200928332 九、發明說明： 【發明所屬之技術領域] 本:發η月係關於在接觸面或加壓部位中測定並記錄壓力 分布所用之壓力測定用材料。 【先前技術】 壓力測定用材料係使用於液晶玻璃之貼合步驟，對茚 刷基板之焊料節刷（soldering print)、輥間壓力調整等用 途。在此種壓力測定用材料有例如富士軟片（股）所提供之 Prescale (商品名）所代表之壓力測定薄膜。 在此壓力測定薄膜之例子方面，在特公昭57- 24852 號公報、有揭示利用到電子給與性無色染料前驅物與電子 受體性化合物的發色反應之壓力測定用薄片，被認爲可在 O.IMPa〜20MPa左右之壓力範圍測定。壓力測定薄膜的特 徵在於，可將薄膜切斷成與測定部位一致之任意大小使 用。又因筆壓所致高度線壓而產生發色反應，與所謂感壓 複寫紙並不相同，壓力測定薄膜具有可測定面壓之特徵。 在壓力測定用材料中，使發色劑或使該發色劑進行發 色之顯色劑被內包於微膠囊。在加諸設定的壓力於微膠囊 時微膠囊被破壞，含於其中之成份釋出微膠囊外而產生發 色反應。相對於壓力測定用材料的壓力之感度可以微膠囊 破壞之容易性等來調節。因此，在低壓測定用壓力測定用 材料（亦即在微膠囊易於被破壞之情形）的處理有必要予以 注意。又，在製造低壓測定用壓力測定用材料之際，在將 此材料捲繞成捲筒狀時使壓力加諸於微膠囊，會有基體上 200928332 所塗布之微膠囊遭受破壞之情形。 以保護基體上之塗布膜爲目的，在特開2002 -號公報有提案一種將比塗布膜之膜厚更厚的塗布部 捲筒狀基體寬方向之兩端邊近旁，而防止塗布膜之 阻塞（blocking)等發生之方法。根據此方法，吾人可 基體上所塗布微膠囊之保護作用。 【發明内容】 發明欲解決之課顆 但是，在具有含有具粒徑分布之微膠囊之塗布 力測定用材料，爲了防止最大徑之微膠囊的破壞有 塗布部成爲相當厚。但是，在含有微膠囊之塗布膜 厚度與塗布部之厚度之差變大時，在製造壓力測定 之步驟，易於發生卷取偏差或卷取縐紋。結果，會 引起微膠囊破壞之情況。亦即，即使依照特開2002 號公報所揭示之方法要保護微膠囊不被破壞則有困 本發明係鑑於上述習知之問題而完成者，其目 提供一種可防止微膠囊之破壞的壓力測定用材料。 解決誤顆之丰铅 本發明之態樣係利用到電子給與性無色染料前 電子受體性化合物的發色反應之壓力測定用材料， 有：基體；含有內包該電子給與性無色染料前驅物 囊且設置於該基體上之發色層；及設置於該基體端 隔件’相對於該微膠囊之體積標準95 %徑A(/z m)， 件之厚度爲（A x 〇.6)y m以上、（A x 1.0)y m以下之 68540 形成於 損傷或 期待在 膜的壓 必要使 的平均 用材料 有因而 -68540 難。 的在於 驅物與 其係具 之微膠 部之間 該間隔 壓力測 200928332 定用材料。 發明效果 根據本發明係提供一種可防止微膠囊破壞之壓力測定 用材料。 【實施方式】 以下，就本發明之壓力測定用材料予以詳細說明。 本發明之壓力測定用材料係在利用到電子給與性無色 染料前驅物（以下稱爲「發色劑」）與電子受體性化合物（以 ® 下稱爲「顯色劑」）之發色反應的壓力測定用材料中，具有： 基體；含有內包該電子給與性無色染料前驅物之微膠囊且 設置於該基體上之發色層；及設置於該基體之端部之間隔 件’相對於該微膠襄之體積標準95 %徑A(/z m)，該間隔件 之厚度爲（A X 0.6)/zm以上、（Ax 1.0)#m以下者》 在本發明之壓力測定用材料中，因在基體端部設置有 具設定之厚度的間隔件，故在使壓力測定用材料疊合之情 形，在基體與基體之間可設置間隙。在此間隙設置發色層 ® 而可防止微膠囊之破壞。此外，在壓力測定用材料所疊合 之狀態方面’可例舉積層有薄片狀壓力測定用材料之狀 態’或使壓力測定用材料捲繞成捲筒狀之狀態等。 間隔件可設置於基體之端部，以在基體有設置發色層 之處，設置間隔件爲佳。藉此，在基體上因存在有間隔件 设置之部分（亦即無發色層設置之部分），故使用者不會觸 及發色層而可處理壓力測定用材料。因此，可使壓力測定 用材料之操作性提高。 在本發明之壓力測定用材料中，相對於微膠囊之體積 200928332 標準95%徑A(;z m)，間隔件之厚度爲（A x 〇.6)/z m以上、 (A x 1.0) μ m以下。間隔件之厚度未達（a χ 0.6) // m時，在 疊合壓力測定用材料之狀態時加諸壓力於微膠囊會使微膠 囊遭受破壞。又’間隔件之厚度比（Ax 1.0)//m更大時， 在壓力測定用材料製造步驟中於捲繞基體之際發生卷取偏 差或卷取縐紋’結果會使得微膠囊遭受破壞。 本發明中間隔件之厚度以（A X 0.62) v m以上、（A X 1.0)ym 以下爲佳’以（A X 0.65)jum 以上、（A X 1.0)Aim 以 〇 下進而爲佳。 此外，在本發明中微膠囊之體積標準95 %徑，係指以 微膠囊全體積爲100%來求得累積曲線（cumulative curve),, 時，其累積曲線成爲95%之點的粒徑。此體積標準95 %徑 係將含有微膠囊1〜40%(質量基準）之溶液塗布於支持體， 其表面以光學顯微鏡在150倍攝影，計測在2公分 x2公 分範圍之所有微膠囊之大小所求得之値。 又，體積標準之中値徑，係指在體積累計成爲50 %之 〇 粒徑分爲二個臨界値時，將微膠囊全體在大徑側與小徑側 之粒子體積合計成爲等量之徑，可以與體積標準95 %徑相 同方法來求得。 本發明之壓力測定用材料，係將內包有電子給與性無 色染料前驅物之微膠囊、及與該電子給與性無色染料前驅 物反應使之發色的電子受體性化合物，設置於單一基體’ 或者個別基體（較佳爲進行塗膜）所構成。 本發明之壓力測定用材料，係微膠囊與電子受體性化 合物以塗膜等而設置在單一基體上之所謂的單片型（mono 200928332 —sheet type)之情形，具有：薄片或薄膜等基體；與自該基 體側依順序設置在基體上之含顯色劑的顯色劑層；及含微 膠囊之發色層所成’將其單獨夾持於欲測定壓力或壓力分 布之部位並予加壓。 又’本發明之壓力測定用材料，係微膠囊與電子受體 性化合物以塗膜等而設置於個別基體之所謂雙片型（tw〇 sheet type)之情形’具有：在薄片或薄膜等基體上，具有含 有顯色劑之顯色劑層的材料A;與在薄片或薄膜等基體上 〇 具有含 有微膠囊之發色層的材料B所構成，以使材料B之 存在微膠囊之面（發色層表面），與材料A之存在電子受體 性化合物之面（顯色劑層表面）互爲相面對之方式，使兩材 料重疊’在重疊狀態夾持於欲測定壓力或壓力分布之部位 進行加壓。 加壓可以任意方法在點、線或面賦予壓力（點壓、線壓 或面壓等）來進行。本發明對於尤其是微膠囊易於破壞之 0.5MPa以下壓力下可發色的壓力測定用材料爲有效。 〇 如上述在加壓下，而使微膠囊被破壞而含有電子給與 性無色染料前驅物之內包物被釋出，藉由使電子給與性無 色染料前驅物與電子受體性化合物反應而可觀察到著色。 在此時，隨著加壓之壓力變大含有電子給與性無色染料前 驅物之內包物會有更多釋出，因與電子受體性化合物之反 應量增加，故可得濃的發色。 在上述中，壓力測定用材料就其保存性或處理性之觀 點而言，以內包電子給與性無色染料前驅物之微膠囊與電 子受體性化合物，構成爲設置塗膜於個別基體等之雙片型 200928332 更佳。 以下’就構成本發明壓力測定用材料之各要素加以說 明。 〈基體> 構成本發明壓力測定用材料之基體，可爲薄片形、薄 膜形、板形、捲筒形等任一種’具體例方面，有紙、塑膠 薄膜、合成紙等。壓力測定用材料爲單片型及雙片型之任 一種形態亦爲相同。 ❹ 該紙之具體例方面’有道林紙（woodfreepaper)、含木 質紙（wood containing paper)' 磨木紙（groundwood paper)、 中性紙、酸性紙、塗料紙（coated paper) '機器塗膜紙、銅 版紙（art paper)、鑄塗（cast coat)紙、微塗膜紙、透明紙 (tracing paper)、再生紙等。該塑膠薄膜之具體例方面，有 聚對酞酸乙二酯薄膜等聚酯薄膜、三乙酸纖維素等纖維素 衍生物薄膜、聚丙烯、聚乙烯等聚烯烴薄膜、聚苯乙烯薄 膜等。 ❹ 又，該合成紙之具體例方面，有例如使聚丙烯或聚對 酞酸乙二酯等進行二軸拉伸使微孔洞（micorvoid)經多數形 成之物（Yupo等），或由聚乙烯、聚丙烯、聚對酞酸乙二酯、 聚醯胺等合成纖維所成之物，將該等積層於紙之一部分、 一面或兩面之物等。 但，在本發明中並非限定於該等。 在該等中就以加壓所產生發色濃度予以更形提高之點 而言，以塑膠薄膜、合成紙爲佳，而以塑膠薄膜更佳。 本發明之壓力測定用材料中，係使用捲筒狀之基體’ -10- 200928332 在此基體寬方向之兩端部以設置間隔件爲佳。藉由使本發 明之壓力測定用材料成爲此種構成，而可在壓力測定用材 料之製造步驟中有效地防止微膠囊之破壞。進而，在保存 捲繞成捲筒狀之本發明壓力測定用材料之際，可有效地防 止微膠囊之破壞。尤其是因可防止微膠囊與塗布面接觸輥 之接觸而被破壞，故在基體發色層所設置之側以設置間隔 件爲佳。 又，在本發明之壓力測定用材料中，亦可使用四角形 〇 基體，亦可在此基體之一對相對向的邊之端部上設置該間 隔件之方式。藉由使本發明壓力測定用材料成爲此種構 成，在使壓力測定用材料積層之狀態進行保存之際，可有 效地防止微膠囊之破壞。 使基體成四角形的本發明之壓力測定用材料，係藉由 將捲筒狀之本發明壓力測定用材料以所期望長度加以切斷 而可得。 <發色層> 〇 在本發明之壓力測定用材料中，係設置發色層於基體 上，該發色層含有內包電子給與性無色染料前驅物之微膠 囊。 (電子給與性無色染料前驅物） 本發明壓力測定用材料之發色層所含有的微膠囊，係 內包電子給與性無色染料前驅物之至少一種。 內包於微膠囊之電子給與性無色染料前驅物，在感壓 複寫紙或感熱記錄紙之用途中可使用周知之物。例如可使 用三苯基甲院酞內酯（triphenyl methane phthalide)系化合 200928332 物、螢光黃母體（flU0ran)系化合物、啡噻阱系化合物、吲 哄基酞內酯系化合物、白色金黃胺（leucoauramine)系化合 物、羅丹明內醯胺系化合物、三苯基甲烷系化合物、二苯 基甲烷系化合物、三氮烯系化合物、螺旋哌喃系化合物、 莽系化合物等各種化合物。 關於該等化合物之詳細內容，係記載於特開平5 -25 7272號公報，電子給與性無色染料前驅物可單獨使用1 種或混合2種以上使用。 ® 電子給與性無色染料前驅物，就可提高在0.5MPa以下 之發色性，在微小壓力下可得高濃度（提高相對於壓力變化 之濃度變化（濃度梯度））之觀點而言，以莫耳吸光係數（ε ) 高之物爲佳。電子給與性無色染料前驅物之莫耳吸光係數 (e )以 10000 mol — 1 · cm- 1 · L 以上爲佳，以 15000 mol - 1 · cm-1· L以上較佳，進而以25000mol_'· cm-1· L以上爲 佳。 ε爲該範圍之電子給與性無色染料前驅物的適當例方 〇 面，有例如3_(4 —二乙基胺基一 2-乙氧苯基）—3— (1_ 乙基一 2 —甲基吲哚一 3 —基）_4 一氮雜酞內酯 (ε =61000)、3-(4 -二乙基胺基-2—乙氧苯基）—3— (1-正辛基-2—甲基吲哚—3 —基）酞內酯（ε =40000)、3 — [2,2 一雙（1—乙基一 2—甲基吲哚一3 —基）乙烯]一 3 — (4 —二乙 基胺基苯基）一酞內酯U =40000)、9—[乙基（3—甲基丁基） 胺基]螺旋[12Η —苯并[a]卩ill I]星一 12,1’（3’Η)異苯并呋喃]一 3’ -酮U =34000)、2 -苯胺基—6—二丁基胺基—3—甲基螢 光黃母體U =220 00)、6 -二乙基胺基-3—甲基一2 - (2,6 -12- 200928332 -二甲代苯胺）一螢光黃母體（e =19000)、2 — (2-氯苯胺基） —6 —二丁基胺基螢光黃母體（ε =21000)、3,3 -雙（4 —二甲 基胺基苯基）一6—二甲基胺基酞內酯（ε =16000)、2—苯胺 基一6 —二乙基胺基一 3 —甲基螢光黃母體（e =1 60 00)等。 單獨使用莫耳吸光係數ε在前述範圍之電子給與性 無色染料前驅物1種，或將含有莫耳吸光係數ε在前述範 圍之電子給與性無色染料前驅物2種以上之電子給與性無 色染料前驅物加以混合使用之情形，就可提高在〇.5MPa以 © 下之發色性，在低壓獲得高濃度（提高相對於壓力變化之濃 度變化（濃度梯度））之觀點而言，在電子給與性無色染料前 驅物之合計量中，莫耳吸光係數（ε )爲10000 mol— 1 · cm_ 1 · L 以上之電子給與性無色染料前驅物所佔之比率，以1〇〜100 質量％範圍爲佳，以20〜100質量％範圍較佳，進而以30 〜100質量％範圍爲佳。 在使用2種以上電子給與性無色染料前驅物之情形， 以倂用ε各自爲10000 mo厂1 .cm_1.L以上之物2種以 © 上爲佳。 莫耳吸光係數（ε )係自使電子給與性無色染料溶解於 95 %乙酸水溶液中時之吸光度所計算出。具體言之，在調節 濃度使吸光度成爲1.0以下之電子給與性無色染料的95% 乙酸水溶液中，使測定用胞室（cell)之長爲Α公分，電子給 與性無色染料之濃度爲B莫耳/升，吸光度爲c時，係以 下述式計算。 莫耳吸光係數（ε )= C/(A X B) 電子給與性無色染料前驅物之量（例如塗布量），就可 -13- 200928332 提高在0.5MPa以下之發色性的觀點而言，在乾燥後質量以 0.1〜5g/ni爲佳，以0.1〜4g/m2較佳，以0.2〜3g/rri更佳。 (溶劑） 本發明中微膠囊可與電子給與性無色染料前驅物一起 內包至少一種之溶劑。 在內包於微膠囊之溶劑方面，可使用於感壓複寫紙用 途中周知之物。例如二異丙基萘等烷基萘類、1一苯基—1 -甲苄基乙烷等二芳基烷類、異丙基聯苯等烷基聯苯類、 © 其他三芳基甲烷類、烷基苯類、苄基萘類、二芳基烷撐類、 芳基茚滿類等芳香族烴；酞酸二丁酯、異石臘等脂肪族烴， 大豆油、玉米油、棉籽油、油菜籽油、橄欖油、椰子油、 篦麻油、魚油等天然動植物油等，礦物油等之天然物高沸 點餾份等。溶劑可單獨使用1種或混合2種以上使用。 又，可因應需要，補助溶劑係添加甲基乙基酮等酮類 或乙酸乙酯等酯類、異丙基醇等醇類等，沸點13〇。(：以下之 溶劑。 G (微膠囊及其製作方法） 電子給與性無色染料前驅物及可因應需要將溶劑內包 之微膠囊’其本身可以周知的任意方法，例如界面聚合法、 內部聚合法、相分離法、外部聚合法、凝聚法等方法來製 造。 該微膠囊之壁材料方面’可自習知之作爲感壓記錄材 料之含電子給與性無色染料前驅物之微膠囊的壁材料所使 用之水不溶性、油不溶性之聚合物中，無特別限定的使用。 其中之壁材料方面’以胺甲酸酯一脲樹脂（聚胺甲酸酯一 -14- 200928332 脲）、三聚氰胺-甲醛樹脂、明膠爲佳，就可在低壓（較佳 爲0.5MPa以下）獲得良好發色之觀點而言，以聚胺甲酸酯 一脲’三聚氰胺-甲醛樹脂較佳，尤以含胺甲酸酯鍵結之 聚fee甲酸乙醋一脈爲佳。 在此’以使用到聚胺甲酸乙酯-脲於膠囊壁材料之情 形爲例加以說明。 內包電子給與性無色染料前驅物之聚胺甲酸乙酯-脲 壁的微膠囊分散液之調製可使用於感壓複寫紙用途中周知 ❹ 方法。例如將電子給與性無色染料前驅物與多價異氰酸酯 溶解於溶劑之溶液（油相），進行乳化分散於含有水溶性高 分子（聚醇、聚胺等膠囊壁形成用物質）之轉水性溶液（例如 水等；水相），將所得乳化分散液中油滴以聚胺甲酸乙酯-脲被覆來進行微膠囊化之方法。在此時，藉由加溫在油滴 界面進行高分子形成反應，而可形成微膠囊壁。 在微膠囊化之步驟中途，可添加多價羥基化合物或多 價胺等反應調整劑。在多價羥基化合物之具體例方面，可 ❹ 例舉脂肪族或芳香族之多價醇、羥基聚酯、羥基聚伸烷醚、 多價胺之環氧烷加成物等。其中以脂肪族或芳香族之多價 醇、多價胺之環氧烷加成物爲佳，更佳爲多價胺之環氧烷 加成物。 多價胺方面，若在分子中具有2個以上一NH基或—NH2 基之物，則任一種均可使用。具體化合物方面’可舉例如 二伸乙三胺、三伸乙四胺' 1,3—伸丙二胺、六亞甲二胺等 脂肪族多價胺；脂肪族多價胺之環氧化合物加成物；六氫 吡畊等脂環式多價胺；3,9 —雙一胺基丙基—2,4,8,10 —四氧 -15- 200928332 雜螺旋一（5,5)十一烷等雜環式二胺等。 多價羥基化合物或多價胺之添加量，可依照使用之多 價異氰酸酯之種類及量，進而可依照所望膠囊壁硬度等而 適宜決定。在添加多價羥基化合物或多價胺之情形，「多價 羥基化合物及/或多價胺之總量：多價異氰酸酯之量」之比 (質量比）以0.1: 99.9〜30: 70爲佳，以1: 99〜25: 75更 佳。又’多價羥基化合物之添加量方面，以多價異氰酸酯： 多價羥基化合物之質量比在99.9: 0.1〜70: 30爲佳，以 © 99: 1〜75: 25較佳，以98: 2〜80: 20更佳。 多價羥基化合物或多價胺之添加時期，可在溶解電子 給與性無色染料前驅物之溶劑或補助溶劑中預先添加，在 乳化分散前或乳化分散後添加亦可。 在親水性溶液中，作爲乳化劑可添加各種兩性高分 子、離子系高分子、非離子系高分子，亦可添加例如明膠、 澱粉、羧甲基纖維素、聚乙烯醇、聚烷基苯磺酸鹽、聚氧 乙烯硫酸鹽、聚氧烷醚或其改性物、異丁烯基一順丁烯二 〇 酸酐共聚物等。 該多價異氰酸酯方面，可使用在感壓複寫紙用途中周 知之物。例如氫化二甲苯基二異氰酸酯（一般稱爲氫化XDI) 之異三聚氰酸酯體、二異氰酸異佛爾酮酯（一般稱爲IPDI) 之異三聚氰酸酯體、二異氰酸4，4’-二苯基甲烷酯、二異 氰酸六亞甲酯與三羥甲基丙烷之加成物、二異氰酸六亞甲 酯之彈（bullet)體、二異氰酸六亞甲酯之異三聚氰酸酯體、 以胺甲酸酯鍵結合有脂肪族二醇（例如伸烷二醇）於二異氰 酸六亞甲酯之異三聚氰酸酯體之化合物、聚亞甲基聚苯基 -16- 200928332 異氰酸酯、碳化二醯亞胺改性二苯基甲烷二異氰酸酯、二 異氰酸甲伸苯酯與三羥甲基丙烷之加成物、二異氰酸二甲 苯酯與三羥甲基丙烷之加成物、二異氰酸甲伸苯酯之異三 聚氰酸酯體、二異氰酸氫化二甲苯酯與三羥甲基丙烷之加 成體，二異氰酸異佛爾酮酯與三羥甲基丙烷之加成體，二 異氰酸二甲苯酯之彈體及三-（對異氰酸酯苯基）硫代亞磷 酸鹽。多價異氰酸酯可單獨使用1種或混合2種以上使用。 又，在微膠囊，除了上述電子給與性無色染料前驅物、 ^ 溶劑、及補助溶劑以外，亦可因應需要內包添加劑。添加 劑方面，有紫外線吸收劑、光穩定化劑、抗氧化劑、蠟、 抑臭劑等。 在內包於微膠囊之溶劑與電子給與性無色染料前驅物 之質量比（溶劑：前驅物）方面，以發色性之點而言則在98 : 2〜30: 70之範圍爲佳，以97: 3〜40: 60之範圍較佳，以 95: 5〜50: 50之範圍更佳。 在微膠囊體積標準之中値徑方面，就可提高在低壓（較 〇 佳爲0.5MPa以下）之發色濃度，在進行掃瞄等以讀取可見 度、濃度之際，以提高濃度再現精度之點而言，以lO/zm 以上爲佳，以10〜40μιη較佳，以13〜30ym更佳，以16 〜2 5 # m特佳。 本發明中係夾持體積標準之中値徑D(" m)的微膠囊於 一對平行的平面間，使一對平面之間隔成爲（Dx 0.25) /Z m 以上、（D x 0.90) /zm以下時所破壞之微膠囊作爲構成發色 層之微膠囊來使用爲佳。藉由使用顯示上述設定之強度的 微膠囊，在使壓力測定用材料於疊合之狀態時，施加壓力 -17- 200928332 於微膠嚢，可得防止微膠囊遭受破壞之效果。 在上述一對平面之間隔方面，以（Dx 0.27) // m以上、 (D X 0.90)#m 以下更佳，以（D X 0.30)/zm 以上、（D X 0.9 0) μ m以下特佳。 在此，微膠囊被破壞時之「一對平面之間隔」可在23 °C 中使用微小硬度計來測定。具體言之，在微小硬度計之樣 本臺設置塗設有微膠囊之基體，在以平面壓痕子（indenter) 加壓著微膠囊時，自微膠囊內包物剛出來時之基體表面與 〇 平面壓痕子之間隔，相對於體積標準之中値徑係就具有 ±10%以內直徑之微膠囊5個來求得，使其平均爲「一對平 面之間隔」。 「基體表面與平面壓痕子之間隔」可使用例如島津製 作所製，MCT— W200來測定。又，微膠囊直徑可以光學顯 微鏡觀察來求得。 上述設定強度之微膠囊，其本身可以周知之任意方 法’例如界面聚合法、內部聚合法、相分離法、外部聚合 G 法、凝聚法（coacervation)法等方法來製造。上述微膠囊之 壁材料方面，若爲在作爲習知感壓記錄材料之含電子給與 性無色染料微膠囊之壁材料所使用之水不溶性、油不溶性 之聚合物，則可無特別限定地使用，而以聚胺甲酸酯脲壁、 三聚氰胺-甲醛壁、明膠壁爲佳，其中以聚胺甲酸酯脲壁、 三聚氰胺一甲醛壁更佳。 關於微膠囊之膠囊壁壁厚，雖依膠囊壁材料種類或膠 囊徑等各種條件而定，但若以微小（至少〇.〇5MPa)之加壓而 可破壞之範圍時，可毫無限制的任意選擇。其中以由在 -18- 200928332 0.5MPa以下壓力可獲得良好發色性之觀點而言，較佳之壁 厚係在0.005〜3.0//m之範圍，更佳爲0.005〜2.8/zm之範 圍，更佳爲在使微膠囊之中値徑爲10〜40ym之情形，則 爲0.06〜1.0/z m。特佳之膠囊壁壁厚，於中値徑爲10〜 40 em之微膠囊的膠囊壁以聚胺甲酸酯-脲所構成之情形 則爲 0.07 〜0.85Aim。 本發明中，壁厚係指形成微膠囊之膠囊粒的樹脂膜（所 謂膠囊壁）之厚度之意，將5個微膠囊之各膠囊壁厚度以掃 〇 描型電子顯微鏡來求得經平均之平均値之意。 (發色層形成用調製液之調製） 微膠囊可以上述方式作爲分散液而得，而此微膠囊之 分散液，亦可照樣作爲形成含有電子給與性無色染料前驅 物之發色層用的調製液（尤其是塗布液）。