TWI232812B

TWI232812B - Heat-sensitive recording material

Info

Publication number: TWI232812B
Application number: TW91110131A
Authority: TW
Inventors: Shigetoshi Seki; Toshiro Hata
Original assignee: Oji Paper Co
Priority date: 2001-05-16
Filing date: 2002-05-15
Publication date: 2005-05-21

Abstract

Disclosed is a heat-sensitive recording material comprising a support and a heat-sensitive recording layer formed on the support and containing a leuco dye, a developer and a binder, wherein the heat-sensitive recording material uses as the developer at least two hydroxy-diphenylsulfone compounds such as 4-hydroxy-4'-isopropoxy-diphenylsulfone, 2,4'-dihydroxy-diphenylsulfone and the like, and uses as the leuco dye a black-color-forming leuco dye such as 3-di (n-butyl) amino-6-methyl-7-anilinofluoran or the like and 0.5 to 3.5 wt.%, relative to the black-color-forming leuco dye, of a red-color-forming leuco dye such as 3-diethylamino-7-chlorofluoran or the like.

Description

1232812 A7 B7 五、發明説明（1 ) [技術領域] (請先閲讀背面之注意事項再填寫本頁) 本發明係有關於一種利用無色染料與呈色劑間之顯色反應之感熱記錄體。 [習知背景] 於由紙、合成紙或塑膠薄膜等所構成之支持體之單面上’設置有含無色染料、呈色劑及黏著劑之感熱記錄層之感熱記錄體，由於使用該感熱記錄體來作為記錄媒體使用之記錄裝置既小型又價廉，並且保養容易，因此，不僅是作為傳真、自動售票機、科學記測器之記錄用媒體來使用，亦廣泛地使用於POS標記、CAD、CRT醫療圖像用等之各種印刷、繪圖器之輸出媒體中。其中，於需具有記錄圖像之均一性、高解析度之CRT 醫療記測用圖像印刷，以及需具有尺寸安定性、細線記錄之CAD描繪器方面，係以使用利用具複層構造之合成紙之感熱記錄體’或配合需要使用利用含有無機顏料之雙轴延伸之熱可塑性樹脂薄膜之感熱記錄體。隨著這些感熱記錄體之利用領域擴大，對於藉由無色染料與呈色劑間之顯色反應所形成之記錄部（=記錄像）之塑化劑、食用油、化妝品等化學藥品具有優異保存性之感熱記錄體，以及受溫度或濕度之影響之長時間之記錄部濃度變化少之感熱記錄體是必要的。於曰本特許公開公報特開平〇2 — 020385缺八4 现公報、特開平02— 249690號公報、特開平05— 286255號八如現公報、特開平7— 172068號公報、特開2000— 263944觫 ^ 现、特開2001 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） 1232812 A7 B7 五、發明説明（2) 歡 — 001647號公報中，揭示有以往用以提高記錄部之保存性而併用至少兩種之4—羥基一4，一異丙氧二苯颯或4,4，一二經二苯颯等之羥二苯颯系呈色劑來作為呈色劑之感熱記錄體，然而，對於因濕度或溫度之影響，減少長時間記錄部之記錄濃度變化方面，以及提昇記錄部之層次性方面，則必須更進一步改善。又’在感熱g己錄體中’依其用途’記錄部色調必須為無色彩之黑色（薄墨色、灰色）。於日本特許公開公報特開平5 — 254254號公報、特開平8— 324130號公報中，則揭示有一感熱記錄體，其併用黑色顯色性無色染料及紅色顯色性無色染料、以使記錄部之色調為無色彩之黑色。然而，這些感熱記錄體在記錄感度、記錄部之色調或層次性上必須進一步提昇。在此，於本說明書中，上述層次性係意味著所施加之記錄能量與記錄部（記錄像）之記錄濃度實質上成正比關係 (直線關係），更詳而言之，係指形成具有與所施加之記錄能量成比例之記錄濃度之記錄像，且記錄部（記錄像）之記錄濃度與所施加之記錄能量大致成一直線關係，結果，使記錄能量階段性地變化（增大或減少）而形成複數之記錄部 (記錄像）時，所得到之複數記錄部（記錄像）之記錄濃度由最低濃度至最高濃度之全範圍内，具有清晰之層次者。層次性愈優異，則記錄畫質愈佳。 [發明之揭示] 本發明之目的係提供一種感熱記錄體，其係記錄部（記本紙張尺錢财BS緒準（⑽）A4規格（2κ)χ297公楚） (請先閲讀背面之注意事項再填窝本頁) -裝， .、一吓丨 •線· 1232812 五、發明説明（3) 錄像）色調為色彩少之黑色，且記錄部（記錄像）之層次性優異’又，對於因濕度或溫度之影響，長時間記錄變化少者。 & 本發明用以解決上述課題之手段係，於具有支持體上 3無色染料、呈色劑及黏著劑之感熱記錄層之感熱記錄體中，使用至少二種以上之羥二笨颯系化合物來作為呈色劑，並以黑色顯色性無色染料，以及相對於黑色顯色性皇色染料，使用0.5〜3.5重量％之紅色顯色性無色染料來作為無色染料者。特別地，本發明係提供下述感熱記錄體者。第1項—種感熱記錄體，係具有⑷支持體及⑻於該 :持體上形成並含有無色染料、呈色劑及黏著劑之感熱記 ^層者’ X，該感熱記錄層係以含有二種以上之經二苯颯么系化合物者作為該呈色劑，以含有黑色顯色性無色染料及色顯色性無色染料者作為該無色染料又，該紅色顯色，色染料係以相對於黑色顯色性無色染料為〇 5〜3 5重量％之量存在者。第2項如上述第1項之感熱記錄體，其中該羥二苯系化合物係，& 2,4，—二經二苯礙及4,4，一二經二苯颯所：成之群中選出之至少一種，及4_經基一4，_異丙氧一笨题。 b第3項如上述第2項之感熱記錄體，其中相對於】本礙所構成之群中選出之至少一種係二經二 ^重篁部之4一羥基一 4，一異丙氧二苯颯，由2,4，一二羥一本题及4,4, 本紙張尺度相切國家標準（⑽Μ規格（雇297公爱） 1232812 A7 , _- - —___B7________ 五、發明説明（4) 使用0.5〜2·〇重量部。第4項如上述第1項之感熱記錄體，其中前述黑色顯色性無色染料係由3—二（η— 丁基）胺基一 6 一甲基一 7 — 苯胺基螢烷、3—二（η 一戊基）胺基_6—甲基一 7 —笨胺基螢烷及3 一二（η—丁基）胺基一 7 ——氯苯胺基）螢烷所構成之群中選出之至少一種。第5項如上述第4項之感熱記錄體，其中前述黑色顯色性無色染料係由3—二（η— 丁基）胺基一 6—甲基一 7 一苯胺基螢烷與3—二（η 一戊基）胺基一 6—甲基一 7 —苯胺基螢烧所構成之群中選出之至少一種，及3—二（η — 丁基）胺基一7 —（〇—氣苯胺基）螢烷之混合物。第6項如上述第5項之感熱記錄體，其中，相對於由3—二（η 一丁基）胺基一6—甲基一 7—苯胺基螢烷及3一一 (η 戊基）胺基一 6 —甲基一 7—苯胺基螢统所構成之群中選出之至少一種，3 一二（η 一丁基）胺基一 7 一（〇一氣苯胺基）螢燒係以30〜300重量％之比例來使用。第7項如上述第1項之感熱記錄體，其中前述紅色顯色性無色染料係3 —二乙胺基一 7 —氣螢烷。第8項如上述第1項之感熱記錄體，其中相對於前述黑色顯色性無色染料，前述紅色顯色性無色染料係含有〇·8〜3.0重量％。第9項如上述第1項之感熱記錄體，其中前述感熱 δ己錄層係相對於黑色顯色性無色染料，更含有〇·5〜5重量 %之藍色顯色性無色染料。本紙張尺度適用中國國家標準（CNS) Α4規格（21〇><297公釐） ----------------------裝-.................訂.................·線· (請先閲讀背面之注意事項再填寫本頁) 1232812 A7 ---- -- B7 五、發明説明（5 ) 第10項如上述第1項之感熱記錄體，其中前述感熱記錄層中之黏著劑係含有水分散性樹脂者。第11項如上述第1項之感熱記錄體，其中前述感熱記錄層更含有增感劑或保存性改良劑或其混合物。第12項如上述第1項之感熱記錄體，其更於前述感熱記錄層上具有保護層。 [發明之詳細說明] 如前所述，本發明係一種於感熱記錄層中，以含有至乂一種以上之羥二笨礙系化合物者來作為呈色劑，並至少含有黑色顯色性無色染料，以及相對於黑色顯色性無色染料，0·5〜3·5重量％之紅色顯色性無色染料者。呈色倒於本發明中，藉由併用至少二種以上之羥二苯颯系化合物來作為呈色劑’可得到具有優異之記錄部層次性及記錄部長時間保存性之效果。 <羥二苯颯系化合物> 經二苯風系化合物之具體例，可列舉如：4—羥基一 4, —甲氧二笨颯、4一羥基一 4, 一異丙氧二苯颯、4一羥基一4, 一 η—丙氧二苯颯、4一羥基一 4，一苄氧二苯颯、2,4,一二羥二苯颯、4,4，一二羥二苯颯、3,3,一二烯丙基一4,4，一二羥二苯颯、3,4—二羥基一4,一甲基二苯颯、2,2，一〔4—(4 一羥苯磺醯基）苯氧基〕二乙醚等。其中，以併用由2,4，一二羥二苯颯及4,4,一二羥二苯颯所構成之群中選出之至少一種，及4一羥基—4,一異丙本紙張尺度適用中關家標Gcns) Μ規格⑵似撕公幻 (請先閲讀背面之注意事項再填寫本頁) 訂---- .線， 1232812 A7 ____B7 五、發明説明（6 ) 氧—本礙者為佳。特別地，相對於1重量部之4 一羥基—4，一異丙氧二笨颯，藉由使用0.2〜5.0重量部，尤其是〇·5〜2.0重量部之由2,4 — 一經二苯礙及4,4’一二經二苯碰所構成之群中選出之至少一種，則即使於記錄部光學濃度為〇·4〜〇 8之低濃度記錄部中，亦可得到色彩少之黑色。 2,4 —二Μ二苯礙及4,4’一二經二苯風中，2,4,一二經二苯礙係具有優異之抗底面霧化性，因此更為理想。相對於感熱記錄層之全固體成分，羥二苯颯系化合物之合計使用量為15〜60重量％，且以20〜50重量％為佳。. <其他呈色劑> 感熱記錄層中，呈色劑係含有上述羥二苯颯系化合物者，然而，依需要於無損於本發明所期望之效果下，亦可併用各種公知之其他呈色劑。其他呈色劑之具體例，可列舉如：1，3,3 —三甲基一 1 —(Ρ—經苯基）一 6—經氫茚、4,4’一亞異丙基二紛、4,4，一亞環己基二酚、2，2_雙（4一羥苯基）一 4一甲基戊烷、4一羥基苯甲酸苄酯、1，1一雙（4一羥苯基）一1 一苯乙烷等之酚性化合物，Ν—（ρ—甲苯續酿基）胺基曱醯酸一 ρ一異丙笨基苯酯、Ν—（〇—甲苯基）一 ρ—甲苯確酸醯胺基、4，4,一雙（Ν 一 ρ—甲苯續酿胺基碳醯胺基）二苯甲燒等之分子内具有一 S02NH—結合者，4一〔2—（ρ—甲氧苯氧基）乙基氧基〕水楊酸鋅、4一〔3—（p—甲苯磺醯基）丙基氧基〕水楊酸鋅、 5—〔ρ—（2 — ρ—甲氧苯氧乙氧基）異丙苯基〕水楊酸鋅等本紙張尺度適用中國國家標準A4規格（210X297公釐） .................¥..................、可…...............緣 (請先閲讀背面之注意事項再填寫本頁) 五發明說明戈秩歿酸之鋅鹽等。 k些其他呈色劑之使用量只要而，一私品+ t 田L遷擇即可，然又σ，相對於上述羥二苯礙系化人铷+ 1 量，係以3〜15,、姑*風系化。物之合計使用編料 I〆’特別是以5〜W重量％為佳。發明之感熱記錄體之感熱記錄層係至少含色性無色染料及特定量之紅色顯色性無色染料者二發明中’加上使用前述二種以上之經二苯礙系化合物，藉由如此組合使用黑色顯色性無色染料及特定量之紅色顯色性無色染料’可使記錄部之色調、記錄部之層次性、抗底面霧化性優異，且耐熱性、耐濕性亦佳。〈黑色顯色性無色染料> 感熱έ己錄層中之黑色顯色性無色染料之具體例係可廣泛使用該領域中所使用之公知之黑色顯色性無色染料，舉例言之，可列舉如：3 — (Ν—乙基一Ν—異戊基）胺基一6 — 甲基一 7 —苯胺基螢烷、3 —（Ν —甲基一 Ν —環己基）胺基一 6 —甲基一7 —苯胺基螢烷、3—二乙胺基一 6 —甲基一 7—苯胺基營烧、3 — -一 (π 一丁基）胺基一 6 —甲基一 7 —苯胺基榮烷、3 —二（η—戊基）胺基一 6—甲基一 7 —苯胺基螢烷、3 — 二（η—丁基）胺基一 7—（〇—氯苯胺基）螢烧、3—二（η—丁基）胺基一 7 —（〇—氟苯基胺基）螢烷、3—（Ν—乙基一 ρ—甲苯胺基）—6 一甲基一7 —苯胺基螢烷、3—（Ν—乙基一 Ν—四氫咬喃甲基胺基）一 6—甲基一 7 —苯胺基螢烧、3 —二乙胺基一 6—氯一 7 —苯胺基螢烷、3一咄咯烷基一 6 一甲基一 7 -10- 本紙張尺度適用中國國家標準Α4規格（210x297公爱） 1232812 A7 B7 五、發明説明（一苯胺基螢烷、3 —哌啶基一6 一甲基—7 一苯胺基螢烷等。 ------------------------裝—— (請先閲讀背面之注意事項再填窝本頁) 其中，以由3—二（n— 丁基）胺基—6 一甲基_7 一苯胺基螢烷、3 —二（η—戊基）胺基一 6 一曱基一7 一苯胺基螢烷及3—二（η—丁基）胺基一 7一（〇一氣苯胺基）螢烷所構成之群中選出之至少一種具有優異之記錄部層次性，且抗底面霧化性佳，因此較為理想。特別是以併用由3一二（η 一丁基）胺基—6一甲基一7一苯胺基螢烷與3—二（η 一戊基）胺基一 6一甲基—7—苯胺基螢烧所構成之群中選出之至少一種，及3—二（η— 丁基）胺基一 7—（〇—氣苯胺基）螢烷者為佳。、τ· 此種情況下、，相對於由3—二（11— 丁基）胺基一 6一甲基一苯胺基螢烷及3一二（11 一戊基）胺基一 6 一甲基—7一苯胺基螢&所構成之群中選出之至少一種，係以使用3〇〜重量％之3 —（η—丁基）胺基一7—（〇—氣苯胺基）螢烷者為佳，且以使用5〇〜15〇重量％者尤佳。 :線- <紅色顯色性無色染料> 感熱。己錄層中之紅色顯色性無色染料之具體例係可自廣範圍適當地選擇該領域中所使用之公知之紅色顯色性無色染料，舉例言之，可列舉如：3,3，—雙（ρ—二甲基胺基苯基m、3-(Ν-乙基—Ν—異戊胺基―卜笨氧基營烧、 3—環己胺基—6一氣螢烷、3 一二乙胺基〜6一曱基氣螢烷、3 一二乙胺基一7,8—苯并螢烷、3一二乙胺基一 7一氣螢烷、若丹明（〇—氣苯胺基）内酿胺、3一二乙胺基一S' 一二甲基螢烧、3,3，-雙（卜卜丁基—2—甲基㈣—乂本紙張尺度適用中國國表標準（q^S) Α4規格（210X297公爱） -11· 1232812 五、發明説明（9) 乙胺基一 7—氣螢燒為佳基）酞等。其中係以當然’並非限定於這歧一…、巴木枓，亦可分別併用二種 (請先閲讀背面之注意事項再填寫本頁) 之黑色顯色性無色染料及紅色顯色性無色染料。發月中相對於上述黑色顯色性無色染料，紅色顯色性無色染料係含有0.5〜3 5 汰董置X 右、，工色顯色性無色木厂小於〇·5 ^量％ ’則特別是記錄部光學濃度為0·2〜0.6 之，濃度記錄部之色調變為略帶綠色之黑色調，若大於3.5 重’則有變為略帶紅色之黑色調之虞，因*匕，紅色顯色：無色染料係以相對於黑色顯色性無色染料為0·8〜3.0 重量/。，特別是以1·〇〜2.0重量％者尤佳。 <其他無色染料> 再者，感熱記錄層中，於無損於本發明所期望之效果下可含有其他無色染料。這些其他無色染料之具體例，可列舉如：3,3—雙（ρ—二甲基胺基苯基）一6一二甲基胺基酞、3—（4 —二乙胺基一 2 —甲基苯基）—3一（4 —二甲基胺基苯基）一6 —二甲基胺基酞、3 一二乙胺基一 7 一二辛胺基一苯并〔a〕螢烷等之藍色顯色性無色染料，3—(Ν一乙基 — Ν—ρ—曱苯基）胺基—7— Ν—曱基苯胺基螢烷、3—二乙胺基一7 —苯胺基螢烷、3—二乙胺基一 7—二苄胺基螢烷等之綠色顯色性無色染料，及3,3—雙〔1 一（4一甲氧苯基）一 1一（4 —二甲基胺基苯基）乙烯一 2 —基〕一 4,5,6,7—四氣酞、3 — ρ—（ρ —二曱基胺基苯胺基）苯胺基一 6—甲基一 7 — 氣螢烧、3 — ρ —（ρ—氣苯胺基）苯胺基一 6—甲基一 7—氣螢烷、3,6—雙（二甲基胺基）荞一 9一螺一 3’一（6, 一二甲基胺本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公爱） -12- 1232812 五、發明説明（i〇 ) 基）酞等之近紅外區具有吸收波長之無色染料等。