之快門或光圏構件係正在替換成塑膠 材料。作爲如此的塑膠材料之光圈，已知將含有碳黑、滑 劑、微粒子及黏結劑樹脂的遮光膜形成在薄膜基材上而得 之遮光性薄膜（專利文獻1、2)。 先前择術文獻 專利文獻 專利文獻1 :特開平9-2742 1 8號公報 專利文獻2 : W02 006/0 1 65 5 5號公報 【發明內容】 [發明所欲解決的問題] 與由金屬材料所成的遮光構件相比，上述遮光性薄膜 由於堅韌性極弱，故若將該遮光性薄膜當作光學機器的快 ' 門或光圈構件使用，則不耐使用，有自與其它構件的接觸 部位發生歪斜、變形或破損的問題。如此問題在要求薄型 化的近年之狀況下，可說是大問題。 -5- 201228829 相對於此，亦考慮將由金屬材料所成的遮光構件直接 薄型化之手法，但若使用該遮光構件當作快門或光圈構件 ’則由於與其它構件的接觸而容易發生變形。該變形由於 在金屬材料的性質上不會返回，如此遮光構件係使用不便 。又’與塑膠材料相比，金屬材料終究成本高。 如此地，要求不使用金屬材料，即使薄型化也具有堅 韌性’不易發生薄膜破損等之光學機器用遮光構件。 [解決問題的手段] 本發明者們對於此’發現藉由成爲在遮光膜中含有羥 値爲l〇〇(mgKOH/g)以上的黏結劑樹脂當作黏結劑樹脂、 與平均粒徑未達Ιμιη的微粒子之遮光構件，可即使薄型化 也具有堅韌性’即使與其它構件接觸也不易發生薄膜的破 損等，而達成本發明。 即’本發明的光學機器用遮光構件，係含有由合成樹 脂薄膜所成的基材’與在前述基材的至少一面上形成的遮 光膜’其特徵爲：前述遮光膜含有羥値爲l〇〇(mgKOH/g) 以上的黏結劑樹脂、碳黑及平均粒徑未達1 μιη的微粒子。 又，於本發明的光學機器用遮光構件中，微粒子較佳 爲無機微粒子。又，該無機微粒子較佳爲碳酸鈣。 另外’於本發明的光學機器用遮光構件中，較佳的遮 光膜含有矽石。 [發明的效果] -6 - 201228829 若依照上述發明，藉由在遮光膜中含有羥値爲100( mgKOH/g)以上的黏結劑樹脂及平均粒徑未達丨μιη的微粒 子’可成爲即使薄型化也具有堅韌性，不易發生薄膜的破 損等之遮光構件。 【實施方式】 [實施發明的形態] 以下說明本發明的光學機器用遮光構件（以下亦稱爲 「遮光構件」）的實施形態。 本發明的遮光構件係含有由合成樹脂薄膜所成的基材 ，與在前述基材的至少一面上形成的遮光膜。該遮光膜含 有羥値爲100(mgKOH/g)以上的黏結劑樹脂、碳黑及平均 粒徑未達，ίμιη的微粒子。 再者’本發明中所言的平均粒徑係指以雷射繞射式粒 度分布測定裝置（例如島津製作所公司：SALD-7000等）所 測定的中位徑（D 5 0)。 作爲由合成樹脂薄膜所成的基材，可舉出由聚酯、 ABS(丙烯腈-丁二烯-苯乙烯）、聚醯亞胺、聚苯乙烯、聚 碳酸酯、丙烯酸酯、聚烯烴、纖維素樹脂 '聚颯、聚苯硫 、聚醚颯、聚醚醚酮等所成者。其中，較宜使用聚酯薄膜 ’從機械強度、尺寸安定性優異之點來看，特佳爲經延伸 加工，尤其經二軸延伸加工的聚酯薄膜。 又’作爲基材，除了透明者，還可使用發泡聚酯薄膜 或含有碳黑等的黑色顔料或其它顏料之合成樹脂薄膜。此 201228829 時，上述基材係可按照各自的用途而選擇適切者。例如， 作爲遮光構件使用時，在構件截面的合成樹脂薄膜部分中 ，由於透鏡等所聚光的光進行反射而受到不利影響，必須 高遮光性時，可使用含有碳黑等黑色顏料的合成樹脂薄膜 ，於其它情況中，可使用透明或經發泡的合成樹脂薄膜。 於本實施形態中，從得到遮光膜本身作爲遮光構件的 充分遮光性來看，當在合成樹脂薄膜中含有黑色顏料時， 只要以合成樹脂薄膜目視爲黑色的程度，即光學濃度爲3 左右的方式含有即可。因此，如以往地，由於在合成樹脂 薄膜中以不損害作爲基材的物性之限度內含有黑色顔料， 故不改變合成樹脂薄膜的物性，可便宜地獲得。 基材的厚度較佳爲4〜50μιη，尤其從薄型化的觀點來 看，更佳爲4〜38 μιη。又，對於基材，從提高與寧光膜的 接著性之觀點來看，視需要亦可進行增黏處理或電暈處理 〇 於基材的至少一面上形成的遮光膜，係含有羥値爲 l〇〇(mgKOH/g)以上的黏結劑樹脂、碳黑及平均粒徑未達 1 μιη的微粒子。 通常，若使用平均粒徑未達Ιμηι的微粒子於黏結劑樹 脂中，則由於粒徑小，微粒子有凝聚的傾向。如此的話， 微粒子無法在黏結劑樹脂中均勻分散，而偏向地存在。若 由該材料來形成遮光膜，則遮光膜中容易形成微粒子的存 在密度低的部分，在遮光膜中形成容易局部變形的部分。 茲認爲若將具備該遮光膜的遮光構件使用一定期間，則自 -8- 201228829 容易變形的部分發生變曲·畸變，未必是堅 另一方面，若使平均粒徑未達Ιμπι的掷 爲100(mgKOH/g)以上的黏結劑樹脂中而使 子被該黏結劑樹脂的羥値所影響，而不會局 可均勻分散。因此，茲認爲於遮光膜全體中 平衡係成爲合適者，即使作爲遮光構件使用 局部的彎曲•畸變，而可成爲堅韌性強者。 作爲羥値爲l〇〇(mgKOH/g)以上的黏結 出聚（甲基）丙烯酸系樹脂、聚酯樹脂、聚醋 '聚氯乙烯、聚乙烯縮丁醛樹脂、纖維素系 烯/聚丁二烯樹脂、聚胺甲酸酯樹脂、醇酸 樹脂、不飽和聚酯樹脂、環氧酯樹脂、環氧 烯酸酯系揮脂、胺甲酸酯丙烯酸酯系樹脂、 系樹脂、聚醚丙烯酸酯系樹脂、酚系樹脂、 尿素系樹脂、苯二甲酸二烯丙酯系樹脂等的 熱硬化性樹脂，亦可混合此等的1種或2種 黏結劑樹脂的羥値爲100(mgK〇H/g)以 結劑樹脂的羥値成爲100(mgKOH/g)以上， 徑未達Ιμπι的微粒子變成均勻分散在遮光膜 光膜薄型化，遮光構件全體也具有堅韌性， 膜的破損等。從進一步發揮堅韌的觀點來看 的羥値較佳爲125(mgKOH/g)以上，更佳爲 以上。另一方面，從防止彎曲應力降低而塗 來看，上限較佳爲250(mgKOH/g)以下。 韌性強者。 :粒子含於羥値 用，則該微粒 部凝聚，變成 微粒子的分散 ，也不易發生 劑樹脂，可舉 酸乙烯酯樹脂 樹脂、聚苯乙 樹脂、丙烯酸 樹脂、環氧丙 聚酯丙烯酸酯 蜜胺系樹脂、 熱塑性樹脂或 以上而使用。 上。藉由使黏 如上述平均粒 中，即使將遮 可不易發生薄 ，黏結劑樹脂 200(mgKOH/g) 膜變脆的觀點 -9' 201228829 羥値爲100(mgKOH/g)以上的黏結劑樹脂之含有率’ 在遮光膜中較佳爲1 5重量％以上，更佳爲20重量％以上 。藉由使前述黏結劑樹脂的含有率成爲在遮光膜中的15 重量％以上，可防止基材與遮光膜的接著性降低。另一方 面，前述黏結劑樹脂的含有率’在遮光膜中較佳爲50重 量％以下，更佳爲45重量％以下，尤佳爲40重量％以下。 藉由使前述黏結劑樹脂的含有率成爲在遮光膜中的50重 量％以下，可防止遮光性的降低。 遮光膜中所含有的碳黑係用於將黏結劑樹脂著色成黑 色而賦予遮光性，同時賦予導電性，而防止靜電所致的帶 電。 爲了得到得充分的遮光性，碳黑的平均粒徑較佳爲 1 μ m以下，更佳爲〇 . 5 μ m以下。 碳黑的含有率在遮光膜中較佳爲10重量％〜50重量％ ，更佳爲15重量％〜45重量％。藉由使在遮光膜中成爲 1 〇重量％以上，可防止遮光性及導電性的降低，藉由使成 爲50重量％以下，可提高接著性或耐擦傷性，而且可防止 塗膜強度的降低及成本高。 又，於遮光膜中，從在表面上形成微細凹凸，而減少 入射光的反射，使表面的光澤度（鏡面光澤度）降低，提高 作爲遮光構件時的消光性之觀點來看，亦可含有無機粒子 。作爲無機粒子，可舉出矽石、偏矽酸鋁酸鎂、氧化鈦等 ’於此等之中’從粒子的分散性·低成本等之觀點來看， 較佳爲使用矽石。 ⑧ -10- 201228829 無機粒子的平均粒徑較佳爲Ιμπι〜ΙΟμιη，更佳爲Ιμιη 〜6 μιη »此係因爲藉由成爲如此的範圍，在遮光構件的表 面上形成微細凹凸，而得到消光性。 無機粒子的含有率在遮光膜中較佳爲0.5重量％〜10 重量％，更佳爲0.5重量％〜5重量％。藉由使在遮光膜中 成爲0.5重量％以上，可防止表面的光澤度（鏡面光澤度） 增加而消光性降低。另一方面，藉由成爲1 〇重量％以下， 可防止遮光構件的滑動所造成的無機粒子之脫落或在遮光 構件本身發生損傷，可防止造成滑動性的降低。 特別地，於要求高的遮光性或導電性時，無機粒子的 含有率更佳爲上述範圍的遮光膜中之5重量％以下。本實 施形態所用的無機粒子，由於即使如前述的少量也可得到 高的消光性，故藉由成爲5重量％以下，可得到充分的消 光性，而且可使相對地增加碳黑、後述的微粒子之含有率 ，可不降低堅韌性而提高遮光性、導電性等物性。 遮光膜中所含有的平均粒徑未達1 μιη的微粒子，係如 上述地藉由與羥値爲100 (mgKOH/g)以上的黏結劑樹脂倂 用，而在遮光膜全體中微粒子的分散平衡成爲合適者，即 使作爲遮光構件使用，可不易發生局部的彎曲·畸變，可 成爲堅韌性強者。又，亦可提高作爲遮光膜時的塗膜硬度 。再者，由於不易發生局部的彎曲•畸變，故成爲不易發 生熱變形者。 作爲如此者，例如可舉出由聚乙烯蠟、石蠟等的烴系 滑劑、硬脂酸、1 2 -羥基硬脂酸等的脂肪酸系滑劑、油醯 -11 - 201228829 胺、芥醯胺等的醯胺系滑劑、硬脂酸單甘油酯等的酯系滑 劑、醇系滑劑、聚矽氧樹脂粒子、聚四氟乙烯蠟等的氟樹 脂粒子、丙烯酸樹脂粒子、交聯丙烯酸樹脂粒子、交聯聚 苯乙烯樹脂粒子等的樹脂微粒子所成者，或由金屬皂、滑 石、二硫化鉬、碳酸鈣、矽石、氫氧化鋁、氧化锆、硫酸 鋇、氧化鈦等的固體潤滑劑等無機微粒子所成者。於此等 之中，從全體粒子的硬度高，可幫助堅韌性的提高之觀點 來看，特佳爲使用由無機微粒子所成者。再者，於無機微 粒子之中，若使用碳酸鈣，由於作爲遮光構件係堅韌性更 強而較佳。此等微粒子係可爲1種或混合2種以上使用。 再者，此處所列舉的矽石係與爲了提高前述消光性而含有 的矽石不同。 微粒子的含有率在遮光膜中較佳爲2.5重量％〜40重 量％，更佳爲10重量％〜35重量％。藉由使在遮光膜中成 爲2 · 5重量％以上，可進一步增強堅韌性，藉由使成爲40 重量％以下，可提高碳黑的相對的含量，可一邊得到堅韌 性一邊防止遮光性的降低。 又，前述微粒子對前述黏結劑樹脂的含有比例，以相 對於前述黏結劑樹脂1〇〇重量份而言，較佳爲含有30〜 200重量份的前述微粒子，更佳爲含有50〜150重量份。 藉由成爲如此的含有比例，可一邊維持遮光性，一邊進一 步地改善遮光膜中的前述微粒子之分散平衡，可成爲堅韌 性更優異的遮光構件。 於基材的至少一面上形成的遮光膜中，在不損害本發 ⑧ -12- 201228829 明的機能時，亦可含有難燃劑、抗菌劑、防黴劑、抗氧化 劑、可塑劑、均平劑、流動調整劑、消泡劑、分散劑等的 各種添加劑。 遮光膜的厚度較佳爲 3μπι〜30μπι，更佳爲 5μηι〜 2 0μπι。藉由成爲3μπι以上，可防止在遮光膜中發生針孔 等，可得到充分的遮光性。又，藉由成爲30μηι以下，可 防止在遮光膜發生破裂。 本實施形態的光學機器用遮光構件，係可藉由在基材 的一面或兩面，塗佈含有如上述羥値爲l〇〇(mgKOH/g)以 上的黏結劑樹脂、碳黑及平均粒徑未達1 μπι的微粒子等之 遮光膜用塗佈液，經由輥塗、桿塗、口模式塗佈、刮板塗 佈、氣刀塗佈等習知的塗佈方法來塗佈，使乾燥後，按照 需要經由加熱·加壓等而獲得。塗佈液的溶劑可使用水或 有機溶劑、水與有機溶劑的混合物等。 