又在如上述方式 所得之微膠囊之分散液，進而可添加澱粉或澱粉衍生物之 微粉末、纖維素纖維粉末等緩衝劑、聚乙烯醇等水溶性高 分子黏合劑、乙酸乙烯酯系，丙烯酸系，苯乙烯一丁二烯 〇 共聚物乳膠等疏水性高分子黏合劑、螢光增白劑、消泡劑、 浸透劑、紫外線吸收劑、防腐劑作爲調製液（尤其是塗布 液）。 將如此所得之調製液（尤其是塗布液），賦予塗膜等於 基體上，進行乾燥藉以形成構成壓力測定用材料之發色層。 在使該發色層形成用之調製液作爲塗布液使用之情 形，塗布液之塗膜方法係使用通常之塗膜機進行塗布、乾 燥。具體塗膜機之例方面，有例如氣刀塗布機、桿塗布機、 棒塗布機、簾幕塗布機、凹版茚刷塗布機、擠壓塗布機、 -19- 200928332 模塗布機、滑動珠（slide bead)塗布機、刮刀塗布機等。 本發明之壓力測定用材料，在電子給與性無色染料前 驅物內包之微膠囊與電子受體性化合物係各自塗膜於個別 基體塗膜等所構成之2薄片形式之情形，例如將上述塗布 液在所望薄片狀基體上，直接或者隔著其他層進行塗布、 乾燥而可藉以獲得至少形成有發色層之薄片材料。又，在 電子給與性無色染料前驅物內包之微膠囊與電子受體性化 合物於單一薄片形基體進行塗膜等所構成之單薄片形式之 ® 情形’例如在所望基體上所形成之後述顯色劑層上使上述 塗布液進行重複塗布、乾燥藉以獲得壓力測定用材料。 <間隔件> 在本發明之壓力測定用材料中，可在基體端部設置間 隔件。構成間隔件之成份及其形成方法並無特別限定，以 將含有顏料、黏合劑與溶劑之間隔件形成溶液塗布於基體 上並設置，就可提高間隔件厚度均一性之點爲佳。 在構成間隔件之顏料方面，有例如高嶺土、燒成高嶺 〇 土'高嶺土凝集體、重質碳酸鈣、各種形態（米粒形'角形、 妨錘形、毯形、球形、文石系柱形、無定形等）之輕質碳酸 耗、滑石、金紅石型或銳鈦礦型之二氧化鈦等，而以高嶺 土凝集體、重質碳酸鈣、輕質碳酸鈣、滑石爲佳、以高嶺 土凝集體、重質碳酸鈣、輕質碳酸鈣進而爲佳。 在構成間隔件之黏合劑方面，有例如聚乙烯醇等水溶 性高分子黏合劑、澱粉、乾酪素、阿拉伯膠、明膠、羧甲 基纖維素、甲基纖維素等合成或天然高分子物質，乙酸乙 嫌酯系、丙烯酸系、苯乙烯一丁二烯共聚物乳膠等疏水性 -20- 200928332 高分子黏合劑，而以聚乙烯醇、苯乙烯-丁二烯共聚物乳 膠、丙烯酸系乳膠、羧甲基纖維素、甲基纖維素爲佳、以 聚乙烯醇、苯乙烯-丁二烯共聚物乳膠、羧甲基纖維素， 甲基纖維素進而爲佳。 在構成間隔件之顏料與黏合劑之比（質量基準）方面’ 以100 : 5〜5 : 100爲佳，以100 : 7〜10 : 100進而爲佳。 在含於間隔件形成溶液的溶劑方面，若爲可使顏料及 黏合劑溶解、分散之物則並無特別限定，有例如水、甲基 © 乙基酮等酮類、乙酸乙酯等酯類、異丙醇等醇類等，沸點 1 30°C以下之溶劑，以水、甲醇、乙醇、異丙醇爲佳，以水、 異丙醇進而爲佳。 。 在間隔件形成溶液，亦可因應需要含有添加劑。在可 含於間隔件形成溶液之添加劑方面，有例如界面活性劑、 消泡劑、防腐劑、黏度調整劑等。 在間隔件形成溶液之塗膜機方面，有例如氣刀塗布 機、桿塗布機、棒塗布機、簾幕塗布機、凹版茚刷塗布機、 〇 擠壓塗布機、模塗布機、滑動珠塗布機、刮刀塗布機等。 藉由使用該等塗膜機，而可設置間隔件於基體上所望之位 置。 在間隔件形成溶液之塗布後，藉由使塗膜乾燥而可形 成間隔件。 本發明之壓力測定用材料係使用捲筒狀之基體，於此 基體之寬方向兩端部設置間隔件而構成之情形，在基體之 寬方向中’於間隔件之寬方面，在使基體之寬爲i時以0.01 〜0.99爲佳，以0.02〜0.98進而爲佳，以0.02〜0.95特佳。 -21- 200928332 在使基體之寬爲1時，使間隔件寬在0.01〜0.99之範圍， 而在壓力測定用材料爲叠合之形態之微膠囊破壞可更有效 地防止。 又，本發明之壓力測定用材料係使用四角形基體，在 此基體之一對相對向的邊之端部設置間隔件而構成之情 形，在設置間隔件之一對邊的對向方向中，在使基體之寬 爲1時，間隔件之寬以0.01〜0_99爲佳，以0.02〜0.98進 而爲佳，以0.02〜0.95特佳。在使基體之寬爲1時，在使 〇 間隔件之寬於〇.〇1〜0.99之範圍，而使壓力測定用材料爲 疊合之狀態下，可進而有效地防止微膠囊破壞。 (電子受體性化合物） 本發明壓力測定用材料之顯色劑層係含有電子受體性 化合物（顯色劑）之至少一種。 在含於本發明顯色劑層之電子受體性化合物方面，有 無機化合物與有機化合物。無機化合物之具體例方面，有 如酸性白土、活性白土、綠坡縷石、沸石、皂土、高嶺土 Ο 之黏土物質等。有機化合物方面、有芳香族羧酸之金屬鹽、 苯酚甲醛樹脂、羧基化萜烯苯酚樹脂之金屬鹽等》其中以 酸性白土、活性白土、沸石、高嶺土、芳香族羧酸之金屬 鹽、羧基化萜烯苯酚樹脂之金屬鹽爲佳，以酸性白土、活 性白土、高嶺土、芳香族羧酸之金屬鹽更佳。 該芳香族羧酸的金屬鹽之適當具體例方面，有3，5-二 —三級丁基水楊酸、3,5 —二一三級辛基水楊酸' 3，5-二一 二級壬基水楊酸、3,5 —二一三級十二基水楊酸、3-甲基 一 5 —二級十二基水楊酸、3-三級十二基水楊酸' 5 —三級 -22- 200928332 十二基水楊酸、5 —環己基水楊酸、3,5 —雙（α:，α -二甲基 节基）水楊酸、3，5—雙（α -甲基苄基）水楊酸' 3—甲基—5 —(α —甲基苄基）水楊酸、3— (α，α —二甲基苄基）—5-甲基水楊酸、3—（〇:，〇: _二甲基苄基）一6_甲基水楊酸、3 —(α —甲基苄基）—5—（α，α —二甲基苄基）水楊酸、3 — { a , a — 一甲基节基）_6_乙基水楊酸、3—苯基—5 — (〇:，〇: —二甲基苄基）水楊酸、羧改性萜烯苯酚樹脂、35 _ 雙（〇： —甲基苄基）水楊酸與苄基氯之反應生成物的水楊酸 〇 樹脂等之鋅鹽、鎳鹽、鋁鹽、鈣鹽等。 該等中以可得水楊酸鋅鹽爲高的發色濃度之點爲特 佳。 (顯色劑分散液之調製） 顯色劑分散液在電子受體性化合物爲上述無機化合物 之情形，藉由使無機化合物以機械方式在水系進行分散處 理而可調製，又，電子受體性化合物爲有機化合物之情形， 可使有機化合物以機械方式於水系進行分散處理，或藉由 〇 溶解於有機溶劑來調製。 詳細內容可參照特開平8 - 20743 5號公報所記載之方 法。 (顯色劑層形成用調製液之調製） 如上述方式所調製之電子受體性化合物分散液，可照 樣作爲形成含有電子受體性化合物之顯色劑層用之調製液 (尤其是塗布液）。又，在形成顯色劑層用之調製液（尤其是 塗布液），黏合劑可添加苯乙烯-丁二烯共聚物乳膠、乙酸 乙烯酯系乳膠、丙烯酸酯系乳膠、聚乙烯醇、聚丙烯酸、 -23- 200928332 順丁烯二酸酐一苯乙烯-共聚物、澱粉、乾酪素、阿拉伯 膠'明膠、羧甲基纖維素、甲基纖維素等合成或天然高分 子物質。又顏料方面可添加高嶺土、燒成高嶺土、高嶺土 凝集體、重質碳酸鈣、各種形態（米粒形、角形 '紡錘形、 毽形、球形、文石系柱形、無定形等）之輕質碳酸鈣、滑石、 金紅石型或銳鈦礦型之二氧化鈦等。再者可依照期望添加 螢光增白劑、消泡劑、浸透劑、防腐劑。 在將該顯色劑層形成用之調製液作爲塗布液使用之情 〇 形，塗布液之塗膜方法方面，係使用通常塗膜機進行塗布、 乾燥。具體塗/膜機之例方面，有例如刮刀塗布機，桿塗布 ,機，氣刀塗布機，簾幕塗布機，凹版茚刷塗布機，棒塗布 撵，輥塗布機，擠壓塗布機，模塗布機，滑動珠塗布機， 刮刀塗布機等。 本發明之壓力測定用材料係在電子給與性無色染料前 驅物內包之微膠囊與電子受體性化合物各自以塗膜等於個 別基體所構成之雙片型之情形，例如將含有顯色劑之塗布 〇 液在所望薄片形基體上直接或者隔著其他層塗布、乾燥藉 以獲得至少形成有顯色劑層之薄片材料。又，電子給與性 無色染料前驅物內包之微膠囊與電子受體性化合物在以塗 膜等於單一薄片形基體上而構成之單片型之情形，例如在 所望的薄片形基體上直接或者隔著其他層，將含有顯色劑 之塗布液進行塗布、乾燥，藉以形成構成壓力測定用材料 之顯色劑層。 在電子受體性化合物（顯色劑）之顯色劑層中，量（塗布 時爲塗布量）方面，乾燥後質量以〇.1〜3(^/11{爲佳，較佳爲 • 24 - 200928332 在無機化合物之情形爲3〜2〇g/nf，有機化合物之情形爲 0.1〜5g/rrf，更佳爲在無機化合物之情形爲5〜15g/nf，有 機化合物之情形爲0.2〜3g/rri。 以下說明本發明的例示實施形態。但是本發明並非限 定於該等。 < 1 >一種壓力測定用材料，其係利用到電子給與性無色 染料前驅物與電子受體性化合物的發色反應之壓力測定用 材料，其係具有： © 基體；含有內包該電子給與性無色染料前驅物之微膠 囊且設置於該基體上之發色層；及設置於該基體端部之間 隔件’相對於該微膠囊之體積標準95 %徑A("m)，該間隔 件之厚度爲（A X 0.6)em以上，（a X i.〇)#m以下。 <2>如<1>之壓力測定用材料，其中該間隔件設置於捲 筒狀之該基體寬方向之兩端部。 <3>如<1>之壓力測定用材料，其中在四角形基體之— 對相對向的邊之端部設置該間隔件。 © <4>如<1〉之壓力測定用材料’其中在該基體具有該發 色層之側，設置該間隔件。 <5>如<1>之壓力測定用材料，其中將體積標準的中値 徑D(/zm)之微膠囊夾持於一對平行的平面間，使該—對平 面之間隔成爲（D X 0_25)//m以上，（d X 0.90)// m以下時所 破壞之微膠囊作爲該微膠囊使用。 <6>如<1>之壓力測定用材料，其中該間隔件係將含 有顏料’黏合劑及溶劑之間隔件形成溶液塗布於基體上而 設置者。 -25- 200928332 其在0.5MPa以下之壓力 其中該電子受體性化合 其中該電子給與性無色 10000 mol— 1 · cm— 1 · L 以 <7>如<1>之壓力測定用材_ 可進行發色。 <8>如<1>之壓力測定用材米斗 物爲水楊酸鋅鹽。 < 9 >如< 1 >之壓力測定用材料， 染料前驅物之莫耳吸光係數（ε )胃 上。 <10>如<1>之壓力測定用材料，其中該微膠囊之壁厚 Ο 爲 0.005 〜3.0 " m。 特願2007 — 314057之揭示係參照其說明書全體內容而 被本說明書所擷取利用。 本說明書所記載之全部文獻、專利申請及技術規格係 參照各文獻、專利申請、及技術規格而加以擷取者，而與 具體的且個別記載之情形相同程度，在本說明書中可予參 照並擷取使用。 【實施例】 〇 以下，根據實施例進而詳細說明本發明，但本發明並 非受下述實施例所限定。此外若無特別限定，「份」係質量 基準。 [實施例1] -電子給與性無色染料前驅物內包微膠囊液（A)之調製-將作爲電子給與性無色染料前驅物之下述化合物（A) 9 份溶解於二芳基乙烷70份獲得溶液A。接著’將溶解於甲 基乙基酮1份之乙二胺之環氧丁烷加成物〇.4份添加於攪 拌著的溶液A獲得溶液B。進而’將溶解於甲基乙基酮1 -26- 200928332200928332 IX. Description of the invention: [Technical field to which the invention pertains] This is a material for pressure measurement for measuring and recording a pressure distribution on a contact surface or a pressurized portion. [Prior Art] The material for pressure measurement is used in the bonding step of liquid crystal glass, and is used for soldering printing of the substrate, pressure adjustment between rolls, and the like. The pressure measuring material is, for example, a pressure measuring film represented by Prescale (trade name) supplied from Fujifilm Co., Ltd. In the example of the pressure-measuring film, a pressure-measuring sheet which discloses a color reaction using an electron-donating leuco dye precursor and an electron-accepting compound is disclosed in Japanese Patent Publication No. 57-24852. It is measured in a pressure range of about 0.1 MPa to 20 MPa. The pressure measuring film is characterized in that the film can be cut into any size in accordance with the measurement site. Further, a color reaction occurs due to the high linear pressure due to the writing pressure, which is different from the so-called pressure sensitive carbon paper, and the pressure measuring film has a feature that the surface pressure can be measured. In the material for pressure measurement, a coloring agent or a coloring agent which chromes the coloring agent is contained in a microcapsule. When the set pressure is applied to the microcapsules, the microcapsules are destroyed, and the components contained therein are released from the microcapsules to produce a chromogenic reaction. The sensitivity to the pressure of the material for pressure measurement can be adjusted by the ease of destruction of the microcapsules and the like. Therefore, it is necessary to pay attention to the treatment of the material for pressure measurement for low pressure measurement (i.e., when the microcapsule is easily broken). Further, when a material for pressure measurement for low pressure measurement is produced, when the material is wound into a roll shape, pressure is applied to the microcapsules, and the microcapsules coated on the substrate 200928332 are damaged. In order to protect the coating film on the substrate, it is proposed to prevent the coating film from being clogged in the vicinity of both end sides in the width direction of the coated portion of the coating portion which is thicker than the coating film. (blocking) and other methods. According to this method, we can protect the microcapsules coated on the substrate. OBJECTS OF THE INVENTION In order to prevent the destruction of the microcapsules having the largest diameter, the coating portion is relatively thick in order to prevent the destruction of the microcapsules having the largest diameter. However, when the difference between the thickness of the coating film containing the microcapsules and the thickness of the coating portion becomes large, the winding deviation or the winding of the winding is liable to occur in the step of manufacturing the pressure measurement. As a result, the microcapsules are destroyed. That is, even if the microcapsules are protected from damage by the method disclosed in Japanese Laid-Open Patent Publication No. 2002, the present invention has been made in view of the above-mentioned conventional problems, and it is intended to provide a pressure measuring method capable of preventing destruction of microcapsules. material. The invention relates to a material for pressure measurement which utilizes a color reaction of an electron-donating leuco-anterior electron-accepting compound, comprising: a matrix; containing the electron-donating leuco dye a precursor sac and a chromonic layer disposed on the substrate; and a substrate having a thickness of 95% of the diameter A (/zm) relative to the volume of the microcapsule (A x 〇.6) ) 68540 which is ym or more and (A x 1.0) ym or less is formed in the damage or is expected to be in the film. Between the drive and the micro-adhesive part of the tie, the interval pressure is measured 200928332. EFFECT OF THE INVENTION According to the present invention, there is provided a material for pressure measurement which can prevent destruction of microcapsules. [Embodiment] Hereinafter, the material for pressure measurement of the present invention will be described in detail. The pressure measuring material of the present invention is a coloring product using an electron-donating leuco dye precursor (hereinafter referred to as "chromogen") and an electron accepting compound (hereinafter referred to as "developer"). The material for