相對於黑色顯色性無色染料，這些其他之無色染料係以併用〇·3〜15重量％，特別是以〇·5〜10重量％者為佳。特別地，於本發明中，上述藍色顯色性無色染料係相對於黑色顯色性無色染料，以併用〇·5〜5重量％，特別是j 〇〜3.0重量％者為佳。於本發明中，上述黑色顯色性無色染料及紅色顯色性 …、色柒料之σ s十使用篁係相對於感熱記錄層之全固體成分，以5〜35重量％，特別是1〇〜25重量％者為佳。感熱記錄辱感熱記錄層係於支持體上塗布感熱記錄層用塗液並使其乾燥而形成者，該感熱記錄層用塗液係，一般將水作為刀散"質，並藉由球磨機、超微粉碎機、砂磨機等授拌Y 粉碎機-同或分別將黑色顯色性無色染料、紅色顯色性無色染料、含有2種以上之羥二苯颯系化合物之呈色劑，以及依需要添加之增感劑、保存性改良劑等微分散為平均粒子徑為2μιη以下後，添加黏著劑來調製者。沒些黏著劑可列舉如··澱粉與聚醋酸乙烯酯之接枝共聚物、聚乙婦醇、叛基變性聚乙婦醇、乙醯乙酿基變性聚乙烯醇、矽變性聚乙烯醇、氧化澱粉、酪蛋白、苯乙烯一順丁烯二酸酐共聚物、甲基乙烯基醚一順丁烯二酸酐共聚物、異丙烯一順丁烯二酸酐共聚物等之水溶性樹脂，及苯乙烯〜丁二烯系乳膠、丙烯酸系乳膠 '胺基甲酸酯系乳膠等之水分散性樹脂。其中係以水分散性樹脂為佳。黏著劑本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公釐） 1232812 A7 ______ —___B7 五、發明説明（11 ) 之使用里並無特殊之限制，然而，對於感熱記錄層係以5 〜40重量％，特別是以20〜35重量％為佳。 (請先閲讀背面之注意事項再填寫本頁) 又’亦可使感熱記錄層中含有用以控制記錄感度之增感劑，及用以提高記錄部保存性之保存性改良劑。增感劑之具體例可列舉如：硬脂酸醯胺、甲撐雙硬脂酸醯胺、對苯二甲酸二苄酯、p一辛氧基苯甲酸苄酯、2一萘苄基醚、m—聯三苯、p 一苄基聯苯、p 一甲苯基聯苯醚、二（4 一甲氧笨氧乙基）醚、丨，2 一二（3 一甲基苯氧基）乙烷、 I，2 一二（4 一甲基苯氧基）乙烷、1，2—二（4—甲氧苯氧基）乙烧、1，2—二（4 一氣苯氧基）乙烷、ι，2 一二苯氧基乙烷、L —(4一曱氧苯氧基）一 2一（3 一甲基苯氧基）乙烷、p —甲硫苯基罕_、二（β—聯苯乙氧基）苯、草酸二一 p一氣苄酯、草酸二苄酯等。 :線_ 保存性改良劑可列舉如：2，2，一甲樓雙（4 一甲基一 6 — tert—丁基苯酚）、4,4,一硫基雙（2—曱基一6— tert— 丁基笨酚）、4一4’一亞丁基雙（6 — tert— 丁基一 m—甲苯酚）、1，3,5 一三（4 一 tert—丁基一3—羥基一2,6—二甲苄基）異三聚氰酸、1，1，3 —三（2 —曱基一 4一羥基一5 — tert—丁基苯基）丁烷、1，1，3 —三（2 —甲基一 4一羥基一 5—環己笨基）丁烷、 2，2 —雙（4 一經基一 3，5—二漠苯基）丙院、2，2’一雙（4 一經基一 3,5—二甲基苯基）丙烷等之化合酚化合物，4,4,一二縮水甘油氧二苯颯、4 一苄氧基一 4，一（2—甲基縮水甘油氧基）一本風、對苯二甲酸二縮水甘油S旨、甲苯盼紛搭固形物型環氧樹脂、苯酚酚醛固形物型環氧樹脂、二酚A型環氧樹本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） -14- !232812 A7 ^ —— _B7 _ 五、發明説明(iTy * ^〜〜-— 脂等之環氧化合物等。 (請先閲讀背面之注意事項再填寫本頁) 增感劑及保存性改良劑之使用量並無特殊之限制，然 =，相對於一般感熱記錄層中1重量部之全無色染料，係分別為〇.1〜4重量部，且以〇·5〜3重量部為佳。 ’、再者’感熱記錄層中，可依需要添加各種助劑，例如· 阿嶺土、輕質碳酸鈣、重質碳酸鈣、燒成高嶺土、氧化鈦、石反酸鎂、氫氧化鋁、無定形二氧化矽、胺甲醯胺·甲醛水樹脂填充物等之顏料類，二辛磺基琥珀酸鈉、十二基笨磺酸納、月桂醇硫酸酯鈉、脂肪酸金屬鹽等之界面活性劑，硬脂酸鋅、硬脂酸鈣、聚乙烯蠟、巴西棕櫚蠟、石蠟、醋蠟等之蠟類，乙二醛、胺甲醯胺甲醛水樹脂、聚醯胺基環氧樹脂、聚醯胺基表氣烷、己二酸二醯肼、硼酸、硼砂、石反酸錢錯等之防水化劑及紫外線吸收劑、消泡劑、勞光染料、著色染料等。感熱記錄層用塗液之塗布量係以乾燥重量為2〜 12g/m2，較佳者為3〜7g/m2。感熱記錄層用塗液係藉由通常該領域中所使用之公知之塗布方法’例如：氣刀塗布、純刮刀塗布、桿塗布、棒塗布、簾塗布、鞍形塗布、照相凹版式塗布等，塗布於支持體上並使其乾燥。支持體上述支持體可使用該領域中所使用之公知之支持體之任一者，特別可舉例如：中性或酸性之道林紙、塗料紙、合成紙、透明塑膠薄膜、著色透明塑膠薄膜、白色塑膠薄本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） 1232812 五、發明説明（i3 ) 膜等支持體之厚度可由廣範圍來適當地選擇，然而… 般而言，係以40〜250μπι為佳。 ”、保護層依需要可於感熱記錄層上設置用以提高記錄部耐藥品性、防水性或提局記錄部走行性之保護層。這些保護層係使感熱記錄層上塗布如含有具成膜性之黏著劑之保護層用塗液並乾燥而形成者。保漢層用塗液中所含有之黏著劑係使用如上述感熱記錄層用塗液中所含有者。這些黏著劑係相對於保護層之全固體成分，以使用20〜100重量％，特別是3〇〜95重量％之量者為佳。再者’可依需要於保護層用塗液中使關熱記錄層用塗液中可含有之前述各種助劑。保護層用塗液之塗布量係以乾燥重量為0.5〜 10g/m2，較佳者為i〜5g/m2。保濩層用塗液係藉由通常該領域中所使用之公知之塗布方法，例如·氣刀塗布、純刮刀塗布、桿塗布、棒塗布、簾塗布、較形塗布、照相凹版式塗布等，塗布於感熱記錄層上並使其乾燥。、再者，為了提高記錄感度與記錄畫質，亦可於支持體與感熱。己錄層間設置以吸油性顏料或空心粒子作為主成分之塗底層，或於保護層上塗布以電子射線或紫外線固化性化口物作為主成分之塗液後，設置照射電子射線或紫外線使其固化之光澤層，並於形成各種層後，施行藉由強度砑本紙張尺度適财關Μ規格⑵GX297公釐〉 12328121232812 A7 B7 V. Description of the Invention (1) [Technical Field] (Please read the precautions on the back before filling out this page) The present invention relates to a thermal recording body that utilizes the color reaction between a leuco dye and a color former. [Knowledge background] A thermal recording body including a thermal recording layer containing a colorless dye, a color former, and an adhesive is provided on one side of a support made of paper, synthetic paper, plastic film, or the like. The recording device used as a recording medium is compact, inexpensive, and easy to maintain. Therefore, it is not only used as a recording medium for facsimiles, automatic ticket vending machines, scientific measuring devices, but also widely used for POS marks, CAD, CRT medical image and other printing, plotter output media. Among them, for the printing of CRT medical recording images that need to have uniformity of recorded images and high resolution, and the CAD drawing device that needs to have dimensional stability and thin-line recording, it is to use composites with multi-layered structures. The thermal recording body of paper or a thermosensitive recording body using a biaxially stretched thermoplastic resin film containing an inorganic pigment is required. With the expansion of the fields of use of these thermal recording bodies, they have excellent preservation of chemicals such as plasticizers, edible oils, and cosmetics in the recording section (= recorded image) formed by the color reaction between the leuco dye and the color former. It is necessary to have a thermal recording body having a high temperature and a thermal recording body having a small concentration change in the recording portion over a long period of time affected by temperature or humidity. In the Japanese Patent Laid-Open Publication No. 02-020385-8, the current bulletin, JP-A 02-249690, JP-A 05-286255, Yaru-now, JP 7-172068, JP-2000-263944觫 ^ Now, JP 2001 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1232812 A7 B7 V. Description of the invention (2) Huan — 001647 published in the past, reveals Thermal recording of at least two kinds of 4-hydroxy-1,4-isopropyloxydiphenylhydrazone or 4,4,2-diphenylhydrazone-based colorants as preservation agents However, it is necessary to further improve the aspect of reducing the change in the recording density of the long-term recording section due to the influence of humidity or temperature, and improving the layering of the recording section. Also, in the "thermosensitive recording", the recording section must have a colorless black (thin ink color, gray color) according to its use. In Japanese Patent Laid-Open Publication Nos. Hei 5-254254 and Hei 8-324130, a thermal recording body is disclosed, which uses a black color-developing leuco dye and a red color-developing leuco dye in combination to make the recording portion The hue is colorless black. However, these thermal recording bodies must be further improved in recording sensitivity, color tone or gradation of the recording portion. Herein, in the present specification, the above-mentioned gradation means that the applied recording energy is substantially proportional to the recording density of the recording portion (recording image) (linear relationship), and more specifically, refers to the formation of The recording image of the recording density is proportional to the applied recording energy, and the recording density of the recording section (recording image) is approximately linear with the applied recording energy. As a result, the recording energy is gradually changed (increased or decreased). When a plurality of recording sections (recording images) are formed, the recording density of the obtained plurality of recording sections (recording images) ranges from the lowest concentration to the highest concentration, and has a clear level. The better the gradation, the better the recording quality. [Disclosure of the invention] The object of the present invention is to provide a thermal recording body, which is a recording unit (recording paper rule, money, BS, and standard (⑽) A4 specification (2κ) × 297). (Please read the notes on the back first (Fill in this page again)-Pack, ..., a freak 丨 • line · 1232812 V. Description of the invention (3) Video) The color tone is black with few colors, and the recording part (recording image) has excellent layering. The effect of humidity or temperature is recorded for a long time with less change. & The means for solving the above-mentioned