如以上，本實施形態的光學機器用遮光構件，由於在 基材的至少一面上含有特定的遮光膜，保持遮光性、導電 性等的遮光膜之物性，故適用作爲高性能單眼反射式相機 、小型相機、攝影機、行動電話、投影機等光學機器的快 門、光圈構件。 特別地，本實施形態的遮光膜，由於含有羥値爲1 00 (mgKOH/g)以上的黏結劑樹脂與平均粒徑未達Ιμιη的微粒 子，微粒子可在遮光膜中均勻分散，故即使薄型化也具有 堅韌性，可成爲不易發生薄膜的破損等之遮光構件。結果 ’尤其適用於近年來特別要求薄型化的附加相機之行動電 -13- 201228829 話的快門、光圈構件等。再者，由於不易發生局部的彎曲 •畸變，故可成爲不易發生熱變形者。 實施例 以下，藉由實施例來進一步說明本發明。再者，「份 」、「％」只要沒有特別指示，則以重量爲基準。 1.遮光構件之製作 [實施例1] 作爲基材，使用厚度25 μιη的黑色聚對苯二甲酸乙二 酯薄膜（Lumirror Χ30 :東麗公司），於該基材的兩面藉由 桿塗法分別塗佈下述處方的遮光膜用塗佈液，進行乾燥， 以得使得乾燥時的厚度成爲1〇μιη，形成遮光膜，而製作 實施例1的光學機器用遮光構件。 <實施例1的遮光膜用塗佈液> •聚酯多元醇 9.68份 (Burnock 1 1-408 : DIC 公司，羥値 200(mgKOH/g)，固體 成分70%) •異氰酸酯 9.37份 (BurnockDN980: DIC 公司，固體成分 75%) .碳黑 4.57份 (Vulcan XC-72: CABOT 公司） •矽石 0.8 9份 ⑧ -14- 201228829 (TS100: Evonik-Degussa曰本公司，平均粒徑作"1) •微粒子（碳酸鈣）7.50份 (Sunlight SL-700:竹原化學工業公司’平均粒徑〇.74 μηι) .甲基乙基酮 36.93份 •甲苯 1 5.8 3份 [實施例2] 除了於實施例1所用的遮光膜用塗佈液中’將聚酯多 元醇變更爲聚酯多元醇（Burnock J-517: DIC公司，羥値 1 40(mgKOH/g)，固體成分70%)，使異氰酸酯的添加量成 爲6.5 6重量份以外，與實施例1同樣地，製作實施例2 的光學機器用遮光構件。 [實施例3] 除了於實施例1所用的遮光膜用塗佈液中，將聚酯多 元醇變更爲聚酯多元醇（Burnock D-144-65BA: DIC公司， 羥値100(mgKOH/g)，固體成分65%) ’使添加量成爲 10.42重量份，更使異氰酸酯的添加量成爲5.04重量份以 外，與實施例1同樣地，製作實施例3的光學機器用遮光 構件。 [實施例4] 除了於實施例1所用的遮光膜用塗佈液中，將微粒子 -15- 201228829 (碳酸鈣）變更爲微粒子（氧化鈦，A-100 :石原產業公司， 平均粒徑〇.15μιη)以外，與實施例1同樣地，製作實施例 4的光學機器用遮光構件。 [實施例5] 除了於實施例1所用的遮光膜用塗佈液中’將微粒子 (碳酸鈣）變更爲微粒子（丙烯酸粒子’ Chemsnow ΜΡ·1600 ，綜硏化學公司，平均粒徑〇 . 8 μιη )以外，與實施例1同樣 地，製作實施例5的光學機器用遮光構件。 [比較例1] 除了於實施例1所用的遮光膜用塗佈液中’將聚酯多 元醇變更爲丙烯酸多元醇（Acrydic A_801P: DIC公司’羥 値50(mgKOH/g)，固體成分50%)，使添加量成爲13.55重 量份，使異氰酸酯的添加量成爲3.28重量份以外，與實 施例1同樣地，製作比較例1的光學機器用遮光構件。 [比較例2] 除了於實施例1所用的遮光膜用塗佈液中’將微粒子 (碳酸鈣）變更爲粒子（硫酸鋇，BMH :堺化學工業公司’平 均粒徑2.5 μηι)以外，與實施例1同樣地，製作比較例2的 光學機器用遮光構件。 2.評價 ⑧ -16- 201228829 對於如以上地實施例1〜5及比較例1〜2所得之光學 機器用遮光構件，藉由下述方法進行物性的評價。表1中 顯示各自的結果。 (1) 遮光性 將上述實施例1〜5及比較例1〜2所得之光學機器用 遮光構件，根據JIS K765 1: 1 988 ’使用光學濃度計（TD-904: Gretag Macbeth公司）來測定光學濃度。將光學濃度超過 4.0而成爲無法測定的範圍之濃度者當作「〇」，將4.0 以下者當作「X」。再者，測定係使用UV濾片。表1中 顯示測定結果。 -17- 201228829 爲2 cm。在該測定裝置1 〇的計測部3與上部固定部2之 間隙，載置上述直徑約3.2 cm的圓筒狀之實施例1〜5及 比較例1〜2之樣品1，以使得其圓筒狀的側面接觸該計測 裝置1 〇的計測部3及上部固定部2，測定樣品1的彈力所 造成的1 〇秒後計測部3之電子天平的計量。測定的結果 係將計量爲lg以上者當作「◎」，將0.7g以上〜未達lg 者當作「〇」，將未達0.7g者當作「X」。表1中顯示測 定結果。 (3)耐久性 使用實施例1〜5及比較例1〜2所得之光學機器用遮 光構件當作照相機的光圈構件，使動作2萬5千次，目視 確認該光學機器用遮光構件有無變形或破損。將無變形或 破損者當作「〇」，將有變形或破損者當作「X」。又， 對於無變形或破損者，再度使動作2萬5千次，然後將目 視確認時也沒有變形或破損者當作「◎」。表1中顯示測 定結果。 (4)熱變形 準備在基材的一面上設有上述實施例1〜5及比較例1〜 2的遮光膜之光學機器用遮光構件。裁切成縱橫lOcmxlOcm ’靜置在8(TC、5分鐘的環境，測定端部的捲曲量。將捲 曲量的四角落之合計爲Omm以上〜未達30mm者當作「〇 」’將30mm以上者當作「X」。表1中顯示測定結果。 ⑧ -18- 201228829 (5)接著性 根據JIS 5600-5-6中的棋盤格膠帶法，測定及評價上 述實驗例1〜5及比較例1〜2所得之光學機器用遮光構件 的遮光膜與基材之接著性。將棋盤格部分的面積有1 0%以 上剝離者當作「X」，將5%以上且未達10%者當作「△」 ，將未達5 %者當作「〇」。 [表1] 遮光性 堅韌性的強度 耐久性 熱變形 接著性 實施例1 〇 ◎ ◎ 〇 〇 實施例2 〇 ◎ 〇 〇 〇 實施例3 〇 〇 〇 〇 〇 實施例4 〇 ◎ 〇 〇 〇 實施例5 〇 〇 〇 〇 〇 比較例1 〇 X X 〇 X 比較例2 〇 X X X Δ 如由表1的結果可知，實施例1〜5所得之光學機器 用遮光構件係含有由合成樹脂薄膜所成的基材、與在前述 基材的至少一面上形成的遮光膜者，由於該遮光膜含有羥 値爲1 00(mgKOH/g)以上的黏結劑樹脂、碳黑、矽石及平 均粒徑未達Ιμηι的微粒子’故可一邊發揮遮光性’―邊即 使薄型化也成爲堅韌性強者’由於耐久性優異而可成爲不 易發生薄膜等的破損等者。 特別地，實施例1、2的光學機器用遮光構件’由於 -19- 201228829 黏結劑樹脂的羥値爲125(mgKOH/g)以上，而堅韌性的強 度成爲特別高，更且實施例1的光學機器用遮光構件，由 於黏結劑樹脂的羥値爲200(mgKOH/g)以上，且使用碳酸 鈣當作微粒子，而成爲堅韌性的強度特別高，耐久性亦特 別高者。 另一方面，比較例1的光學機器用遮光構件，由於使 用羥値未達100(mgKOH/g)的黏結劑樹脂，而微粒子無法 均勻地分散在遮光膜中，成爲堅韌性弱者。又，因此，成 爲亦缺乏耐久性者。 又，比較例2的光學機器用遮光構件，由於使用平均 粒徑爲Ιμιη以上的粒子，而微粒子無法均勻地分散在遮光 膜中’成爲堅韌性弱者》又，因此，成爲亦缺乏耐久性者 〇 實施例1〜5所得之光學機器用遮光構件，由於該遮 光膜含有羥値爲100(mgKOH/g)以上的黏結劑樹脂、碳黑 、矽石及平均粒徑未達Ιμπι的微粒子，故遮光膜全體中微 粒子的分散平衡係合適，即使作爲遮光構件將遮光膜設置 於基材的一面時，也不易發生局部的彎曲•畸變，而成不 易發生熱變形者。 比較例1所得之光學機器用遮光構件，由於該遮光膜 中的顏料比例高’而不易發生起因於黏結劑樹脂的熱變形 。然而’由於顏料比例高或微粒子無法均勻地分散，而成 爲與基材的接著性差者。 比較例2所得之光學機器用遮光構件雖然與實施例1 ⑧ -20- 201228829 所得之光學機器用遮光構件，在該遮光膜中的顏料比例係 相同，但由於不含有平均粒徑未達Ιμπι的微粒子，而微粒 子無法均勻地分散在遮光膜中’發生局部的彎曲.畸變， 成爲發生熱變形者。又，與基材的接著性亦比實施例1差 【圖式簡單說明】 圖1係說明測定光學機器用遮光構件的堅韌性強度用 之測定裝置的圖。 【主要元件符號說明】 1:本發明的光學機器用遮光構件 2 :上部固定部 3 :計測部 1 〇 :測定裝置 -21 -201228829 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a light shielding member for an optical device which can be used for a shutter or a diaphragm member of various optical apparatuses. [Prior Art] In recent years, since various optical devices such as high-performance single-lens reflex cameras, compact cameras, and cameras have been required to be smaller and lighter, the shutter or diaphragm member of an optical device formed of a metal material is being replaced. Plastic material. As the aperture of such a plastic material, a light-shielding film in which a light-shielding film containing carbon black, a lubricant, fine particles, and a binder resin is formed on a film substrate is known (Patent Documents 1 and 2). CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. Hei 9-2742 No. Hei. No. Hei 9-2742 No. 1 Patent Publication No. 2: WO 02006/0 1 65 5 5 [Invention] [Problems to be Solved by the Invention] Since the light-shielding film is extremely weak in toughness as compared with the light-shielding member, when the light-shielding film is used as a quick