pressure measurement of the reaction has: a substrate; a chromonic layer containing microcapsules containing the electron-donating leuco dye precursor and disposed on the substrate; and a spacer disposed at an end of the substrate The thickness of the spacer is (AX 0.6)/zm or more and (Ax 1.0)#m or less with respect to the volume standard 95% diameter A (/zm) of the microcapsule, and is used in the pressure measuring material of the present invention. Since the spacer having the set thickness is provided at the end of the base body, a gap can be provided between the base body and the base body in the case where the pressure measuring material is superposed. The coloring layer ® is placed in this gap to prevent damage to the microcapsules. In addition, the state in which the material for pressure measurement is superposed may be exemplified by a state in which a sheet-like pressure measuring material is laminated or a state in which a pressure measuring material is wound into a roll shape. The spacer may be disposed at the end of the substrate so that a spacer is preferably provided where the substrate has a chromonic layer. Thereby, since the portion where the spacer is provided (i.e., the portion where the coloring layer is not provided) exists on the substrate, the user can handle the material for pressure measurement without touching the coloring layer. Therefore, the workability of the material for pressure measurement can be improved. In the pressure measuring material of the present invention, the thickness of the spacer is (A x 〇.6)/zm or more, (A x 1.0) μ m with respect to the volume of the microcapsule 200928332 95% diameter A (; zm). the following. When the thickness of the spacer is less than (a χ 0.6) // m, applying pressure to the microcapsules in the state of superimposing the pressure measuring material may cause damage to the microcapsules. Further, when the thickness ratio of the spacer is larger than (Ax 1.0)//m, the occurrence of the winding deviation or the winding of the crepe at the time of winding the substrate in the step of producing the pressure-measuring material causes the microcapsule to be damaged. In the present invention, the thickness of the spacer is preferably (A X 0.62) v m or more and (A X 1.0) ym or less. It is preferably (A X 0.65) jum or more and (A X 1.0) Aim. Further, in the present invention, the volume standard of the microcapsules is 95%, which means that the cumulative curve is obtained by taking the cumulative curve of the whole volume of the microcapsules at 100%, and the cumulative curve becomes a particle diameter of 95%. This volume standard 95% diameter system applies a solution containing 1 to 40% (mass basis) of microcapsules to a support, and the surface thereof is photographed by an optical microscope at 150 times, and the size of all microcapsules in a range of 2 cm x 2 cm is measured. Get it right. In addition, the diameter of the volume standard means that when the volume is 50% and the particle size is divided into two critical enthalpies, the total volume of the microcapsules on the large diameter side and the small diameter side is equal to the same diameter. It can be obtained in the same way as the volume standard 95% diameter. The pressure measuring material of the present invention is a microcapsule containing an electron-donating leuco dye precursor and an electron accepting compound which reacts with the electron-donating leuco dye precursor to form a color. It consists of a single substrate 'or an individual substrate (preferably a coating film). The pressure measuring material of the present invention is a so-called monolithic type (mono 200928332-sheet type) in which a microcapsule and an electron acceptor compound are provided on a single substrate by a coating film or the like, and has a substrate such as a sheet or a film. And a color developer layer containing the developer disposed on the substrate in this order from the substrate side; and the coloring layer containing the microcapsules are formed as 'separately clamped to the portion where the pressure or pressure distribution is to be measured and given Pressurize. Further, the material for pressure measurement according to the present invention is a case where a microcapsule and an electron acceptor compound are provided in a so-called two-sheet type of a single substrate by a coating film or the like, and have a substrate such as a sheet or a film. a material A having a developer layer containing a color developing agent; and a material B having a coloring layer containing microcapsules on a substrate such as a sheet or a film, so that the surface of the microcapsule of the material B is present ( The surface of the chromonic layer, in a manner that faces the surface of the material A in which the electron accepting compound is present (the surface of the developer layer), so that the two materials overlap 'in the overlapping state, the pressure or pressure distribution is to be measured. The part is pressurized. Pressurization can be carried out by applying pressure (point pressure, line pressure, surface pressure, etc.) to a point, a line or a surface by any method. The present invention is effective for a material for pressure measurement which is color-developable under a pressure of 0.5 MPa or less which is easily broken by microcapsules. For example, under the pressure, the microcapsules are destroyed and the inclusions containing the electron-donating leuco dye precursor are released by reacting the electron-donating leuco dye precursor with the electron accepting compound. Coloring can be observed. At this time, as the pressure of the pressurization becomes larger, the inclusions containing the electron-donating leuco dye precursor are more released, and the amount of reaction with the electron acceptor compound is increased, so that a strong hair can be obtained. color. In the above, the pressure-measuring material is a microcapsule and an electron-accepting compound containing an electron-donating leuco dye precursor, and is provided with a coating film on an individual substrate or the like in terms of storage stability and handleability. The two-piece type 200928332 is even better. Hereinafter, each element constituting the material for pressure measurement of the present invention will be described. <Base> The substrate constituting the material for pressure measurement of the present invention may be any of a sheet shape, a film shape, a plate shape, a roll shape, and the like. Specific examples include paper, a plastic film, synthetic paper, and the like. The pressure measuring material is also the same in any of a single-piece type and a two-piece type.具体 Specific examples of the paper 'woodfreepaper, wood containing paper' groundwood paper, neutral paper, acid paper, coated paper 'machine film Paper, art paper, cast coat paper, micro coated paper, tracing paper, recycled paper, and the like. Specific examples of the plastic film include a polyester film such as a polyethylene terephthalate film, a cellulose derivative film such as cellulose triacetate, a polyolefin film such as polypropylene or polyethylene, and a polystyrene film. Further, as a specific example of the synthetic paper, for example, polypropylene or polyethylene terephthalate or the like is biaxially stretched to form a microporous body (Yupo or the like), or by poly. A synthetic fiber such as ethylene, polypropylene, polyethylene terephthalate or polyamidamide, which is laminated on one part, one side or both sides of the paper. However, the present invention is not limited to these. In such a case, it is preferable to use a plastic film or a synthetic paper in order to further increase the color density of the color produced by the pressurization, and it is preferable to use a plastic film. In the material for pressure measurement of the present invention, a roll-shaped base body ’-10-200928332 is preferably used, and spacers are preferably provided at both end portions in the width direction of the base body. By making the pressure measuring material of the present invention into such a configuration, it is possible to effectively prevent the destruction of the microcapsules in the manufacturing step of the material for pressure measurement. Further, when the material for pressure measurement of the present invention wound in a roll shape is stored, the destruction of the microcapsules can be effectively prevented. In particular, since the microcapsules are prevented from being broken by contact with the coated surface contact roller, it is preferable to provide a spacer on the side where the base coloring layer is provided. Further, in the pressure measuring material of the present invention, a square 〇 base may be used, or the spacer may be provided on one end of the base opposite to the opposite side. By making the pressure measuring material of the present invention into such a configuration, it is possible to effectively prevent the destruction of the microcapsules when the pressure measuring material is deposited in a state of being deposited. The pressure measuring material of the present invention in which the base body has a square shape is obtained by