problems of the present invention is to use at least two or more hydroxydibenzyl compounds in a thermal recording body having a thermal recording layer with 3 colorless dyes, color formers and adhesives on a support. As a coloring agent, a black color-developing leuco dye, and 0.5 to 3.5% by weight of a red color-developing leuco dye relative to the black color-developing emerald dye are used as the colorless dye. In particular, the present invention provides a thermal recording body described below. Item 1-A thermosensitive recording body having a thermophilic support and a thermophilic recording layer 'X formed on the support and containing a colorless dye, a color former, and an adhesive, and the thermosensitive recording layer contains Two or more diphenylhydrazone compounds are used as the coloring agent, and those containing a black color-developing leuco dye and a color-developing leuco dye are used as the leuco dye. The red color is developed, and the color dye is The color-developing leuco dye in black is present in an amount of 0.05 to 35 wt%. Item 2 is a thermosensitive recording body as described in Item 1 above, wherein the hydroxydibenzene-based compound is & At least one selected from the list, and 4_ Jingji-4, _ isopropoxyl-a puzzle. b. The thermal recording body according to item 3 as described in item 2 above, in which at least one selected from the group consisting of this problem is 4-hydroxyl-4,1-isopropyloxydibenzene of the two-by-two-threatening part.飒, by 2,4, one dihydroxyl question and 4,4, the national standard of paper tangent (⑽M specifications (hiring 297 public love) 1232812 A7, _--— _B7________ V. Description of the invention (4) Use 0.5 ~ 2 · 〇 by weight. The fourth item is the thermal recording body as described in the first item above, wherein the black color-developing leuco dye is composed of 3-bis (η-butyl) amino-6-methyl-7-aniline Fluoranil, 3-di (η-pentyl) amino-6-methyl-7-benzylaminofluorane and 3-di (η-butyl) amino-7-chloroaniline) fluoran At least one selected from the group formed. Item 5 is the thermosensitive recording body according to item 4 above, wherein the black color-developing leuco dye is composed of 3-bis (η-butyl) amino-6-methyl-7-aniline fluoranil and 3-di At least one selected from the group consisting of (η-pentyl) amino-6-methyl-7-aniline fluorescein, and 3-di (η-butyl) amino-7- (0-gas aniline Base) mixture of fluorane. Item 6 is the thermal recording body according to item 5 above, wherein the thermal recording body is composed of 3-bis (η-butyl) amino-6-methyl-7-aniline fluoranil and 3-di (η pentyl). At least one selected from the group consisting of amino-6-methyl-7-aniline fluorescein, 3 di (η-butyl) amino-7-7 (0-aniline aniline) fluorescing is based on 30 ~ 300% by weight. Item 7 is the thermosensitive recording material according to item 1 above, wherein the aforementioned red color-developing leuco dye is 3-diethylamino-7-aerofluorane. Item 8 is the thermal recording body according to item 1 above, wherein the red color-developing leuco dye contains 0.8 to 3.0% by weight relative to the black color-developing leuco dye. Item 9 is the thermosensitive recording material according to item 1 above, wherein the thermosensitive δ-recorded layer contains 0.5 to 5 wt% of a blue color-developing leuco dye relative to a black color-developing leuco dye. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 > < 297 mm) ---------------------- pack -... .............. Order ...... line · (Please read the precautions on the back before filling this page) 1232812 A7 -----B7 V. Description of the invention (5) Item 10 The thermosensitive recording body as described in item 1 above, wherein the adhesive in the thermosensitive recording layer contains a water-dispersible resin. Item 11 is the thermosensitive recording material according to the above Item 1, wherein the thermosensitive recording layer further contains a sensitizer or a preservative improver or a mixture thereof. Item 12 is a thermal recording body according to the above item 1, further comprising a protective layer on the thermal recording layer. [Detailed description of the invention] As described above, the present invention relates to a thermosensitive recording layer that contains at least one kind of hydroxydibenzyl compound as a coloring agent, and contains at least a black color-developing leuco dye. And 0.5 to 3.5% by weight of the red color-developing leuco dye relative to the black color-developing leuco dye. Color development In the present invention, by using at least two or more hydroxydiphenylfluorene-based compounds as a coloring agent ', it is possible to obtain an effect of excellent recording layer gradation and long-term storage stability of the recording portion. < Hydroxydiphenylhydrazone-based compounds > Specific examples of diphenylwind-based compounds include 4-hydroxy-1, 4-methoxydibenzidine, 4-hydroxy-1, 4-isopropyloxydiphenylhydrazone , 4-hydroxy-1, 4-eta-propoxydiphenylhydrazone, 4-hydroxy-1, 4-benzyloxydiphenylhydrazone, 2, 4, dihydroxydiphenylhydrazone, 4, 4, dihydroxydiphenylhydrazone , 3,3, diallyl-4,4,1-dihydroxydiphenylhydrazone, 3,4-dihydroxy-4,1-methyldiphenylhydrazone, 2,2,1- [4-—4-hydroxyl Benzenesulfonyl) phenoxy] diethyl ether and the like. Among them, a combination of at least one selected from the group consisting of 2,4,1-dihydroxydiphenylhydrazone and 4,4,1-dihydroxydiphenylhydrazone, and 4-hydroxy-4,1-isopropyl paper are applicable. Zhongguanjiabiao Gcns) Μ specifications seem to tear off the magic (please read the precautions on the back before filling this page) Order ---- .line, 1232812 A7 ____B7 V. Description of the invention (6) Oxygen-the one with the obstacle is better. In particular, with respect to 1 part by weight of 4 monohydroxy-4, 1-isopropyloxydibenzamine, by using 0.2 to 5.0 parts by weight, especially 0.5 to 2.0 parts by weight, 2,4- If at least one selected from the group consisting of 4,4′-two diphenyl bumps is affected, even in a low-concentration recording portion having an optical density of 0.4 to 0.8 in the recording portion, a black with few colors can be obtained. . In the 2,4-dimethyldiphenyl barrier and 4,4′-diphenyl barrier, the 2,4,1-diphenyl barrier is more ideal because it has excellent anti-bottom fogging properties. The total used amount of the hydroxydiphenylfluorene-based compound relative to the total solid content of the thermosensitive recording layer is 15 to 60% by weight, and preferably 20 to 50% by weight. < Other coloring agents > In the thermosensitive recording layer, the coloring agent contains the above-mentioned hydroxydiphenylfluorene-based compound. However, various known other materials may be used in combination without impairing the desired effect of the present invention. Coloring agent. Specific examples of other color formers include, for example, 1,3,3-trimethyl-1- (P- via phenyl) -6-hydroindene, 4,4'-isopropylidene, 4,4,1-cyclohexylene diphenol, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4-hydroxybenzoic acid benzyl ester, 1,1-bis (4-hydroxyphenyl) )-1-Phenyl compounds such as phenyl ethane, N- (ρ-toluene) aminoamino