door or aperture member of an optical device, it is not resistant to use and has a contact portion with other members. A problem of skew, deformation, or breakage. Such a problem can be said to be a big problem in the recent years when thinning is required. -5-201228829 On the other hand, a method of directly thinning a light-shielding member made of a metal material is considered. However, if the light-shielding member is used as a shutter or a diaphragm member, deformation is likely to occur due to contact with other members. Since the deformation does not return in the nature of the metal material, the shading member is inconvenient to use. Moreover, compared with plastic materials, metal materials are ultimately costly. In this way, it is required to use a light-shielding member for an optical device which is less resistant to film breakage even if it is made thinner. [Means for Solving the Problem] The present inventors have found that a binder resin containing oxonium oxide (mgKOH/g) or more in a light-shielding film is used as a binder resin, and the average particle diameter is not reached. The light-shielding member of the fine particles of Ιμηη can be made tough even if it is thinned. Even if it is in contact with other members, the film is less likely to be damaged or the like, and the present invention has been achieved. In other words, the light-shielding member for an optical device according to the present invention includes a base material 'made of a synthetic resin film and a light-shielding film formed on at least one surface of the base material. The light-shielding film contains oxonium. A binder resin (carbon KOH/g) or more, carbon black, and fine particles having an average particle diameter of less than 1 μm. Further, in the light shielding member for an optical device of the present invention, the fine particles are preferably inorganic fine particles. Further, the inorganic fine particles are preferably calcium carbonate. Further, in the light shielding member for an optical device of the present invention, a preferred light shielding film contains vermiculite. [Effects of the Invention] -6 - 201228829 According to the above invention, the binder resin containing oxonium of 100 (mgKOH/g) or more and the fine particles having an average particle diameter of less than 丨μη can be made into a thin type. It also has a toughness and is less likely to cause light-shielding members such as breakage of the film. [Embodiment] Embodiments of the light-shielding member for optical devices (hereinafter also referred to as "light-shielding member") of the present invention will be described below. The light shielding member of the present invention contains a base material made of a synthetic resin film and a light shielding film formed on at least one surface of the base material. The light-shielding film contains a binder resin having a hydroxyindole of 100 (mgKOH/g) or more, carbon black, and fine particles having an average particle diameter of less than ίμιη. Further, the average particle diameter as used in the present invention means a median diameter (D 5 0) measured by a laser diffraction type particle size distribution measuring apparatus (for example, Shimadzu Corporation: SALD-7000, etc.). Examples of the substrate made of a synthetic resin film include polyester, ABS (acrylonitrile-butadiene-styrene), polyimine, polystyrene, polycarbonate, acrylate, and polyolefin. Cellulose resin 'polyfluorene, polyphenylene sulfide, polyether oxime, polyether ether ketone and the like. Among them, the polyester film is preferably used. From the viewpoint of excellent mechanical strength and dimensional stability, it is particularly preferred to be a polyester film which has been subjected to elongation processing, particularly by biaxial stretching. Further, as the substrate, in addition to being transparent, a foamed polyester film or a synthetic resin film containing a black pigment such as carbon black or another pigment may be used. At the time of 201228829, the above-mentioned base materials can be selected according to their respective uses. For example, when used as a light-shielding member, in the synthetic resin film portion of the cross-section of the member, the light collected by the lens or the like is adversely affected by reflection, and when high light-shielding property is required, a synthetic resin containing a black pigment such as carbon black can be used. For the film, in other cases, a transparent or foamed synthetic resin film can be used. In the present embodiment, when the black light pigment is contained in the synthetic resin film from the viewpoint of sufficient light-shielding property of the light-shielding film itself as a light-shielding