cutting a roll of the pressure measuring material of the present invention to a desired length. <Coloring layer> 〇 In the material for pressure measurement of the present invention, a coloring layer containing a microcapsule containing an electron-donating leuco dye precursor is provided on a substrate. (Electron-donating leuco dye precursor) The microcapsules contained in the chromonic layer of the pressure-measuring material of the present invention contain at least one of electron-donating leuco dye precursors. The electron-donating leuco dye precursor contained in the microcapsules can be used in the use of pressure sensitive carbon paper or thermal recording paper. For example, a triphenyl methane phthalide compound 200928332, a fluorescent yellow mother (flU0ran) compound, a morphine compound, a decyl azlactone compound, and a white golden amine can be used. Various compounds such as a leucoauramine compound, a rhodamine amide compound, a triphenylmethane compound, a diphenylmethane compound, a triazene compound, a spiropyranoid compound, and an anthraquinone compound. For the details of the above-mentioned compounds, the electron-donating leuco dye precursors may be used alone or in combination of two or more. ® electron-donating leuco dye precursors, which improve the color developability below 0.5 MPa, and at high pressures (higher concentration change (concentration gradient) relative to pressure change) It is preferable that the molar absorption coefficient (ε) is high. The molar absorption coefficient (e) of the electron-donating leuco dye precursor is preferably 10000 mol - 1 · cm - 1 · L or more, more preferably 15000 mol - 1 · cm -1 · L or more, and further 25,000 mol - · cm-1·L or more is preferred. ε is a suitable example of an electron-donating leuco dye precursor in this range, for example, 3-(4-diethylamino 2-ethoxyphenyl)-3-(1_ethyl-2-yl)吲哚吲哚3-3)_4-azaindole (ε = 61000), 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-n-octyl-2 —methyl hydrazine-3-enyl lactone (ε = 40000), 3 — [2, 2 bis(1-ethyl-2-methylindole-3-yl)ethene]-3 — 4-diethylaminophenyl)-decalactone U=40000), 9-[ethyl(3-methylbutyl)amino]helix[12Η-benzo[a]卩ill I] star 12,1'(3'Η)isobenzofuran]-3'-ketone U=34000), 2-anilino-6-dibutylamino-3-methylfluorescein yellow parent U=220 00) 6-Diethylamino-3-methyl-2 - (2,6 -12- 200928332 -dimethylaniline)-fluorescent yellow matrix (e = 19,000), 2- (2-chloroanilinyl) —6—Dibutylamino-based fluorescent yellow mother (ε = 21000), 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminodecanolide (ε = 16000) 2-anilino-6-diethylamine A 3 - methyl Lucifer Yellow precursor (e = 1 60 00) and the like. One type of electron-donating leuco dye precursor having a molar absorption coefficient ε within the above range, or two or more electron-donating leuco dye precursors having a molar absorption coefficient ε within the above range When the leuco dye precursor is used in combination, the color development at 〇5 MPa can be improved, and the high concentration at a low pressure (increasing the concentration change (concentration gradient with respect to pressure change)) In the total amount of electron-donating leuco dye precursors, the molar absorption coefficient (ε) is a ratio of electron-donating leuco dye precursors of 10000 mol-1 / cm · 1 · L or more, from 1 〇 to 100 The range of the mass% is preferably in the range of 20 to 100% by mass, more preferably in the range of 30 to 100% by mass. In the case where two or more kinds of electron-donating leuco dye precursors are used, it is preferable to use two kinds of ε ε each of which is 1.00 mol or more of 1.cm_1.L or more. The Mohr absorbance coefficient (?) was calculated from the absorbance when the electron-donating leuco dye was dissolved in a 95% aqueous acetic acid solution. Specifically, in the 95% aqueous acetic acid solution of the electron-donating leuco dye having a concentration adjusted to have an absorbance of 1.0 or less, the length of the cell for measurement is Αcm, and the concentration of the electron-donating leuco dye is B. Mohr/L, when the absorbance is c, it is calculated by the following formula. Mohr absorbance coefficient (ε) = C / (AXB) The amount of electron-donating leuco dye precursor (for example, coating amount) can be improved from -13 to 28,283,32 in terms of color development of 0.5 MPa or less. The mass after drying is preferably 0.1 to 5 g/ni, more preferably 0.1 to 4 g/m2, more preferably 0.2 to 3 g/rri. (Solvent) The microcapsules of the present invention may contain at least one solvent together with the electron-donating leuco dye precursor. In terms of the solvent contained in the microcapsules, it can be used for the purpose of using pressure sensitive carbon paper. For example, alkylnaphthalenes such as diisopropylnaphthalene, diarylalkanes such as monophenyl-1-methylbenzylethane, alkylbiphenyls such as isopropylbiphenyl, and other triarylmethanes. Aromatic hydrocarbons such as alkylbenzenes, benzylnaphthalenes, diarylalkylenes, and arylindans; aliphatic hydrocarbons such as dibutyl phthalate and isoparaffin; soybean oil, corn oil, cottonseed oil, Natural oil and vegetable oil such as rapeseed oil, olive oil, coconut oil, castor oil, fish oil, etc., high-boiling fraction of natural oil such as mineral oil. The solvent may be used alone or in combination of two or more. Further, if necessary, the solvent may be added with a ketone such as methyl ethyl ketone or an ester such as ethyl acetate or an alcohol such as isopropyl alcohol, and has a boiling point of 13 Å. (: the following solvents. G (microcapsules and methods for producing the same) Electron-donating leuco dye precursors and microcapsules which can be encapsulated in a solvent as needed. Any method known per se, such as interfacial polymerization, internal polymerization The method of the method, the phase separation method, the external polymerization method, the coacervation method, etc. The wall material of the microcapsule is a wall material of the microcapsule containing the electron-donating leuco dye precursor which can be used as a pressure sensitive recording material. The water-insoluble, oil-insoluble polymer used is not particularly limited. Among the wall materials, the urethane-urea resin (polyurethane--14-200928332 urea), melamine-formaldehyde resin Preferably, gelatin is preferred, and a polyurethane-urea-melamine-formaldehyde resin is preferred from the viewpoint of obtaining good color development at a low pressure (preferably 0.5 MPa or less), particularly a urethane-containing bond. It is preferred to use a mixture of Fee formic acid and vinegar. Here, the case of using polyurethane-urea in the capsule wall material is described as an example. The electron-donating leuco dye precursor is encapsulated. The preparation of a microcapsule dispersion of polyurethane-urea wall can be used in a known method for use in pressure-sensitive carbon paper, for example, a solution in which an electron-donating leuco dye precursor and a polyvalent isocyanate are dissolved in a solvent (oil phase). Emulsifying and dispersing in a water-transfering solution (for example, water or the like) containing a water-soluble polymer (a substance for forming a capsule wall such as a polyalcohol or a polyamine), and the oil droplets in the obtained emulsified dispersion are made of polyurethane- A method in which urea is coated to carry out microencapsulation. At this time, a microcapsule wall can be formed by heating at the oil droplet interface to form a microcapsule wall. In the middle of the microencapsulation step, a polyvalent hydroxy compound or a polyvalent hydroxy compound can be added. A reaction regulator such as a polyvalent amine. In the specific examples of the polyvalent hydroxy compound, an aliphatic or aromatic polyvalent alcohol, a hydroxy polyester, a hydroxypolyalkylene ether, and a polyvalent amine alkylene oxide may be exemplified. The product is preferably an aliphatic or aromatic polyvalent alcohol or an alkylene oxide adduct of a polyvalent amine, more preferably an alkylene oxide adduct of a polyvalent amine. There are 2 in the molecule Any one of an NH group or an -NH2 group may be used. Specific compound aspects may, for example, be diethylenetriamine, triethylenetetramine' 1,3-propylenediamine, hexamethylenediamine Aliphatic polyvalent amines; epoxy compound adducts of aliphatic polyvalent amines; alicyclic polyvalent amines such as hexahydropyrrol; 3,9-bis-aminopropyl-2,4,8,10 —tetraoxane-15- 200928332 Heterocyclic diamine such as heterohelix-(5,5)undecane, etc. The amount of polyvalent hydroxy compound or polyvalent amine can be added according to the type and amount of polyvalent isocyanate used. Further, it can be appropriately determined depending on the hardness of the capsule wall, etc. In the case of adding a polyvalent hydroxy compound or a polyvalent amine, the ratio of "the amount of the polyvalent hydroxy compound and/or the polyvalent amine: the amount of the polyvalent isocyanate" (quality) The ratio is preferably 0.1: 99.9 to 30: 70, and more preferably 1:99 to 25:75. Further, in terms of the amount of the polyvalent hydroxy compound added, the mass ratio of the polyvalent