acid-ρ-isopropylbenzyl phenyl ester, N- (〇-tolyl) -ρ-toluene Sulfuric acid amine group, 4,4, a bis (N-ρ-toluene continuation amine carbamide group) dibenzyl, etc. have a S02NH-binding in the molecule, 4 one [2— (ρ— Methoxyphenoxy) ethyloxy] zinc salicylate, 4- [3- (p-tosylsulfonyl) propyloxy] zinc salicylate, 5- [ρ— (2 — ρ—methyl Oxyphenoxyethoxy) cumyl] zinc salicylate, etc. This paper size is applicable to the Chinese national standard A4 specification (210X297 mm) .... ¥. ......., can ............... Fate (Please read the notes on the back before filling this page) 5 Description of the invention Zinc acid of zinc. The use amount of some other coloring agents is as long as one private product + t field L can be selected, but it is also σ, relative to the above-mentioned hydroxydiphenyl hindering human 铷 + 1 amount, it is 3 ~ 15, Aunt * wind system. The total use of the materials I〆 'is particularly preferably 5 to W% by weight. In the invention, the thermal recording layer of the thermal recording body contains at least a chromatic leuco dye and a specific amount of a red chromogenic leuco dye. In the invention, two or more of the aforementioned diphenyl hindering compounds are used, and the combination is thus combined. The use of a black color-developing leuco dye and a specific amount of red color-developing leuco dye 'can make the recording section excellent in color tone, recording layer gradation, and anti-fogging underside, and also has good heat resistance and humidity resistance. <Black color-developing leuco dyes> Specific examples of the black color-developing leuco dyes in the thermosensitive recording layer are widely known black color-developing leuco dyes used in this field. For example, they can be listed. For example: 3- (N-ethyl-N-isopentyl) amino-6-methyl-7-aniline fluoranil, 3- (N-methyl-N-cyclohexyl) amino-6-methyl 7-aniline fluoranil, 3-diethylamino-6-methyl-7-aniline camphor, 3-((monobutyl) amino-6-methyl-7-aniline Rowan, 3-bis (η-pentyl) amino-6-methyl-7-aniline fluoranil, 3-bis (η-butyl) amino-7- (0-chloroaniline) fluorination , 3-bis (η-butyl) amino-7- (〇-fluorophenylamino) fluorane, 3- (N-ethyl-ρ-tolylamino) -6-methyl-7-aniline Fluoranil, 3- (N-ethyl-N-tetrahydromethylamino) -6-methyl-7-aniline fluorescein, 3-diethylamino-6-chloro-7-aniline Trifluorene, 3-pyrrolidinyl-6 Methyl- 7 -10- This paper size applies to Chinese national standard A4 specifications (210x297 public love) 1232812 A7 B7 V. Description of the invention (monophenylaminofluorane, 3-piperidinyl-6-methyl-7 monoaniline Fluorane, etc. ------------------------ Packing-(Please read the precautions on the back before filling in this page) Among them, by 3 —Bis (n-butyl) amino-6-methyl-7-aniline fluoranil, 3-di (η-pentyl) amino-6-fluorenyl-7-aniline fluoranil and 3-di At least one selected from the group consisting of (η-butyl) amino-7- (anisinoanilide) fluorane has excellent recording layer gradation and is excellent in anti-fogging of the bottom surface, and is therefore preferable. The combination of 3-di (η-butyl) amino-6-methyl-7-aniline fluoranil and 3-di (η-pentyl) amino-6-methyl-7-aniline fluorin At least one selected from the group consisting of sintering and 3-di (η-butyl) amino-7- (0-anilino) fluorane is preferred. Τ · In this case, relative to 3-di (11-butyl) amino At least one selected from the group consisting of 6-methyl-anilinofluoran and 3-di (11-pentyl) amino-6-methyl-7-anilinofluorene & 3-wt%-(η-butyl) amino-7- (0-anilino) fluorane is preferred by weight%, and especially 50-50% by weight is used.: Line-< Red color Chromogenic leuco dyes > Sensitive. Specific examples of the red chromogenic leuco dye in the recorded layer can be appropriately selected from a wide range of well-known red chromogenic leuco dyes used in the field. Examples are: 3,3, -bis (ρ-dimethylaminophenylphenyl m, 3- (N-ethyl-N-isopentylamino-butoxybenzyl), 3-cyclohexylamino- 6-gas fluorane, 3-diethylamino ~ 6-fluorenyl aerofluorane, 3-diethylamine-7,8-benzofluorane, 3-diethylamine-7-fluoranil, rhodan Ming (〇- aniline) internal amine, 3-diethylamine-S '-dimethyl fluorescent, 3, 3,-bis (bububutyl-2-methyl hydrazone-乂) paper size applicable to China National watch standard (q ^ S) Α4 specification (210X297 male Love) -11 · 1232812 V. Description of the invention (9) Ethylamino-7-gas fluorination is the best base) Phthalide and so on. Among them, of course, 'is not limited to this difference ..., Bamuya, you can also use two kinds (please read the precautions on the back before filling out this page) black chromogenic leuco dye and red chromogenic leuco dye . Compared with the black color-developing leuco dye in the hair month, the red color-developing leuco dye contains 0.5 ~ 3 5 Tie X, right, and the working color-developing colorless wood factory is less than 0.5%. The optical density of the recording part is 0 · 2 ~ 0.6. The hue of the density recording part becomes a slightly greenish black tone. If it is greater than 3.5, it may become a reddish black tone. Color development: The leuco dye is from 0.8 to 3.0 wt./ with respect to the black color-developing leuco dye. In particular, it is particularly preferred that it is 1.0 to 2.0% by weight. < Other leuco dyes > The thermosensitive recording layer may contain other leuco dyes without impairing the desired effect of the present invention. Specific examples of these other colorless dyes include 3,3-bis (ρ-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2— Methylphenyl) -3 (4-dimethylaminophenyl) -6-dimethylaminophthalide, 3-diethylamino-7-dioctylamino-benzo [a] fluorane Blue color-developing leuco dyes, 3- (N-ethyl-N-ρ-fluorenyl) amino-7-N-fluorenylaniline flurane, 3-diethylamino-7-aniline Green chromogenic colorless dyes such as fluoranthene, 3-diethylamino-7-dibenzylaminofluoranine, and 3,3-bis [1- (4-methoxymethoxyphenyl)-1- (4 —Dimethylaminophenyl) vinyl—2—yl] —4,5,6,7—tetragasphthalein, 3—ρ— (ρ—diamidoaminoaniline) aniline—6-methyl One 7 — gas fired, 3 — ρ — (ρ — gas aniline) aniline — 6 — methyl — 7 — gas fluorane, 3, 6 — bis (dimethylamino) buckwheat — 9 — helical — 3 '-(6, dimethylamine) This paper is sized for China National Standard (CNS) Α4 (210X297) -12-1232812 V. Description of the Invention (i〇) yl) phthalate, etc. leuco dye having near infrared absorption wavelengths and the like. With respect to the black color-developing leuco dye, these other leuco dyes are used in combination of from 0.3 to 15% by weight, particularly preferably from 0.5 to 10% by weight. In particular, in the present invention, it is preferable that the blue color-developing leuco dye is used in combination with 0.5 to 5 wt%, especially j 0 to 3.0 wt% with respect to the black color-developing leuco dye. In the present invention, the above-mentioned black color-developing leuco dyes and red color-developing properties ..., σ s of the color material are used in the total solid content of the thermosensitive recording layer in an amount of 5 to 35% by weight, especially 10%. ~ 25% by weight is preferred. The thermal recording layer is formed by coating and drying a coating liquid for a thermal recording layer on a support. The coating