member, the optical resin concentration is about 3, that is, the optical density is about 3 The method can be included. Therefore, conventionally, since the black pigment is contained in the synthetic resin film so as not to impair the physical properties as the substrate, the physical properties of the synthetic resin film are not changed, and it can be obtained inexpensively. The thickness of the substrate is preferably from 4 to 50 μm, particularly from the viewpoint of thinning, more preferably from 4 to 38 μm. Further, from the viewpoint of improving the adhesion to the light-sensitive film, the substrate may be subjected to a tackifying treatment or a corona treatment, if necessary, to form a light-shielding film on at least one side of the substrate, which contains oxindole. l 〇〇 (mgKOH / g) or more of binder resin, carbon black and particles with an average particle size of less than 1 μηη. In general, when fine particles having an average particle diameter of less than Ιμηι are used in the binder resin, the fine particles tend to aggregate due to the small particle size. In this case, the microparticles cannot be uniformly dispersed in the binder resin and are present in a biased manner. When the light-shielding film is formed of the material, a portion having a low density of fine particles is easily formed in the light-shielding film, and a portion which is easily deformed locally is formed in the light-shielding film. It is considered that when the light-shielding member having the light-shielding film is used for a certain period of time, the portion which is easily deformed from -8 to 201228829 is deformed and distorted, and it is not necessarily the other. On the other hand, if the average particle diameter is less than Ιμπι, In the binder resin of 100 (mgKOH/g) or more, the child is affected by the oxindole of the binder resin, and it is not uniformly dispersed. Therefore, it is considered that the balance system is suitable for the entire light-shielding film, and even if it is used as a light-shielding member, local bending and distortion can be used, and it can become a strong toughness. A condensed poly(meth)acrylic resin, a polyester resin, a polyester vinegar, a polyvinyl butyral resin, a cellulose olefin/polybutylene having a hydroxy hydrazine of 1 〇〇 (mgKOH/g) or more Diene resin, polyurethane resin, alkyd resin, unsaturated polyester resin, epoxy ester resin, epoxy acrylate ester, urethane acrylate resin, resin, polyether acrylic acid A thermosetting resin such as an ester resin, a phenol resin, a urea resin, or a diallyl phthalate resin may be mixed with one or two kinds of binder resins, and the oxindole may be 100 (mgK〇). H/g) The hydroxy oxime of the binder resin is 100 (mgKOH/g) or more, and the fine particles having a diameter of less than Ιμπι are uniformly dispersed in the light-shielding film, and the light-shielding member is also tough, and the film is damaged. The oxindole from the viewpoint of further exerting the toughness is preferably 125 (mgKOH/g) or more, more preferably the above. On the other hand, from the viewpoint of preventing the bending stress from being lowered, the upper limit is preferably 250 (mgKOH/g) or less. Strong toughness. When the particles are contained in oxindole, the fine particles are agglomerated and become fine particles, and the resin is less likely to occur. Examples thereof include vinyl acetate resin, polystyrene resin, acrylic resin, and propylene-propylene acrylate melamine. It is used as a resin, a thermoplastic resin or the like. on. By sticking the above-mentioned average granules, even if the masking is less likely to occur, the binder resin 200 (mgKOH/g) film becomes brittle. -9' 201228829 Hydroxime is a binder resin of 100 (mgKOH/g) or more. The content rate ' is preferably 15% by weight or more, and more preferably 20% by weight or more in the light shielding film. By setting the content of the binder resin to 15% by weight or more in the light-shielding film, it is possible to prevent the adhesion between the substrate and the light-shielding film from being lowered. On the other hand, the content rate of the above-mentioned binder resin is preferably 50% by weight or less, more preferably 45% by weight or less, and particularly preferably 40% by weight or less in the light shielding film. By setting the content of the above-mentioned binder resin to 50% by weight or less in the light-shielding film, it is possible to prevent a decrease in light-shielding property. The carbon black contained in the light-shielding film is used to color the binder resin to black, impart light-shielding properties, and impart conductivity while preventing charging due to static electricity. In order to