isocyanate: polyvalent hydroxy compound is preferably 99.9: 0.1 to 70: 30, preferably 99: 1 to 75: 25, and 98: 2 ~80: 20 is better. The addition period of the polyvalent hydroxy compound or the polyvalent amine may be previously added to the solvent or the auxiliary solvent for dissolving the electron-donating leuco dye precursor, and may be added before or after the emulsification dispersion. In the hydrophilic solution, various amphoteric polymers, ionic polymers, and nonionic polymers may be added as an emulsifier, and for example, gelatin, starch, carboxymethylcellulose, polyvinyl alcohol, polyalkylbenzenesulfonate may be added. An acid salt, a polyoxyethylene sulfate, a polyoxyalkyl ether or a modified product thereof, an isobutylene-m-butylene anhydride copolymer, and the like. As the polyvalent isocyanate, those known in the use of pressure-sensitive carbon paper can be used. For example, isomeric cyanurate of hydrogenated xylylene diisocyanate (generally referred to as hydrogenated XDI), isomeric isocyanate diisocyanate (generally known as IPDI), diisocyanate Acid 4,4'-diphenylmethane ester, adduct of hexamethylene diisocyanate and trimethylolpropane, bullet body of hexamethylene diisocyanate, diisocyanate An isomeric cyanurate of hexamethylene methyl ester, an isomeric isocyanate of hexamethylene diisocyanate bound with an aliphatic diol (for example, an alkylene glycol) with a urethane bond Compound, polymethylene polyphenyl-16- 200928332 isocyanate, carbodiimide modified diphenylmethane diisocyanate, diphenyl phenyl diisocyanate and trimethylolpropane adduct, diiso Addition of xylyl cyanate to trimethylolpropane, isomeric cyanurate of diphenylcyanatoin, addition of xylyl diisocyanate to trimethylolpropane , an adduct of isophorone diisocyanate and trimethylolpropane, an elastomer of dylyl isocyanate and a tris-(p-isocyanate phenyl) thiophosphite . The polyvalent isocyanate may be used alone or in combination of two or more. Further, in the microcapsules, in addition to the above-mentioned electron-donating leuco dye precursor, the solvent, and the auxiliary solvent, an additive may be included as needed. As the additive, there are an ultraviolet absorber, a photostabilizer, an antioxidant, a wax, a deodorant, and the like. In terms of the mass ratio of the solvent and the electron-donating leuco dye precursor contained in the microcapsule (solvent: precursor), it is preferably in the range of 98: 2 to 30: 70 in terms of color development. The range of 97: 3 to 40: 60 is better, and the range of 95: 5 to 50: 50 is better. In terms of the diameter of the microcapsule volume standard, the color development density at a low pressure (less preferably 0.5 MPa or less) can be increased, and when the scanning is performed to read the visibility and the concentration, the density reproduction accuracy can be improved. In terms of point, it is preferably lO/zm or more, preferably 10 to 40 μm, more preferably 13 to 30 μm, and 16 to 2 5 #m. In the present invention, the microcapsules having the diameter D (" m) in the volumetric standard are placed between a pair of parallel planes so that the interval between the pair of planes becomes (Dx 0.25) / Z m or more, (D x 0.90). The microcapsules destroyed at /zm or less are preferably used as the microcapsules constituting the coloring layer. By using the microcapsules which exhibit the above-described set strength, when the pressure measuring material is placed in a superposed state, a pressure of -17-200928332 is applied to the microcapsules to obtain an effect of preventing the microcapsules from being damaged. The interval between the pair of planes is preferably (Dx 0.27) / //m or more, (D X 0.90) #m or less, and more preferably (D X 0.30) / zm or more and (D X 0.9 0) μ m or less. Here, the "space between a pair of planes" when the microcapsules are destroyed can be measured at 23 ° C using a micro hardness tester. Specifically, the substrate coated with the microcapsules is placed on the sample table of the micro hardness tester, and when the microcapsules are pressed by the flat indenter, the surface of the substrate and the crucible when the package is just emerging from the microcapsules The interval between the planar indentations is obtained by taking five microcapsules having an inner diameter of ±10% with respect to the diameter standard, and averaging the "interval of a pair of planes". The "interval between the surface of the substrate and the plane indentation" can be measured, for example, by Shimadzu Corporation, MCT-W200. Further, the diameter of the microcapsules can be obtained by optical microscopic observation. The microcapsules having the above-described set strength can be produced by any method known per se, for example, an interfacial polymerization method, an internal polymerization method, a phase separation method, an external polymerization G method, or a coacervation method. The wall material of the above-mentioned microcapsules is not particularly limited as long as it is a water-insoluble or oil-insoluble polymer used as a wall material of an electron-containing leuco dye-containing microcapsule which is a conventional pressure-sensitive recording material. The polyurethane wall, the melamine-formaldehyde wall and the gelatin wall are preferred, and the polyurethane wall and the melamine-formaldehyde wall are more preferred. The wall thickness of the capsule wall of the microcapsule may be determined by various conditions such as the type of the material of the capsule wall or the diameter of the capsule, but it may be unrestricted if it is in a range that can be destroyed by a slight (at least MPa.〇5 MPa) pressurization. Free to choose. The preferred wall thickness is in the range of 0.005 to 3.0/m, more preferably 0.005 to 2.8/zm, from the viewpoint of obtaining good color developability under the pressure of -18-200928332 0.5 MPa or less. In the case where the diameter of the microcapsules is 10 to 40 μm, it is 0.06 to 1.0/zm. The wall of the capsule of the special capsule is thick, and the capsule wall of the microcapsule having a medium diameter of 10 to 40 em is composed of polyurethane-urea and is 0.07 to 0.85 Aim. In the present invention, the wall thickness means the thickness of the resin film (so-called capsule wall) forming the capsule particles of the microcapsule, and the thickness of each capsule wall of the five microcapsules is averaged by a scanning electron microscope. The mean is mean. (Preparation of Preparation Liquid for Formation of Coloring Layer) The microcapsules can be obtained as a dispersion liquid in the above manner, and the dispersion liquid of the microcapsules can also be used as a coloring layer for forming a precursor containing an electron-donating leuco dye. Modulation liquid (especially coating liquid). Further, in the dispersion of the microcapsules obtained as described above, a fine powder such as starch or a starch derivative, a buffering agent such as cellulose fiber powder, a water-soluble polymer binder such as polyvinyl alcohol, or a vinyl acetate-based acrylic acid may be added. A hydrophobic polymer binder such as styrene-butadiene fluorene copolymer latex, a fluorescent whitening agent, an antifoaming agent, a penetrating agent, a UV absorber, and a preservative as a preparation liquid (especially a coating liquid). The preparation liquid (particularly, the coating liquid) thus obtained is applied to the coating film to be equal to the substrate, and dried to form a coloring layer constituting the material for pressure measurement. In the case where the preparation liquid for forming the coloring layer is used as a coating liquid, the coating method of the coating liquid is applied and dried using a usual coater. Examples of specific coating machines include, for example, air knife coaters, rod coaters, bar coaters, curtain coaters, gravure brush coaters, extrusion coaters, -19-200928332 die coaters, sliding beads ( Slide bead) coater, knife coater, and the like. In the case of the pressure-measuring material of the present invention, the microcapsules and the electron-accepting compound-coated in the electron-donating leuco dye precursor are each coated on a sheet form of an individual base coating film or the like. The coating liquid can be applied to the desired sheet-like substrate directly or through another layer to obtain a sheet material in which at least the coloring layer is formed. Further, in the case of a single-sheet form in which a microcapsule and an electron-accepting compound contained in an electron-donating leuco dye precursor are coated on a single sheet-shaped substrate, for example, it is formed on a desired substrate. The coating liquid was repeatedly applied and dried on the developer layer to obtain a material for pressure measurement. <Spacer> In the material for pressure measurement of the present invention, a spacer may be provided at the end of the base. The component constituting the spacer and the method for forming the separator are not particularly limited, and it is preferable to apply a solution containing a spacer of a pigment, a binder and a solvent to a substrate, and to improve the thickness uniformity of the