liquid system for a thermal recording layer generally uses water as a knife powder, and uses a ball mill, Superfine pulverizer, sand mill, etc. Y pulverizer-same or separate black color-developing leuco dye, red color-developing leuco dye, coloring agent containing two or more hydroxydiphenylfluorene series compounds, and If necessary, a micro-dispersion such as a sensitizer, a storage improver, or the like is added so that the average particle diameter is 2 μm or less, and then an adhesive is added to prepare it. Examples of these adhesives include graft copolymers of starch and polyvinyl acetate, polyvinyl ethyl alcohol, modified ethyl ethyl alcohol, ethyl modified ethyl alcohol, silicon modified polyvinyl alcohol, Water-soluble resins such as oxidized starch, casein, styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, isopropylene-maleic anhydride copolymer, etc., and styrene ~ Water-dispersible resins such as butadiene-based latex, acrylic-based latex and urethane-based latex. Among them, a water-dispersible resin is preferred. Adhesive This paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1232812 A7 ______ —___ B7 5. There are no special restrictions on the use of the invention (11). However, the thermal recording layer is 5 ~ 40% by weight, particularly preferably 20 to 35% by weight. (Please read the precautions on the back before filling this page.) Also, the thermosensitive recording layer may contain a sensitizer for controlling the recording sensitivity and a preservative improver for improving the preservability of the recording section. Specific examples of the sensitizer include ammonium stearate, ammonium bisstearate, dibenzyl terephthalate, benzyl p-octyloxybenzoate, 2-naphthylbenzyl ether, m-bitriphenyl, p-benzylbiphenyl, p-tolylbiphenyl ether, bis (4-methoxybenzyloxyethyl) ether, 1,2,2- (3-methylphenoxy) ethane , I, 2-di (4-methylphenoxy) ethane, 1,2-bis (4-methoxyphenoxy) ethane, 1,2-bis (4-monophenoxy) ethane, ι, 2 diphenoxyethane, L — (4-monophenyloxyphenoxy) — 2 1 (3-methylphenoxy) ethane, p —methylthiophenylamine —, di (β— Biphenylethoxy) benzene, dip-oxazyl oxalate, dibenzyl oxalate, and the like. : Line_ Preservative improvers can be listed as: 2,2,1-methyl-bis (4-methyl-6-tert-butylphenol), 4,4, monothiobis (2-fluorenyl-6- tert-butyl benzylphenol), 4-4'-butylene bis (6-tert-butyl-m-cresol), 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2 , 6-Dimethylbenzyl) isocyanuric acid, 1,1,3-tris (2-fluorenyl-4 4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-Methyl-4-Hydroxy-5-cyclohexylbenzyl) butane, 2,2-Bis (4-coryl-3,5-dimophenyl) propanone, 2,2'-bis (4 Once compounded with phenol such as 3,5-dimethylphenyl) propane, 4,4,1-glycidyloxydiphenylhydrazone, 4-benzyloxy-4,1- (2-methylglycidyloxy) Basic) Yifeng, terephthalic acid diglycidyl ether, toluene-type solid epoxy resin, phenol novolac solid epoxy resin, and diphenol A epoxy resin. The paper dimensions are applicable to Chinese national standards. (CNS) A4 specifications (210X297 mm) -14-! 232812 A7 ^ _B7 _ 5. Description of the invention (iTy * ^ ~~ -— epoxy compounds such as grease. (Please read the precautions on the back before filling out this page) There are no special restrictions on the amount of sensitizers and storage improvers. , Ran =, relative to 1 part by weight of all colorless dyes in the general thermosensitive recording layer, it is 0.1 ~ 4 parts by weight, and preferably 0.5 ~ 3 parts by weight. ', Moreover', the thermosensitive recording layer In addition, various auxiliary agents can be added as needed, such as: alinite, light calcium carbonate, heavy calcium carbonate, calcined kaolin, titanium oxide, magnesite, aluminum hydroxide, amorphous silicon dioxide, amine methylamine Pigments such as ammonium and formaldehyde resin fillers, surfactants such as sodium dioctylsulfosuccinate, sodium dodecylbenzylsulfonate, sodium lauryl sulfate, fatty acid metal salts, zinc stearate, hard Waxes such as calcium stearate, polyethylene wax, carnauba wax, paraffin wax, vinegar wax, etc., glyoxal, carbamate formaldehyde water resin, polyamine-based epoxy resin, polyamidoepioxane, hexane Waterproofing agent and UV absorber for diacid dihydrazide, boric acid, borax, stone acid reflux, etc. Antifoaming agent, matte dye, coloring dye, etc. The application amount of the coating liquid for the thermosensitive recording layer is 2 to 12g / m2, preferably 3 to 7g / m2. The coating liquid for the thermosensitive recording layer is borrowed. By a known coating method commonly used in this field, for example, air knife coating, pure blade coating, bar coating, rod coating, curtain coating, saddle coating, gravure coating, etc. The support can be any of the well-known supports used in the field, and in particular, it can be, for example, neutral or acidic forest paper, coated paper, synthetic paper, transparent plastic film, transparent and colored Plastic film, white plastic thin This paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1232812 V. Description of the invention (i3) The thickness of the support such as film can be appropriately selected from a wide range, but ... In general It is better to use 40 ~ 250μm. ", The protective layer may be provided on the heat-sensitive recording layer as needed to improve the chemical resistance, water resistance of the recording part, or the runability of the recording part. These protective layers are made by coating the heat-sensitive recording layer with a film. It is formed by drying the coating liquid for the protective layer of the protective adhesive. The adhesive contained in the coating liquid for the baohan layer is the one contained in the coating liquid for the thermal recording layer described above. These adhesives are relative to the protection. The total solid content of the layer is preferably 20 to 100% by weight, especially 30 to 95% by weight. Furthermore, the coating liquid for the thermal recording layer can be used in the coating liquid for the protective layer as required. The aforementioned various additives may be contained. The coating liquid for the protective layer is applied in a dry weight of 0.5 to 10 g / m2, preferably i to 5 g / m2. The coating liquid for the protective layer is generally used in this field. The well-known coating methods used, for example, air knife coating, pure blade coating, rod coating, rod coating, curtain coating, conformal coating, gravure coating, etc., are applied to the thermosensitive recording layer and allowed to dry. In order to improve the recording sensitivity and recording The recording quality can also be between the support and the heat. A coating layer with oil-absorbing pigment or hollow particles as the main component is set between the recording layers, or an electron beam or ultraviolet curable mouthpiece is coated on the protective layer as the main component. After applying the liquid, a gloss layer that is cured by irradiating electron rays or ultraviolet rays is provided, and after forming various layers, the strength is applied (the paper size is suitable for financial specifications and the specifications are GX297 mm> 1232812).