obtain sufficient light blocking properties, the average particle diameter of carbon black is preferably 1 μm or less, more preferably 〇 5 μm or less. The content of carbon black is preferably from 10% by weight to 50% by weight, more preferably from 15% by weight to 45% by weight, based on the light-shielding film. When the amount of the light-shielding film is 1% by weight or more, the light-shielding property and the conductivity can be prevented from being lowered, and if it is 50% by weight or less, the adhesion and scratch resistance can be improved, and the film strength can be prevented from being lowered. And high cost. Further, in the light-shielding film, fine irregularities are formed on the surface, and reflection of incident light is reduced, and the glossiness (mirror gloss) of the surface is lowered, and the matte property when the light-shielding member is improved may be included. Inorganic particles. Examples of the inorganic particles include vermiculite, magnesium metasilicate aluminate, and titanium oxide. Among them, it is preferable to use vermiculite from the viewpoint of dispersibility of particles, low cost, and the like. 8 -10- 201228829 The average particle diameter of the inorganic particles is preferably Ιμπι ΙΟ ιμηη, more preferably Ιμιη ～6 μιη » This is because, by such a range, fine irregularities are formed on the surface of the light-shielding member, and matting property is obtained. . The content of the inorganic particles is preferably from 0.5% by weight to 10% by weight, more preferably from 0.5% by weight to 5% by weight, based on the light-shielding film. By making the light-shielding film 0.5% by weight or more, it is possible to prevent the surface glossiness (mirror gloss) from increasing and the matte property from being lowered. On the other hand, when it is 1% by weight or less, it is possible to prevent the inorganic particles from falling off due to the sliding of the light-shielding member or damage to the light-shielding member itself, thereby preventing deterioration of the sliding property. In particular, when high light-shielding property or electrical conductivity is required, the content of the inorganic particles is more preferably 5% by weight or less of the light-shielding film in the above range. In the inorganic particles used in the present embodiment, even when the amount is 5% by weight or less, sufficient matting properties can be obtained, and carbon black and microparticles to be described later can be relatively increased. The content ratio can improve physical properties such as light blocking properties and electrical conductivity without lowering the toughness. The fine particles having an average particle diameter of less than 1 μm contained in the light-shielding film are used as described above by using a binder resin having a hydroxyindole of 100 (mgKOH/g) or more, and the dispersion balance of the fine particles in the entire light-shielding film. If it is used as a light-shielding member, local bending and distortion may not easily occur, and it may become a strong toughness. Further, the hardness of the coating film when used as a light shielding film can be improved. Further, since local bending and distortion are less likely to occur, it is less likely to cause thermal deformation. As such, for example, a hydrocarbon-based slipper such as polyethylene wax or paraffin, a fatty acid-based slipper such as stearic acid or 12-hydroxystearic acid, or the like, oil 醯-11 - 201228829 amine, mustardamine An ester slip agent such as a guanamine slip agent or a stearic acid monoglyceride, an alcohol slip agent, a polyfluorene resin particle, a fluororesin particle such as a polytetrafluoroethylene wax, an acrylic resin particle, or a crosslinked acrylic acid. A resin fine particle such as a resin particle or a crosslinked polystyrene resin particle, or a solid such as a metal soap, talc, molybdenum disulfide, calcium carbonate, vermiculite, aluminum hydroxide, zirconium oxide, barium sulfate, or titanium oxide. An inorganic fine particle such as a lubricant. Among these, from the viewpoint of the high hardness of the entire particles and the improvement of the toughness, it is particularly preferable to use inorganic fine particles. Further, among the inorganic fine particles, if calcium carbonate is used, it is preferable because it is stronger as a light-shielding member. These fine particle systems may be used alone or in combination of two or more. Further, the vermiculite listed here is different from the vermiculite contained in order to improve the aforementioned matting property. The content of the fine particles is preferably from 2.5% by weight to 40% by weight, more preferably from 10% by weight