spacer. In terms of the pigment constituting the spacer, there are, for example, kaolin, calcined kaolin bauxite 'kaolin aggregate, heavy calcium carbonate, various forms (rice shape 'angle shape, hammer shape, blanket shape, spherical shape, aragonite column shape, Amorphous, etc.) light carbonic acid consumption, talc, rutile or anatase type titanium dioxide, etc., and kaolin aggregate, heavy calcium carbonate, light calcium carbonate, talc is preferred, kaolin aggregate, heavy Calcium carbonate and light calcium carbonate are further preferred. Examples of the binder constituting the spacer include a water-soluble polymer binder such as polyvinyl alcohol, a synthetic or natural polymer substance such as starch, casein, gum arabic, gelatin, carboxymethyl cellulose, or methyl cellulose. Hydrophobic -20-200928332 polymer binder such as acrylic acid ethyl ester, acrylic or styrene-butadiene copolymer latex, and polyvinyl alcohol, styrene-butadiene copolymer latex, acrylic latex, Carboxymethyl cellulose, methyl cellulose is preferred, polyvinyl alcohol, styrene-butadiene copolymer latex, carboxymethyl cellulose, and methyl cellulose are further preferred. The ratio of the pigment to the binder constituting the spacer (mass basis) is preferably 100:5 to 5:100, and more preferably 100:7 to 10:100. The solvent to be used for forming the solution in the separator is not particularly limited as long as it can dissolve and disperse the pigment and the binder, and examples thereof include ketones such as water and methyl ethyl ketone, and esters such as ethyl acetate. An alcohol such as isopropyl alcohol or the like having a boiling point of not more than 30 ° C is preferably water, methanol, ethanol or isopropanol, and more preferably water or isopropanol. . A solution is formed in the spacer, and an additive may be contained as needed. As the additive which can form a solution for the spacer, there are, for example, a surfactant, an antifoaming agent, a preservative, a viscosity adjusting agent and the like. Examples of the film coating machine for forming a solution in a spacer include, for example, an air knife coater, a bar coater, a bar coater, a curtain coater, a gravure brush coater, a squeezing coater, a die coater, and a sliding bead coating. Machine, knife coater, etc. By using these film applicators, the position of the spacer on the substrate can be set. After the coating of the spacer forming solution, the spacer can be formed by drying the coating film. The material for pressure measurement according to the present invention is a base material having a roll shape, and a spacer is provided at both end portions in the width direction of the base body. In the width direction of the base body, the width of the spacer is made in the width of the spacer. When the width is i, it is preferably 0.01 to 0.99, more preferably 0.02 to 0.98, and particularly preferably 0.02 to 0.95. -21- 200928332 When the width of the substrate is 1, the width of the spacer is in the range of 0.01 to 0.99, and the destruction of the microcapsules in the form of a superposition of the pressure measuring material can be more effectively prevented. Further, in the pressure measuring material of the present invention, a square-shaped base body is used, and in the case where one of the base members is provided with a spacer at the end of the opposite side, in the direction in which the opposite side of the spacer is disposed, When the width of the substrate is 1, the width of the spacer is preferably 0.01 to 0-99, more preferably 0.02 to 0.98, and particularly preferably 0.02 to 0.95. When the width of the substrate is set to 1, the thickness of the spacer is wider than 〇.〇1 to 0.99, and the pressure measuring material is superposed, whereby the microcapsule destruction can be effectively prevented. (Electron acceptor compound) The developer layer of the material for pressure measurement of the present invention contains at least one of an electron acceptor compound (developer). In the case of the electron acceptor compound contained in the developer layer of the present invention, there are inorganic compounds and organic compounds. Specific examples of the inorganic compound include clay clay, activated clay, attapulgite, zeolite, bentonite, kaolin clay, and the like. Examples of the organic compound include a metal salt of an aromatic carboxylic acid, a phenol formaldehyde resin, a metal salt of a carboxylated terpene phenol resin, and the like, among which acid white clay, activated clay, zeolite, kaolin, metal salt of an aromatic carboxylic acid, and carboxylation The metal salt of the terpene phenol resin is preferred, and the metal salt of acid clay, activated clay, kaolin, and aromatic carboxylic acid is more preferable. As a suitable specific example of the metal salt of the aromatic carboxylic acid, there are 3,5-di-tris-butylsalicylic acid, 3,5-di-tris-octylsalicylic acid 3,5-two one Grade sulfhydryl salicylic acid, 3,5-223 tridecyl salicylic acid, 3-methyl-5-tertiary dodecyl salicylic acid, 3-tris-dodecylsalicylic acid 5 — tertiary-22-2228328332 Twelve-based salicylic acid, 5-cyclohexylsalicylic acid, 3,5-bis(α:,α-dimethylnosyl)salicylic acid, 3,5-bis(α -methylbenzyl)salicylic acid '3-methyl-5-(α-methylbenzyl)salicylic acid, 3-(α,α-dimethylbenzyl)-5-methylsalicylic acid , 3-(〇:,〇: _dimethylbenzyl)- 6-methylsalicylic acid, 3-(α-methylbenzyl)-5-(α,α-dimethylbenzyl) water Salicylic acid, 3 - { a , a - monomethyl ketone) _6_ethyl salicylic acid, 3-phenyl-5- (〇:, 〇: -dimethylbenzyl) salicylic acid, carboxy modification A zinc salt, a nickel salt, an aluminum salt, a calcium salt or the like of a salicylic acid barium resin such as a terpene phenol resin or a reaction product of 35 _bis(〇:-methylbenzyl)salicylic acid and benzyl chloride. Among these, it is preferred that the zinc salicylic acid salt has a high coloring concentration. (Preparation of a developer dispersion) The developer dispersion can be prepared by subjecting an inorganic compound to a water-based dispersion treatment in the case where the electron-accepting compound is the above-mentioned inorganic compound, and electron acceptor In the case where the compound is an organic compound, the organic compound may be mechanically dispersed in an aqueous system or may be prepared by dissolving hydrazine in an organic solvent. For details, refer to the method described in JP-A-8-20743. (Preparation of a preparation liquid for forming a coloring agent layer) The electron-accepting compound-dispersed liquid prepared as described above can be used as a preparation liquid for forming a color developer layer containing an electron-accepting compound (especially a coating liquid) ). Further, in the preparation of a developer liquid (especially a coating liquid) for a developer layer, a styrene-butadiene copolymer latex, a vinyl acetate emulsion, an acrylate latex, a polyvinyl alcohol, a polyacrylic acid may be added to the binder. -23- 200928332 Synthetic or natural high molecular substances such as maleic anhydride-styrene-copolymer, starch, casein, gum arabic 'gelatin, carboxymethyl cellulose, methyl cellulose. In addition, kaolin, calcined kaolin, kaolin aggregate, heavy calcium carbonate, and various forms of light calcium carbonate can be added in various forms (rice shape, angular 'spindle shape, scorpion shape, spherical shape, aragonite column shape, amorphous shape, etc.). , talc, rutile or anatase type titanium dioxide. Further, a fluorescent whitening agent, an antifoaming agent, a penetrating agent, and a preservative may be added as desired. In the case where the preparation liquid for forming the developer layer is used as a coating liquid, the coating method of the coating liquid is applied and dried using a usual coater. Examples of the specific coating/film machine include, for example, a knife coater, a rod coating machine, a machine, an air knife coater, a curtain coater, a gravure brush coater, a bar coater, a roll coater, an extrusion coater, and a die. A coater, a slide bead coater, a knife coater, and the like. The pressure measuring material of the present invention is a case where the microcapsule and the electron accepting compound contained in the electron-donating leuco dye precursor are each in the form of a two-piece type in which the coating film is equal to an individual substrate, for example, a color developing agent is contained. The coating mash is applied or dried on the desired sheet-shaped substrate directly or through other layers to obtain a sheet material on which at least a developer layer is formed. Further, the microcapsule and the electron accepting compound encapsulated in the electron-donating leuco dye precursor are in the form of a monolithic type in which the coating film is equal to a single sheet-shaped substrate, for example, directly on the desired sheet-shaped substrate or The coating liquid containing the color developing agent is applied and dried through the other layers to form a color developer layer constituting the material for pressure measurement. In the color developer layer of the electron acceptor compound (developer), the amount (the amount of coating at the time of coating) is preferably 11 to 3 (^/11{, preferably 24 - 200928332 In the case of an inorganic compound, it is 3 to 2 g/nf, the case of an organic compound is 0.1 to 5 g/rrf, more preferably 5 to 15 g/nf in the case of an inorganic compound, and 0.2 to 3 g in the case of an organic compound. / rri. Hereinafter, an exemplary embodiment of the present invention will be described. However, the present invention is not limited to the above. < 1 > A pressure measuring material which is a material for pressure measurement using a color reaction of an electron-donating leuco dye precursor and an electron accepting compound, comprising: a matrix; a microcapsule of an electron-donating leuco dye precursor and a chromonic layer disposed on the substrate; and a spacer 95 disposed at the end of the substrate with respect to a volume standard of the microcapsule 95% ("m) The thickness of the spacer is (AX 0.6)em or more, and (a X i.