五、發明說明（Μ 光機之平滑化處理等。X，可依需要來附加其他體製造領域中之各種公知技術。、、”、、° 、、 [發明之實施形態] 以下藉由實施例更具體地說明本發明，然@，當然本發:月之轭圍並非限定於此。χ，只要無特別說明，例中之邛」及「％」係分別表示「重量部」及「重量％」。實施例1V. Description of the invention (Smoothing treatment of the M light machine, etc.) X, various well-known technologies in the field of other body manufacturing can be added as required. [,,,,,,,,,,,,,] [Inventive embodiments] The following examples are used To explain the present invention more specifically, of course, @, of course, this issue: The yoke of the moon is not limited to this. Χ, unless otherwise specified, "邛" and "%" in the examples indicate "weight part" and "weight%" Example 1.

二~~1^劑分散液（Α液彳之謂率J 藉由超黏磨機〈”（艾美克斯〈τ 彳夕y夕只〉公司製造）將1〇部之4 —羥基一4,一異丙氧二苯颯，及4部之颯變性聚乙烯醇之1〇%水溶液、8部之羥丙基甲基纖維素之5%水溶液所構成之組成物粉碎平均粒子徑為1·5μηι後，得到a液。二-1^色劑分墘液（B液）之舖半藉由超黏磨機（艾美克斯公司製造）將1〇部之2,4，一二二苯颯，及4部之颯變性聚乙烯醇之10%水溶液、8部之經丙基甲基纖維素之5%水溶液所構成之組成物粉碎至平均粒子徑1 ·5μηι後，得到b液。二顯色性無色染料分散液（C液）之調贺藉由超黏磨機（艾美克斯公司製造）將1〇部之3一二（η 一丁基）胺基一 ό —曱基一 7 —苯胺基螢烷，10部之颯變性聚乙烯醇10%水溶液及1〇部之水所構成之組成物粉碎至平均粒子徑為1 _0μπι後，得到C液。本紙張尺度適用中國國家標準（CNS) Α4規格（2Κ)><297公釐） ................••奉.................、訂..................緣 (請先閲讀背面之注意事項再填寫本頁) -17- 1232812 A7 —----—_ 五、發明説明（15 ) ----- 液)之調- —藉由超黏磨機（艾美克斯公司製造）將1〇部之3一二（11 (請先閲讀背面之注意事项再填寫本頁) —I基）胺基―7 —(0一氣苯胺基）螢燒，10 m變性聚乙稀醇10%水〉谷液及1G部之水所構成之組成物粉碎至平均粒子fe為1 ·〇μηι後，得到D液。 ~~4色顯色性無色染料液（E洛彳夕舖f 藉由超黏磨機（艾美克斯公司製造）將1〇部之3—二乙胺基7一氣螢烷，1〇部之颯變性聚乙烯醇10%水溶液及 10部之水所構成之組成物粉碎至平均粒子徑為i 〇pm後，得到E液。二顯色性無色染料分散液（F洛彳夕镅率藉由超黏磨機（艾美克斯公司製造）將1〇部之3,3 一雙 (P 一甲基胺基笨基）一 6—二甲基胺基酞，部之礙變性聚乙烯醇10%水溶液及10部之水所構成之組成物粉碎至平均粒子徑為1 ·0μπι後，得到F液。二Jt感劑分散液（G洛、之镅f 藉由超黏磨機（艾美克斯公司製造）將1〇部之1，2 一二 —(3 —甲基苯氧基）乙烷，丨0部之颯變性聚乙烯醇丨〇%水溶液及10部之水所構成之組成物粉碎至平均粒子徑為 1·5μπι後，得到g液。二感熱記錄層用塗液之調製將30部之a液、30部之Β液、30部之C液、30部之 D液、0.6部之E液、1.0部之F液、18部之G液、45部之苯乙烯一丁二烯系乳膠〔玻璃轉移溫度一 5艺，固體成分本紙張尺度適用中國國家標準（CNS) A4規格（2】0X297公釐） 1232812 A7 B7 五、發明説明（16 濃度48%〕、95部之聚乙烯醇〔商品名：PVA105，克拉里 (夕歹b)公司製造〕之13%水溶液、12部之無定形二氧化矽〔商品名：水卡席爾（S X力シ一少）P — 527，水澤化學工業公司製造〕及60部之水所構成之組成物混合攪拌後，得到感熱記錄層用塗液。 •保護層用塗液之調f 將70部之高嶺土〔平均粒徑〇· 8μηι〕之60%水性泥衆、 15部之硬脂酸鋅水分散體〔商品名：海德林（/、彳κ y ^ )Ζ —7 — 30，固體成分濃度31.5%〕、2.00部之乙醯乙醯基變性聚乙烯醇〔商品名：高成費馬（rf 一七7 77 —）Ζ — 200，曰本合成化學工業公司製造〕之1〇%水溶液、3部之乙二醛10%水溶液及120部之水所構成之組成物混合攪拌後’得到保護層用塗液。二感熱記錄體之製作於合成紙之單面上塗布感熱記錄層用塗液及保護層用塗液並乾燥以使乾燥後之塗布量分別為5g/m2、3g/m2，得到感熱記錄體。於形成保護層後，施行藉由強度砑光機之平滑化處理。實施例2〜11及比fe例1〜4 丄呈色劑分液）之調芻藉由超黏磨機（艾美克斯公司製造）將10部之4,4, 一二羥二苯颯，及4部之颯變性聚乙烯醇10%水溶液、8部之經丙基曱基纖維素5%水溶液所構成之組成物粉碎平均粒子徑為1·5μηι後，得到Η液。本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公釐） ...... .........…裝..................ΤΓ..................線· (請先閲讀背面之注意事項再填寫本頁) -19- 1232812 A7 _B7__ 五、發明説明（I7 ) •增感劑分散液（I液）將市售之硬脂酸醯胺分散液〔商品名：高微子（/、彳s 夕口 V)G — 270，固體成分濃度21% ，中京油脂公司製造〕作為I液。於實施例1之感熱記錄層用塗液之調製中，除了使用下述表1所示者以取代30部之A液、30部之B液、30部之C液、30部之D液、0.6部之E液、1.0部之F液、18 部之G液之外，其他作成與實施例1相同，分別得到感熱記錄體。 (請先閲讀背面之注意事項再填寫本頁)Two ~~ 1 ^ agent dispersion liquid (the ratio of A liquid 彳 J by a super-viscosity mill 〈(made by Ammex <τ 彳彳夕夕 only> company) will be 4 of 10 parts-hydroxy 1-4 A composition consisting of 10% isopropyloxydiphenylhydrazone, 10% aqueous solution of denatured polyvinyl alcohol and 8% 5% aqueous solution of hydroxypropyl methylcellulose, and a mean particle size of 1 · After 5 μηι, a liquid A was obtained. The bis-1 ^ toner separating solution (liquid B) was spread in half by using a super-viscous mill (manufactured by Amex Corporation). Rhenium, and 4 parts of a 10% aqueous solution of denatured polyvinyl alcohol and 8 parts of a 5% aqueous solution of propylmethylcellulose were pulverized to an average particle diameter of 1.5 μm to obtain a liquid B. Concentration of color-developing leuco dye dispersion liquid (C liquid) Using a super-visco mill (manufactured by Amex) 7 —Anilinofluorane, a composition consisting of 10 parts of fluorene-denatured polyvinyl alcohol 10% aqueous solution and 10 parts of water is crushed to an average particle diameter of 1 _0 μπι to obtain a liquid C. The paper size is applicable to China Standard (CNS) Α4 Specification (2K) > < 297 mm) ... •• Feng .............. ... 、 Order ........ (Please read the notes on the back before filling this page) -17- 1232812 A7 —----—_ Five 、 Explanation of the invention (15) ----- Liquid)--With a super stick mill (manufactured by Amex), the 3 of the 10th part (11 (please read the precautions on the back before Fill in this page) —I group) Amine group —7 — (0 monogas aniline group) Fluorescent, 10 m denatured polyvinyl alcohol 10% water> Valley composition and water composed of 1G part crushed to average particle size fe After it was 1.0 μm, D liquid was obtained. ~~ 4-color color-developing leuco dye liquid (E Luoxixipu f) 3 to 2 of 10 by a super stick mill (manufactured by Amex) The composition consisting of ethylamine 7 monofluorescein, 10 parts of fluorene-denatured polyvinyl alcohol 10% aqueous solution and 10 parts of water was pulverized to an average particle diameter of IOpm, and liquid E was obtained. Dye Dispersion Liquid (Floxyl) by a super-visco mill (manufactured by Amex Corporation) will be 10 parts of 3,3 pairs (P-methylaminobenzyl)-6-2 A composition consisting of a 10% aqueous solution of denatured polyvinyl alcohol and 10 parts of water, which is hindered by denaturation, is pulverized to an average particle diameter of 1.0 μm to obtain a liquid F. Two Jt sensitizer dispersion liquid (Glo,镅 f Using a super-viscosity mill (manufactured by Amex), 10 parts of 1,2- (3-methylphenoxy) ethane, and 0 parts of denatured polyvinyl alcohol 丨A composition composed of a 0% aqueous solution and 10 parts of water was pulverized to an average particle diameter of 1.5 μm to obtain a g liquid. The preparation of the coating liquid for the two thermal recording layers consists of 30 parts of a liquid, 30 parts of B liquid, 30 parts of C liquid, 30 parts of D liquid, 