to 35% by weight, based on the light-shielding film. When it is 25% by weight or more in the light-shielding film, the toughness can be further enhanced, and when it is 40% by weight or less, the relative content of the carbon black can be increased, and the reduction in light-shielding property can be obtained while obtaining toughness. . Further, the content ratio of the fine particles to the binder resin is preferably 30 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 1 part by weight of the binder resin. . By having such a content ratio, it is possible to further improve the dispersion balance of the fine particles in the light-shielding film while maintaining the light-shielding property, and it is possible to provide a light-shielding member which is more excellent in toughness. The light-shielding film formed on at least one side of the substrate may also contain a flame retardant, an antibacterial agent, an antifungal agent, an antioxidant, a plasticizer, and a leveling agent, without impairing the functions of the present invention 8-12-201228829. Various additives such as a agent, a flow regulator, an antifoaming agent, a dispersing agent, and the like. The thickness of the light-shielding film is preferably from 3 μm to 30 μm, more preferably from 5 μm to 2 0 μm. When it is 3 μm or more, pinholes and the like can be prevented from occurring in the light-shielding film, and sufficient light-shielding properties can be obtained. Further, by setting it to 30 μm or less, cracking of the light-shielding film can be prevented. In the light-shielding member for an optical device of the present embodiment, a binder resin, carbon black, and an average particle diameter containing oxonium oxide (mgKOH/g) or more may be applied to one surface or both surfaces of the substrate. The coating liquid for a light-shielding film such as fine particles of less than 1 μm is applied by a conventional coating method such as roll coating, rod coating, die coating, blade coating, or air knife coating, and after drying. It is obtained by heating, pressurization, etc. as needed. As the solvent of the coating liquid, water or an organic solvent, a mixture of water and an organic solvent, or the like can be used. As described above, the light-shielding member for an optical device of the present embodiment is suitable as a high-performance single-lens reflex camera because it contains a specific light-shielding film on at least one surface of the substrate and retains the physical properties of the light-shielding film such as light-shielding property and conductivity. Shutters and aperture members of optical devices such as compact cameras, video cameras, mobile phones, and projectors. In particular, since the light-shielding film of the present embodiment contains a binder resin having a hydroxyindole of 100 or more (mgKOH/g) or more and fine particles having an average particle diameter of less than Ιμηη, the fine particles can be uniformly dispersed in the light-shielding film, so that the thickness is even thinned. It also has toughness and can be a light-shielding member which is less likely to cause breakage of a film. As a result, it is particularly suitable for shutters, aperture members, and the like, which are particularly required to be thinner in recent years. Further, since local bending and distortion are less likely to occur, it is possible to cause thermal deformation. EXAMPLES Hereinafter, the present invention will be further illustrated by way of examples. In addition, "parts" and "%" are based on weight unless otherwise specified. 1. Production of light-shielding member [Example 1] As a substrate, a black polyethylene terephthalate film (Lumirror Χ 30: Toray Industries, Inc.) having a thickness of 25 μm was used, and the rod coating method was applied to both sides of the substrate. The coating liquid for a light-shielding film of the following prescription was applied and dried so that the thickness at the time of drying became 1 μm, and a light-shielding film was formed, and the light-shielding member for optical devices of Example 1 was produced. <Coating liquid for light-shielding film of Example 1> • 9.68 parts of polyester polyol (Burnock 1 1-408: DIC company, oxindole 200 (mgKOH/g), solid content 70%) • Isocyanate 9.37 parts ( BurnockDN980: DIC company, solid content 75%). Carbon black 4.57 parts (Vulcan XC-72: CABOT company) • Vermiculite 0.8 9 parts 8 -14- 201228829 (TS100: Evonik-Degussa曰, average particle size for " ;1) • Microparticles (calcium carbonate) 7.50 parts (Sunlight SL-700: Takehara Chemical Industry Co., Ltd. 