〇) #m or less. <2><1> The material for pressure measurement, wherein the spacer is provided at both end portions of the cylindrical body in the width direction. <3><1> The material for pressure measurement, wherein the spacer is provided at an end portion of the quadrangular base body facing the opposite side. © <4><1> The material for pressure measurement' wherein the spacer is provided on the side of the substrate having the coloring layer. <5><1> A material for pressure measurement in which a microcapsule of a volume standard medium diameter D (/zm) is sandwiched between a pair of parallel planes so that the interval between the planes becomes (DX 0_25)// The microcapsules destroyed at m or more and (d X 0.90) / m or less are used as the microcapsules. <6><1> The material for pressure measurement, wherein the spacer is provided by applying a solution of a spacer containing a pigment > binder and a solvent to a substrate. -25- 200928332 which is at a pressure of 0.5 MPa or less, wherein the electron accepting compound is wherein the electron imparting colorless is 10000 mol - 1 · cm - 1 · L <7><1> Pressure measurement material _ Color development is possible. <8> The pressure measuring material of <1> is a zinc salicylate. < 9 >< 1 > The material for pressure measurement, the molar absorption coefficient (ε) of the dye precursor on the stomach. <10><1> The material for pressure measurement, wherein the microcapsule has a wall thickness Ο of 0.005 to 3.0 " m. The disclosure of Japanese Patent Application No. 2007-314057 is incorporated herein by reference in its entirety. All documents, patent applications, and technical specifications described in the specification are referred to the respective documents, patent applications, and technical specifications, and are to the same extent as the specific and individual descriptions, and may be referred to in this specification. Use it. [Examples] Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited by the following examples. In addition, "parts" are quality standards unless otherwise specified. [Example 1] - Preparation of electron-donating leuco dye precursor-incorporated microcapsule liquid (A) - Dissolving 9 parts of the following compound (A) as an electron-donating leuco dye precursor in diaryl B Solution A was obtained in 70 parts of alkane. Next, 4 parts of a butylene oxide adduct of ethylenediamine dissolved in 1 part of methyl ethyl ketone was added to the stirred solution A to obtain a solution B. Further 'will dissolve in methyl ethyl ketone 1 -26- 200928332
份之二異氰酸甲伸苯酯之三羥甲基丙烷加成物2份添加於 攪拌著的溶液B，獲得溶液C。接著，在溶解聚乙烯醇6 份於水150份之溶液中添加上述溶液C，進行乳化分散。 在乳化分散後之乳化液添加水300份，一邊攪拌一邊加溫 至70°C爲止，經1小時攪拌後予以冷卻。添加水來調整濃 度，獲得固形成份濃度1 8 %之電子給與性無色染料前驅物 內包微膠囊液（A)。在含於電子給與性無色染料前驅物內包 微膠囊液（A)之微膠囊的體積標準95 %徑爲35μιη，微膠襄 被破壞時一對平面之間隔爲18vm，體積標準之中値徑爲A portion of the trimethylolpropane adduct of methyl phenylisocyanate is added to the stirred solution B to obtain a solution C. Next, the above solution C was added to a solution in which 6 parts of polyvinyl alcohol was dissolved in 150 parts of water, and emulsified and dispersed. To the emulsion after the emulsification and dispersion, 300 parts of water was added, and the mixture was heated to 70 ° C while stirring, and stirred for 1 hour, followed by cooling. Water was added to adjust the concentration to obtain an electron-donating leuco dye precursor containing a solid component concentration of 18% of the microcapsule liquid (A). The volume standard 95% of the microcapsules containing the microcapsule liquid (A) contained in the electron-donating leuco dye precursor is 35 μm, and the interval between the pair of planes is 18 vm when the microcapsule is broken, and the volume standard is 値Trail is
化合物(A) -間隔件形成溶液（B)之調製— 將水7 5份、聚丙烯酸鈉5份、碳酸鈣1 00份混合於砂 磨機經分散後，添加SBR乳膠相當固形成份15份、羧甲基 纖維素1%水溶液15份、十二基苯磺酸鈉25 %水溶液1份 並混合，進而添加水使固形成份濃度成爲41.5%，來製作 間隔件形成溶液（B)。 -電子給與性無色染料薄片之製作一 搬送寬400mm之長條形聚對酞酸乙二酯薄膜（基體）， -27- 200928332 在此薄膜上將電子給與性無色染料前驅物內 與間隔件形成溶液（B)，於150mm寬之電子給 前驅物內包微膠囊液（A)之寬方向兩端，各自 間隔件形成溶液（B)接觸，同時使電子給與性 物內包微膠囊液（A)乾燥後之質量爲5.0g/nf 成溶液（B)乾燥後質量成爲33.0g/nf，以藉由 進行同時塗布後，予以乾燥，獲得電子給與 片。 〇 _含有顯色劑液之調製- 將3,5_雙（α _甲基苄基）水楊酸鋅1(H 份、六偏磷酸鈉1份及水200份使用砂磨器 平均粒徑3/zm，來調製分散液。接著在此分 乙烯醇之10 %水溶液100份，及作爲固形成 丁二烯乳膠10份、水450份來調製含有顯隹 -顯色劑薄片之製作- 將所得含有顯色劑液在厚度7 5 // m之聚 〇 (PET)薄片上，以棒塗布機進行塗布、乾燥， 布量爲10g/m2，來形成顯色劑層獲得顯色劑 如以上方式，來製作由電子給與性無色 色劑薄片所成雙片型的本發明壓力測定用材 一評價一測定一 就所得壓力測定用材料進行下述評價。 1所示。 (1)發色性能 將電子給與性無色染料薄片捲繞成捲筒 包微膠囊液（A) 與性無色染料 與50mm寬之 無色染料前驅 ，使間隔件形 滑動珠塗布機 性無色染料薄 &、碳酸鈣100 予以分散成爲 散液，添加聚 份之苯乙烯一 .劑液。 對酞酸乙二酯 使固形成份塗 薄片" 染料薄片及顯 料。 評價結果如表 狀。其後解開 -28- 200928332 該輥並切斷成5公分 x5公分之尺寸。將該電子給與性無 色染料薄片與切斷成5公分 x5公分尺寸之顯色劑薄片進 行疊合，以使電子給與性無色染料薄片之發色層表面與顯 色劑薄片之顯色劑層表面爲相面對，並使經疊合之兩薄片 以表面爲平滑的玻璃板2片加以夾持，在其上藉由擺上紡 錘以0.30MPa之壓力加壓，進行發色。其後，將疊合的兩 薄片剝離，使用濃度計RD — 19(GretagMacbeth公司製），測 定在顯色劑薄片所形成之發色部之濃度（DA)。 © 又’與此相區別，就未使用之顯色劑薄片以同樣方法 測定初期濃度（DB)。接著，自濃度DA減去初期濃度DB， 求得發色濃度AD’依照下述評價基準進行評價。此外，「b」 係實際使用上可容許的範圍。 一評價基準- Α(〇.〇4 ^ Δ D) :可確認明確的發色。 Β(0.01 ^ Δ D< 0.04):可確認微弱的發色。 C(A D< 0.01) :無法確認發色。 〇 (2)微膠囊破壞之有無 將電子給與性無色染料薄片捲繞成捲筒狀。其後將該 輥解開，以150倍光學顯微鏡觀察該薄片之微膠囊塗布面， 藉由以下基準進行膠囊破壞之評價。此外，「B」係實際使 用上可容許的範圍。 A:被破壞膠囊之個數比率未達1% B :被破壞膠囊之個數比率爲1%以上，未達5% C:被破壞之膠囊之個數比率爲5 %以上 (3)捲繞形態 -29- 200928332 以目視確認捲繞成捲筒狀的電子給與性無色染料薄片 之有無縐紋發生，根據下述基準進行評價。此外，「B」係 實使用上可容許的範圍。 一評價基準- A :無法確認縐紋。 B :雖有縐紋發生卻爲微小的縐紋。 C :發生大的縐紋。 [實施例2] ❹ 在實施例1中，除了將所得電子給與性無色染料前驅 物內包微膠囊液（A)使用孔徑10# m之過濾器重複多次橫 流（cross flow)過濾處理（所得體積標準之中値徑爲 2 4 // m)，進行塗布使間隔件形成溶液（B)乾燥後質量成爲 5 5. Og/rri以外，其他則與實施例1相同，獲得實施例2之電 子給與性無色染料薄片，進行評價測定。評價結果如表1 所示。 [實施例3] 〇 -含有顯色劑液之調製- 將40%氫氧化鈉水溶液5份，及水300份添加於硫酸 處理活性白土（電子受體性化合物）100份，以均化器分散， 在此進而添加乾酪素之鈉鹽10 %水溶液50份及苯乙烯-丁 二烯乳膠30份，來調製含有電子受體性化合物（顯色劑）之 含有顯色劑液。 一顯色劑薄片之製作- 將所得含有顯色劑液，在厚度75 "m之聚對酞酸乙二 酯（PET)薄片上藉由棒塗布機塗布，使固形成份塗布量成爲 -30- 200928332 10g/iri，形成顯色劑層，獲得顯色劑薄片。 除了使用如此所得之顯色劑薄片以外，其他則與實施 例1相同，進行評價測定。評價結果如表1所示。 [實施例4] 除了在實施例1中，進行塗布使間隔件形成溶液（B)乾 燥後質量成爲46.0g/nf，且以下列方式來調製電子給與性 無色染料前驅物內包微膠囊液（C)以替代實施例1的電子給 與性無色染料前驅物內包微膠嚢液（A)之調製以外，其他則 Ο 與實施例1相同，獲得實施例4之電子給與性無色染料薄 片，進行評價測定。評價結果如表1所示。 _電子給與性無色染料前驅物內包微膠囊够（C)之調製- 將聚乙烯磺酸之一部份鈉鹽（National starch公司製， VERSA、TL500、平均分子量500,000)5份一邊攪拌一邊添 加於約80°C之熱水95份，予以溶解後進行冷卻。於該水溶 液添加20質量％氫氧化鈉水溶液成爲pH4.0。一方面，將 作爲電子給與性無色染料前驅物之上述化合物（A)9份溶解 ❹ 於二芳基乙烷70份之液，予以乳化分散於該聚乙烯苯磺酸 之一部份鈉鹽之5%水溶液100份。另外將三聚氰胺6份與 37質量％甲醛水溶液11份混合，在60°C加熱攪拌於30分 後獲得透明的三聚氰胺與甲醛及三聚氰胺一甲醛初期縮合 物之混合水溶液。此混合水溶液之pH爲6〜8。以下，此 三聚氰胺與甲醛及三聚氰胺-甲醛初期縮合物之混合水溶 液稱爲初期縮合物溶液。將以上述方法所得初期縮合物溶 液添加混合於上述乳化液，一邊攪拌一邊使用3·6質量％鹽 酸溶液調節pH至6.0，將液溫上昇至65°C，持續攪拌360 -31- 200928332 分。將此膠囊液冷卻至室溫，以20質量％氫氧化鈉水溶液 調節至PH9.0，添加水且調整濃度，並調製固形成份濃度 18 %之含電子給與性無色染料前驅物的微膠囊液（C)。含於 電子給與性無色染料前驅物內包微膠囊液（C)之微膠囊的 體積標準95%徑爲35/zm，在微膠囊被破壞時一對平面之 間隔爲33 μιη，體積標準之中値徑爲20 vm。 [比較例1 ] 除了在實施例1中，塗布間隔件形成溶液（B)之乾燥後 ❹ 質量成爲13.0g/m2以外，其他則與實施例1相同，獲得比 較例1之電子給與性無色染料薄片，進行評價測定。評價 結果如表1所示。 [比較例2 ] 除了在實施例1中，塗布間隔件形成溶液（B)乾燥後質 量成爲9 5.0 g / m2以外，其他則與實施例1相同，獲得比較 例2之電子給與性無色染料薄片，進行評價測定。評價結 果如表1所示。 〇 【表πPreparation of Compound (A) - Spacer Forming Solution (B) - Mixing 75 parts of water, 5 parts of sodium polyacrylate, and 100 parts of calcium carbonate in a sand mill, after dispersing, adding 15 parts of SBR latex to a solid content, 15 parts of a 1% aqueous solution of carboxymethylcellulose and 1 part of a 25% aqueous solution of sodium dodecylbenzenesulfonate were mixed and further added with water to have a solid content of 41.5% to prepare a spacer-forming solution (B). - Preparation of electron-donating leuco dye sheets - Transfer of a long strip of polyethylene terephthalate film (base) 400 mm wide, -27- 200928332 On the film, the electron-donating leuco dye precursor is interposed and spaced The solution forms a solution (B), and the electrons of 150 mm width are supplied to the precursor in the width direction of the microcapsule liquid (A), and the respective spacers form a solution (B) contact, and at the same time, the electron-donating substance contains the microcapsules. The mass of the liquid (A) after drying was 5.0 g/nf into a solution (B), and the mass after drying was 33.0 g/nf, and after simultaneous coating, it was dried to obtain an electron-donating sheet. 