0.6 parts of E liquid, 1.0 parts of F liquid, and 18 parts of G Liquid, 45 parts of styrene-butadiene-based latex [glass transition temperature 1-5, solid content This paper size applies to Chinese National Standard (CNS) A4 specifications (2) 0X297 mm) 1232812 A7 B7 V. Description of the invention ( 16% concentration 48%], 95 parts of polyvinyl alcohol [trade name: PVA105, manufactured by Clary (Xiye b) Co., Ltd.] 13% aqueous solution, 12 parts of amorphous silicon dioxide [trade name: Water Cassier ( SX force is small) P — 527, manufactured by Mizusawa Chemical Industry Co., Ltd.] and 60 parts of water composition are mixed and stirred to obtain a coating solution for the thermosensitive recording layer. Kaolin [average particle size 0.8 μm] 60% water-based mud mass, 15 parts of zinc stearate aqueous dispersion [trade name: Heidelin (/, 彳 κ y ^) Z — 7 — 30, solid component concentration 31.5%], 2.00 ethyl acetoacetate modified polyvinyl alcohol [trade name: Gao Cheng Fermat (rf 177 77 —) Z — 200 A composition consisting of 10% aqueous solution, 3 parts of glyoxal 10% aqueous solution, and 120 parts of water was mixed and stirred to obtain a coating solution for a protective layer. Production of two thermal recording bodies Apply the coating liquid for the thermosensitive recording layer and the coating liquid for the protective layer on one side of the synthetic paper and dry so that the coating amounts after drying are 5g / m2 and 3g / m2, respectively, to obtain a thermal recording body. After forming the protective layer, The smoothing treatment by the intensity calender was performed. Examples 2 to 11 and the specific examples 1 to 4 (color separation of the toner) were adjusted by using a supervising mill (manufactured by Amex) The composition consisting of 4, 4, dihydroxybiphenyl hydrazone, and 4 fluorene-denatured polyvinyl alcohol 10% aqueous solution, and 8 propyl fluorenyl cellulose 5% aqueous solution, the average particle size is 1 • After 5 μm, mash was obtained. This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm) .................. ..TΓ ........ line · (Please read the notes on the back before filling this page) -19- 1232812 A7 _B7__ V. Description of the Invention (I7) • Sensitizer Dispersion Liquid (Liquid I) A commercially available ammonium stearate dispersion liquid [trade name: Takasu (/, 彳 s 口口 V) G — 270, 21% solid content, manufactured by Zhongjing Oil Co., Ltd. ] As I liquid. In the preparation of the coating liquid for the thermosensitive recording layer of Example 1, except that the liquid shown in Table 1 below was used instead of the 30 liquid A, 30 liquid B, 30 liquid C, 30 liquid D, Except for the 0.6 parts of the E liquid, the 1.0 parts of the F liquid, and the 18 parts of the G liquid, the other parts were prepared in the same manner as in Example 1, and thermal recording bodies were obtained. (Please read the notes on the back before filling this page)

•、可I 線_ 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） -20- 1232812 A7 B7 五、發明説明（18)• 、 I line _ This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -20-1232812 A7 B7 V. Description of invention (18)

% 命 t2» 邮 00 00 〇〇 00 f-H 〇〇〇〇 00 00 00 00 00 00 00 r—^ 00 f-^ 餐餐餐餐喻〇〇〇 ϋ 〇〇 HH 〇 Ο 〇〇 α 〇〇 % t2L 匕唉餐 4- _4_ (X) _L pH _L PU| _1_ _L 4- Ui _L pH 4- Ρη _L· 4- 4- 眾 1 t2_ 邮 Ί~ 匕箭眾荥萊命 VO Ό Ό (Jh VO VO 00 VO VO CN 〇 VO v〇 d d 〇 + d d d 〇· d d cn d d % 餐餐唉餐 ω ω W v〇 ω ω ω ω ω ω W ω tu ω 实 + + + d + + + + + + + + + + 餐 t£I- ，0 t2_ t2_ 〇 m 〇 m 〇 cn m + */Ί 寸 »Γϊ ο m 〇 m 〇 m 〇〇 m Ο m 〇 m 〇 m 超超挺唉挺趑疼唉澳疼餐 Q -L· Q -L Q 4- § Q 4- Q 4- Q -L Q -L Q 4- Q _L Q -L Q j_ Q 4- Q 4- 眾眾丁 t21> 邮眾 1 t2_ 〇 ΓΟ 〇〇 ΓΠ U iTi 寸 Ο m 〇 ΓΟ 〇 ΓΠ 〇 ΓΠ 〇 fT) ο ΓΠ 〇 C<) 〇 rn 餐疼餐疼餐唉唉起 U U U U U U U U U U u U U . % 命 t2- 命〇〇〇 CN 〇 ΓΠ 〇 rn 〇 rn ο 〇 ΓΠ 〇〇〇 Ο 趑餐餐餐唉疼餐赵唉 % X _1_ PQ j_ PQ 4- PQ 4- PQ _(_ PQ 4- ffi J. 03 _L 0Q 4- PQ 4- PQ _L « j_ 〇 VD 冢眾命命祆命卞命 OHl 〇〇〇 ΓΟ 〇 ΓΠ 〇 m Ο ro 〇 m 〇 ^Τί 〇 r—^ 〇 m ο m < ffi < < < < < < < < < < < < m 寸 VO 卜 00 〇\ 〇 r—Η f«-H (N m 寸 : 碧 IK IK ίΚ λ3 -ϋ JJ (請先閲讀背面之注意事項再填寫本頁) 袭丨 ·、^τ· :線丨本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公釐） -21 - 1232812 A7 _ B7 五、發明説明（l9 ) 實施例12 於調製實施例1之C液中，除了使用3 —二（η—戊基) 胺基一 6 —曱基一 7 —苯胺基螢院以取代3—二（η— 丁基）胺基一 6—甲基—7—苯胺基螢烷之外，其他作成與實施例j 相同，得到感熱記錄體。% Life t2 »Post 00 00 〇0000 fH 〇〇〇〇〇00 00 00 00 00 00 00 00 r— ^ 00 f- ^ Meals Meals 〇〇〇ϋ 〇〇HH 〇〇〇〇α 〇〇% t2L Dagger meal 4- _4_ (X) _L pH _L PU | _1_ _L 4- Ui _L pH 4- Ρη _L · 4- 4- Zhong 1 t2_ Ί Ί ~ Dagger 荥荥 life VO Ό Ό (Jh VO VO 00 VO VO CN 〇VO v〇dd 〇 + ddd 〇 · dd cn dd% Meal ω ω ω W v ω ω ω ω ω ω W ω tu ω Real + + + d + + + + + + + + + Meal t £ I-, 0 t2_ t2_ 〇m 〇m 〇cn m + * / Ί inch »Γ ο m 〇m 〇m 〇〇m 〇 m 〇m 〇m Super super 唉唉趑Q -L · Q -LQ 4- § Q 4- Q 4- Q -LQ -LQ 4- Q _L Q -LQ j_ Q 4- Q 4- Zhongzhongding t21 > Youzhong1 t2_ 〇Γ〇〇〇ΓΠ U iTi inch 〇 m 〇ΓΟ 〇ΓΠ 〇ΓΠ 〇fT) ο ΓΠ 〇C <) 〇rn UUUUUUUUUUU u UU. Fate 〇〇〇CN 〇ΓΠ 〇rn 〇rn ο 〇ΓΠ 〇〇〇〇趑 Meals Meal Pain Meal Zhao 唉% X _1_ PQ j_ PQ 4- PQ 4- PQ _ (_ PQ 4- ffi J. 03 _L 0Q 4- PQ 4- PQ _L «j_ 〇VD Tzu Zhongming's life and death fate OHl 〇〇〇〇Γ〇〇ΓΠ 〇m 〇 ro 〇m 〇 ^ Τί 〇r— ^ 〇m ο m < ffi < < < < < < < < < < < < m inch VO 00 00 〇 \ 〇r—Η f «-H (N m inch: Bi IK IK ίΚ λ3 -ϋ JJ ( Please read the notes on the back before filling in this page.) 丨丨, ^ τ ·: Line 丨 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -21-1232812 A7 _ B7 V. Description of the invention (L9) Example 12 In the liquid C of the preparation example 1, except that 3-di (η-pentyl) amino-6-fluorenyl-7-anilide fluorene was used instead of 3-di (η-butyl Except for amino) 6-methyl-7-aniline fluoranil, the rest of the preparation was the same as in Example j, and the thermal recording was obtained. Body.