'average particle size 〇.74 μηι). Methyl ethyl ketone 36.93 parts • Toluene 1 5.8 3 parts [Example 2] In the coating liquid for a light-shielding film used in Example 1, 'the polyester polyol was changed to a polyester polyol (Burnock J-517: DIC Corporation, oxindole 40 (mgKOH/g), solid content 70%), A light-shielding member for an optical device of Example 2 was produced in the same manner as in Example 1 except that the amount of the isocyanate added was 6.5 6 parts by weight. [Example 3] In addition to the coating liquid for a light-shielding film used in Example 1, the polyester polyol was changed to a polyester polyol (Burnock D-144-65BA: DIC Corporation, oxindole 100 (mgKOH/g) In the same manner as in Example 1, a light-shielding member for an optical device of Example 3 was produced in the same manner as in Example 1 except that the amount of the added component was changed to 10.42 parts by weight and the amount of the isocyanate added was 5.04 parts by weight. [Example 4] In addition to the coating liquid for a light-shielding film used in Example 1, the fine particles -15 - 201228829 (calcium carbonate) were changed into fine particles (titanium oxide, A-100: Ishihara Sangyo Co., Ltd., average particle diameter 〇. A light-shielding member for an optical device of Example 4 was produced in the same manner as in Example 1 except for 15 μm. [Example 5] In addition to the coating liquid for a light-shielding film used in Example 1, 'microparticles (calcium carbonate) were changed to fine particles (acrylic particles 'Chemsnow ΜΡ·1600, comprehensive chemical company, average particle diameter 〇. 8 μιη In the same manner as in the first embodiment, a light shielding member for an optical device of Example 5 was produced. [Comparative Example 1] In the coating liquid for a light-shielding film used in Example 1, the polyester polyol was changed to an acrylic polyol (Acrydic A_801P: DIC Corporation's oxindole 50 (mgKOH/g), and the solid content was 50%. In the same manner as in Example 1, a light-shielding member for an optical device of Comparative Example 1 was produced, except that the amount of the addition was 13.55 parts by weight and the amount of the isocyanate added was 3.28 parts by weight. [Comparative Example 2] Except that the fine particles (calcium carbonate) were changed to particles (barium sulfate, BMH: 堺Chemical Industries, Inc., average particle size 2.5 μηι) in the coating liquid for a light-shielding film used in Example 1, In the same manner as in Example 1, a light shielding member for an optical device of Comparative Example 2 was produced. 2. Evaluation 8 -16-201228829 The physical properties of the light-shielding members for optical devices obtained in the above Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated by the following methods. The respective results are shown in Table 1. (1) Light-shielding property The optical device for the optical device obtained in the above Examples 1 to 5 and Comparative Examples 1 and 2 was measured for optical using an optical densitometer (TD-904: Gretag Macbeth Co., Ltd.) in accordance with JIS K765 1: 1 988 ' concentration. Those who have an optical density of more than 4.0 and are in a range that cannot be measured are regarded as "〇", and those below 4.0 are regarded as "X". Further, the measurement system used a UV filter. The measurement results are shown in Table 1. -17- 201228829 is 2 cm. In the gap between the measuring unit 3 and the upper fixing portion 2 of the measuring device 1 , the cylindrical samples 1 to 5 and the comparative examples 1 to 2 having a diameter of about 3.2 cm were placed so that the cylinder thereof The side surface of the measuring device contacts the measuring unit 3 and the upper fixing unit 2 of the measuring device 1 , and measures the measurement of the electronic balance of the measuring unit 3 after 1 second caused by the elastic force of the sample 1 . As a result of the measurement, those who measured the amount of lg or more were regarded as "◎", those who did not exceed lg were regarded as "〇", and those who did not reach 0.7g were regarded as "X". The measurement results are shown in Table 1. (3) Durability The light-shielding members for optical devices obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were used as the diaphragm members of the camera, and the operation was performed 25,000 times, and it was visually confirmed whether or not the light-shielding members for optical devices were deformed or damaged. Those who are not deformed or damaged will be treated as "〇", and those who are deformed or damaged will be treated as "X". In addition, if there is no deformation or damage, the operation is again performed 25,000 times, and then the person who has not been deformed or damaged when visually confirmed is regarded as "◎". The measurement results are shown in Table 1. (4) Thermal deformation A light-shielding member for an optical device in which the light-shielding films of the above-described Examples 1 to 5 and Comparative Examples 1 to 2 were provided on one surface of the substrate was prepared. Cut into vertical and horizontal lOcmxlOcm 'Stand in 8 (TC, 5 minutes environment, measure the amount of curl at the end. The total of the four corners of the curl amount is Omm or more ~ less than 30mm as "〇"' will be 30mm or more The result is shown as "X". The measurement results are shown in Table 1. 