〇_Modulation with developer solution - 3,5_bis(α-methylbenzyl)salicylic acid zinc 1 (H part, sodium hexametaphosphate 1 part and water 200 parts using sander average particle size) 3/zm to prepare a dispersion. Then, 100 parts of a 10% aqueous solution of vinyl alcohol, and 10 parts of a butadiene latex and 450 parts of water are prepared to prepare a sheet containing a sensitizer-developer sheet. The obtained developer solution was coated on a polythene (PET) sheet having a thickness of 7 5 // m, coated with a bar coater, and dried to have a cloth amount of 10 g/m 2 to form a developer layer to obtain a color developing agent such as the above. In the method of producing a two-piece type of pressure-measuring material of the present invention, the pressure-measuring material of the present invention was evaluated as follows: (1) Color development performance. The electron-donating leuco dye sheet is wound into a roll-package microcapsule liquid (A) and a leuco dye and a 50 mm-wide leuco dye precursor, so that the spacer-shaped sliding bead coating machine-like leuco dye thin & calcium carbonate 100 Disperse into a dispersion and add a portion of the styrene-based solution. Ingredients coated sheets "Dye flakes and materials. The evaluation results are as shown. The roll is then unwrapped -28-200928332 and cut into 5 cm x 5 cm. The electron-donating leuco dye sheet is cut off. The developer toner sheet of 5 cm x 5 cm size is laminated so that the surface of the chromonic layer of the electron-donating leuco dye sheet faces the surface of the developer layer of the developer sheet, and is superposed The two sheets were sandwiched by two sheets of glass sheets having a smooth surface, and were subjected to color development by pressurizing the spindle with a pressure of 0.30 MPa, and then the laminated sheets were peeled off using a densitometer. RD — 19 (manufactured by GretagMacbeth Co., Ltd.), the concentration (DA) of the coloring portion formed on the developer sheet was measured. © In addition, the initial concentration was measured in the same manner as the undeveloped developer sheet. Then, the initial concentration DB is subtracted from the concentration DA, and the color development density AD' is evaluated according to the following evaluation criteria. Further, "b" is an allowable range for practical use. .〇4 ^ Δ D) : Confirmed clear hair Β (0.01 ^ Δ D < 0.04): A weak coloration can be confirmed. C (A D < 0.01): Color development cannot be confirmed 〇 (2) The presence or absence of microcapsule destruction is carried out by winding an electron-donating leuco dye sheet The roll was rolled out, and the roll was unwound, and the microcapsule-coated surface of the sheet was observed with a 150-fold optical microscope, and the capsule damage was evaluated by the following criteria. Further, "B" is an allowable range for practical use. A: The ratio of the number of damaged capsules is less than 1% B: The ratio of the number of damaged capsules is 1% or more, less than 5% C: The ratio of the number of damaged capsules is 5% or more (3) Wrap-around -29-200928332 The presence or absence of crepe of the electron-donating leuco dye sheet wound in a roll shape was visually confirmed, and evaluated according to the following criteria. In addition, "B" is a tolerable range. One evaluation criterion - A: The crepe cannot be confirmed. B: Although there are crepe lines, they are tiny crepe lines. C: A large crepe pattern occurs. [Example 2] ❹ In Example 1, except that the obtained electron-donating leuco dye precursor-incorporated microcapsule liquid (A) was repeatedly subjected to cross flow filtration treatment using a filter having a pore size of 10 # m ( In the obtained volume standard, the diameter of the obtained volume was 2 4 // m), and the coating was carried out so that the separator forming solution (B) was dried and the mass was 5 5. Og/rri. Otherwise, the same as in Example 1, and Example 2 was obtained. The electron-donating leuco dye sheet was evaluated and evaluated. The evaluation results are shown in Table 1. [Example 3] Preparation of 〇-containing developer solution - 5 parts of 40% aqueous sodium hydroxide solution and 300 parts of water were added to 100 parts of sulfuric acid-treated activated clay (electron accepting compound), and dispersed by a homogenizer Further, 50 parts of a 10% aqueous solution of casein sodium salt and 30 parts of a styrene-butadiene latex were further added to prepare a coloring agent-containing liquid containing an electron acceptor compound (developer). Preparation of a developer sheet - The resulting developer-containing solution was applied to a polyethylene terephthalate (PET) sheet having a thickness of 75 "m by a bar coater to form a solid coating amount of -30. - 200928332 10g/iri, forming a developer layer to obtain a developer sheet. The evaluation and measurement were carried out in the same manner as in Example 1 except that the developer sheet thus obtained was used. The evaluation results are shown in Table 1. [Example 4] Except that in Example 1, coating was carried out so that the mass of the spacer-forming solution (B) was dried to 46.0 g/nf, and the electron-donating leuco dye precursor-incorporated microcapsule liquid was prepared in the following manner. (C) An electron-donating leuco dye sheet of Example 4 was obtained in the same manner as in Example 1 except that the electron-donating leuco dye precursor was substituted for the microcapsule (A). , evaluation test was performed. The evaluation results are shown in Table 1. - Electron-donating leuco dye precursor contains microcapsules (C) - A portion of the sodium salt of polyvinyl sulfonic acid (National starch, VERSA, TL500, average molecular weight 500,000) is stirred while stirring 95 parts of hot water added to about 80 ° C was dissolved and then cooled. A 20% by mass aqueous sodium hydroxide solution was added to the aqueous solution to obtain a pH of 4.0. In one aspect, 9 parts of the above compound (A) as an electron-donating leuco dye precursor is dissolved in a solution of 70 parts of diarylethane, and emulsified and dispersed in a part of the sodium salt of the polyvinylbenzenesulfonic acid. 100 parts of 5% aqueous solution. Further, 6 parts of melamine and 11 parts by mass of a 37% by mass aqueous formaldehyde solution were mixed, and the mixture was heated and stirred at 60 ° C for 30 minutes to obtain a mixed aqueous solution of transparent melamine and formaldehyde and melamine-formaldehyde initial condensate. The pH of the mixed aqueous solution is 6 to 8. Hereinafter, a mixed aqueous solution of this melamine and formaldehyde and melamine-formaldehyde initial condensate is referred to as an initial condensate solution. The solution of the initial condensate obtained by the above method was added to the emulsion, and the pH was adjusted to 6.0 using a 3.6 mass% hydrochloric acid solution while stirring, and the temperature of the solution was raised to 65 ° C, and stirring was continued for 360 - 31 - 200928332 minutes. The capsule liquid was cooled to room temperature, adjusted to pH 9.0 with a 20% by mass aqueous sodium hydroxide solution, water was added and the concentration was adjusted, and a microcapsule liquid containing an electron-donating leuco dye precursor having a solid content concentration of 18% was prepared. (C). The volume standard of the microcapsules contained in the electron-donating leuco dye precursor microcapsule liquid (C) is 95% diameter 35/zm, and the interval between the pair of planes is 33 μm when the microcapsule is broken, the volume standard The middle diameter is 20 vm. [Comparative Example 1] The electron-donating colorlessness of Comparative Example 1 was obtained in the same manner as in Example 1 except that the mass of the coating spacer forming solution (B) after drying was 13.0 g/m2. The dye flakes were evaluated for evaluation. The evaluation results are shown in Table 1. [Comparative Example 2] An electron-donating leuco dye of Comparative Example 2 was obtained in the same manner as in Example 1 except that in Example 1, the coating spacer forming solution (B) was dried to have a mass of 9 5.0 g / m 2 . The sheet was evaluated for evaluation. The evaluation results are shown in Table 1. 〇 【Table π
體積標準 95% 徑Mm 平面間隔 him 體積標準 的中値徑 /m m 間隔件厚度 /jum 顯色劑 發色性能 微膠囊有無破壞 捲繞狀態 寅施例 1 35 18 20 25 水楊酸鋅鹽 A A A 寅施例 2 40 20 24 40 水楊酸鋅鹽 A A A 寅施例 3 35 18 20 25 活性白土 B A A 寅施例 4 35 33 20 35 水楊酸鋅鹽 B B A 比較例 1 35 18 20 10 水楊酸鋅鹽 C C A 比較例 2 Γ 35 18 20 70 水楊酸鋅鹽 A B C -32- 200928332 由表1可知，相對於微膠囊之體積標準95 %徑Μ M m)， 使間隔件厚度爲（A x 0.6)/zm以上、（A x 1.0)ym以下，可 藉以防止微膠囊破壞或捲繞時縐紋之發生。 【圖式簡單說明】 te 。 【主要元件符號說明】 Μ 〇 ❹Volume standard 95% Diameter Mm Plane interval him Volume standard median diameter / mm Spacer thickness / jum Color developer chromogenic properties Microcapsules with or without damage winding state 寅 Example 1 35 18 20 25 Salicylic acid zinc salt AAA 寅Example 2 40 20 24 40 Salicylic acid zinc salt AAA 寅 Example 3 35 18 20 25 Activated clay BAA 寅 Example 4 35 33 20 35 Salicylic acid zinc salt BBA Comparative Example 1 35 18 20 10 Salicylic acid zinc salt CCA Comparative Example 2 Γ 35 18 20 70 Zinc salicylate ABC -32- 200928332 It can be seen from Table 1 that the thickness of the spacer is (A x 0.6) / relative to the volume standard of the microcapsule 95% diameter Μ M m) Above zm, (A x 1.0) ym or less, it is possible to prevent the occurrence of crepe when the microcapsules are broken or wound. [Simple description of the diagram] te. [Main component symbol description] Μ 〇 ❹
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