8 -18-201228829 (5) Adhesiveness The above Experimental Examples 1 to 5 and Comparative Examples were measured and evaluated according to the checkerboard tape method in JIS 5600-5-6. The adhesion between the light-shielding film of the light-shielding member for optical devices obtained in 1 to 2 and the substrate. The area where the area of the checkerboard portion is 10% or more is regarded as "X", and the case where 5% or more and less than 10% are used as "△" is used as "〇", and less than 5% is regarded as "〇". [Table 1] Strength and durability of light-shielding toughness Thermal deformation Next example 1 ◎ ◎ 〇〇 Example 2 〇 ◎ 〇〇〇 Example 3 〇〇〇〇〇 Example 4 〇 ◎ 〇〇〇 Example 5 〇〇〇〇〇 Comparative Example 1 〇 XX 〇 X Comparative Example 2 〇 XXX Δ As can be seen from the results of Table 1, Examples 1 to 5 were obtained. The light-shielding member for an optical device contains a base material made of a synthetic resin film, and the base A light-shielding film formed on at least one side of the material, the light-shielding film contains a binder resin having a hydroxy hydrazine of 100 (mgKOH/g) or more, carbon black, vermiculite, and fine particles having an average particle diameter of less than Ιμηι. In the case of the light-shielding property of the optical device, the light-shielding member for the optical device of the first and second embodiments is -19- 201228829 The hydroxy oxime of the binder resin is 125 (mgKOH/g) or more, and the strength of the toughness is particularly high, and the light-shielding member for optical devices of Example 1 has a hydrazine of 200 (mgKOH/g) because of the binder resin. In addition, the use of the calcium carbonate as the fine particles is particularly high in the strength of the toughness, and the durability is also particularly high. On the other hand, the light-shielding member for an optical device of Comparative Example 1 has a hydroxyindole of less than 100 (mgKOH). /g) of the binder resin, and the fine particles are not uniformly dispersed in the light-shielding film, and are weak in toughness. Therefore, the film is also inferior in durability. In the case of using particles having an average particle diameter of Ιμηη or more, and the fine particles are not uniformly dispersed in the light-shielding film, the film becomes weaker and weaker. Therefore, it is also a lack of durability. The light-shielding members for optical devices obtained in Examples 1 to 5 are used. Since the light-shielding film contains a binder resin having a hydroxyindole of 100 (mgKOH/g) or more, carbon black, vermiculite, and fine particles having an average particle diameter of less than Ιμπι, the dispersion balance of the fine particles in the entire light-shielding film is appropriate even if When the light-shielding member is provided on one surface of the substrate, local bending and distortion are less likely to occur, and it is less likely to cause thermal deformation. The light-shielding member for an optical device obtained in Comparative Example 1 was less likely to cause thermal deformation due to the binder resin because the ratio of the pigment in the light-shielding film was high. However, since the ratio of the pigment is high or the fine particles are not uniformly dispersed, the adhesion to the substrate is inferior. The light-shielding member for an optical device obtained in Comparative Example 2 has the same pigment ratio in the light-shielding film as the light-shielding member for an optical device obtained in Example 18-20-201228829, but does not contain an average particle diameter of less than Ιμπι. Microparticles, and the microparticles cannot be uniformly dispersed in the light-shielding film. Local bending and distortion occur, and they become heat-deformed. In addition, the adhesion to the substrate is also inferior to that of the first embodiment. [Brief Description of the Drawings] Fig. 1 is a view showing a measuring device for measuring the toughness of the light shielding member for an optical device. [Description of main component symbols] 1: Light-shielding member for optical device according to the present invention 2: Upper fixing portion 3: Measuring portion 1 〇 : Measuring device - 21 -