實施例U 於調製實施例1之C液中，除了使用3—（N—乙基—N 一異戊基）胺基一 6—甲基一7—苯胺基螢烷以取代3—二一丁基）胺基一 6—甲基一 7—苯胺基螢烧之外，其他作成與實施例1相同，得到感熱記錄體。實施例1 4 於調製實施例1之B液中，除了使用3,3, 一二烯丙基 —4,4’一二羥二苯颯以取代2,4,一二羥二苯颯之外，其他作成與實施例1相同，得到感熱記錄體。實施例15 於實施例1之感熱記錄層用塗液之調製中，除了未使用1 ·0部之F液之外，其他作成與實施例1相同，得到感熱記錄體。使如上述所得到之感熱記錄體進行下述之評價試驗，其結果如表2所示。 A己錄》農度及層次性使用影像印刷機〔商品名：UP — 880，新力公司製造〕，將所得到之感熱記錄體進行17階段之層次記錄，並使用麥本紙張尺度適用中國國表標準（CNS) A4規格（210X297公楚) f請先閲讀背面之注意事项再填窝本頁) 裝· .訂· ·線· -22- 1232812 五、發明説明（2〇克貝斯濃度計〔商品名：RD914型，麥克貝斯公司製造〕以目視法測定記錄部濃度。若依據發明人之研究，則於苐 6階段之記錄濃度與未記錄部間之濃度差為0·3± 0·1時，層次性優異。顯色色調於上述記錄濃度之評價中，以目視來判定記錄部濃声為〇·4〜0.8之顯色色調。耐濕保存松將上述記錄後之感熱記錄體於4〇°c、9〇% RH之條件下進行24小時之處理，以麥克貝斯濃度計目視法來測定處理前記錄部濃度位於〇·7〇〜〇·9〇之階段之處理後記錄部濃度，並藉由下式求取其殘存率。殘存率（％ )= (Di/D〇)xl〇〇上述式中’ D!係表示處理後之記錄濃度，Dg係表示處理刖之記錄濃度。耐熱保存料將記錄後之感熱記錄體於5〇°c、3〇% RH之條件下進行24小時之處理，以麥克貝斯濃度計目視法來測定處據前。己錄部濃度位於〇·7〇〜〇·9〇之階段之處理後記錄部濃度，並藉由下式求取其殘存率。殘存率（％ )=(D2/D〇)xl〇〇上述式中，D2係表示處理後之記錄濃度，Dq係表示處理之記錄濃度。前 (請先閱讀背面之注意事項再填寫本頁} .裝丨訂— :線， -23- 1232812 A7 _B7_ 五、發明説明（U ) (請先閲讀背面之注意事項再填寫本頁) 將感熱記錄體於50°C、30% RH之條件下放置24小時後，以麥克貝斯濃度計目視法來測定感熱記錄層側之抗底面霧化性。本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） -24- 1232812 A7B7 五、發明説明（22) 表2 I 記錄濃度财熱保存性殘存率 (% ) 耐濕保存性殘存率 (% ) 抗底面霧化性顯色色調層次性第9 階段第17 階段未處理 50°C 30°/〇 RH |實施例 0.29 0.81 1.75 114 108 0.08 0.14 色彩少之黑色實施例 0.28 0.79 1.77 120 154 0.08 0.15 色彩少之黑色實施例 3 0.25 0.77 1.77 106 91 0.08 0.14 色彩少之黑色實施例 0.31 0.84 1.70 120 117 0.08 0.14 色彩少之黑色實施例 5 0.24 0.79 1.71 122 119 0.08 0.12 色彩少之黑色實施例 6 0.28 0.76 1.71 105 101 0.08 0.14 色彩少之黑色. 實施例 7 0.30 0.79 1.71 122 113 0.08 0.15 色彩少之黑色實施例 8 0.23 0.75 1.72 109 102 0.08 0.14 色彩少之黑色實施例 9 0.24 0.75 1.72 109 100 0.08 0.15 色彩少之黑色實施例 10 0.35 0.83 1.70 127 109 0.08 0.13 色彩少之黑色實施例 11 0.23 0.74 1.79 100 85 0.08 0.14 色彩少之黑色實施例 12 0.30 0.80 1.75 117 104 0.08 0.14 色彩少之黑色實施例 13 0.33 0.81 1.78 127 121 0.10 0.25 色彩少之黑色實施例 14 0.35 0.85 1.79 111 108 0.09 0.20 略帶綠色之黑色實施例 15 0.21 0.75 1.68 112 105 0.08 0.14 色彩少之黑色比較例 1 0.29 0.80 1.75 114 108 0.08 0.14 帶綠色之黑色比較例 2 0.24 0.75 1.72 108 101 0.08 0.18 帶紅色之黑色比較例 3 0.12 0.28 1.53 81 42 0.07 0.12 色彩少之黑色比較例 4 0.11 0.26 1.38 83 45 0.07 0.12 色彩少之黑色 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） -25- 1232812 A7 ~" --—----B7 五、發明説明（23 ) -----— 处旦_於實施例！及比較例3之感熱記錄體施加之記錄二（依照上述影像印刷機之17階段之層次記錄所施加 (請先閲讀背面之注意事项再填寫本頁) 之：！)及所形成之記錄部記錄濃度間之關係圖表係於第1圖中。 ^第1圖可知，與本發明相異之僅使用丨種呈色劑之、車六彳彳3之感熱記錄體於第6階段之記錄濃度僅0·2，且於第6 Ρ皆段之記錄濃度與未記錄部之濃度差只有〇12。又：相較於第9階段前之低記錄濃度，於第9階段以後記錄/辰度激增。因此，若由第1階段至第17階段之全範圍來看，可知表示施加能量與記錄濃度間之關係之圖表並非直線狀而為曲線，且層次性差。相對於此，本發明之實施例1之感熱記錄體於第6階段之記錄濃度約0.4，且於第6階段之記錄濃度與未記錄部之濃度差為0.29，濃度差於〇·3± 〇」之範圍内。又，於第1階段至第17階段之全範圍中，可知表示所施加之能量與記錄濃度間之關係之圖表實質上為直線，且具有優異之層次性。又，由上述表2之第17階段之記錄濃度項可知，相較於比較例之感熱記錄體，本發明之實施例1〜15之感熱記錄體之飽和濃度（最高記錄濃度）亦較高。 [產業上可利用性] 如表2所示，本發明之感熱記錄體係記錄部之色調為色彩少之黑色，且記錄濃度（記錄感度）、層次性及抗底面霧化性優異，又，記錄部之飽和濃度（最高記錄濃度）高，本紙張尺度適用中國國家標準（CNS〉Α4規格（210X297公釐） -26 - A7 B7 1232812 五、發明説明（24 且有優異之耐熱性及耐濕性，故具有長時間濃度變化小之優異之效果。 [圖式之簡單說明] 第1圖係顯示關於實施例1及比較例3之感熱記錄體施加之記錄能量及記錄部濃度間關係之圖表。本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） .......................裝-…..............ΤΓ------------------線· (請先閲讀背面之注意事項再填寫本頁) -27-Example U In the solution C prepared in Example 1, except that 3- (N-ethyl-N-isopentyl) amino-6-methyl-7-aniline fluoranil was used instead of 3-dibutyl Except for amino) 6-aminomethyl-7-aniline fluorescein, the other procedures were the same as in Example 1 to obtain a thermal recording body. Example 1 4 In the solution B prepared in Example 1, except that 3,3, diallyl-4,4'-dihydroxydiphenylhydrazone was used instead of 2,4, dihydroxydiphenylhydrazone The other preparations were the same as in Example 1 to obtain a thermal recording body. Example 15 In the preparation of the coating liquid for a thermosensitive recording layer of Example 1, the same procedure as in Example 1 was carried out except that the F liquid of 1.0 part was not used to obtain a thermosensitive recording body. The thermal recording medium obtained as described above was subjected to the following evaluation tests. The results are shown in Table 2. "A Jilu" uses an image printing machine [brand name: UP — 880, manufactured by Sony Corp.] for agronomy and gradation. The obtained thermal recording body is subjected to 17-level gradation recording. Standard (CNS) A4 specifications (210X297). F Please read the precautions on the back before filling in this page.) Assembling · Ordering · · Line · -22-1232812 V. Description of the invention (20 grams bass concentration meter [commodity Name: RD914, manufactured by Macbeth Corporation] Measure the concentration of the recording section visually. According to the research by the inventor, when the difference between the recorded concentration at stage 6 and the unrecorded section is 0 · 3 ± 0 · 1 In the evaluation of the above-mentioned recording density, the color development color tone of the recording part was determined to be 0.4 to 0.8 visually. The moisture-resistant storage loosened the thermal recording body after the recording to 40%. ° C, 90% RH for 24 hours, and the concentration of the recording part after the treatment was recorded at a stage of 0.70 ~ 0.90 with the Macbeth concentration meter visually, and Find the residual ratio by the following formula Residual rate (%) = (Di / D〇) x 100. In the above formula, 'D!' Represents the recorded concentration after treatment, and Dg represents the recorded concentration of treated radon. The heat-resistant storage material records the thermosensitive recording body after recording at 5 ℃ ° C, 30% RH for 24 hours, and measured by the Macbeth concentration meter visual method. The recorded concentration is recorded after the treatment at the stage of 0.7 ～ 0 ～ 90. The residual concentration was determined by the following formula: Residual ratio (%) = (D2 / D0) x 100 In the above formula, D2 is the recorded concentration after processing, and Dq is the recorded concentration after processing. Before (please read the precautions on the back before filling out this page). Binding and ordering:: Thread, -23- 1232812 A7 _B7_ V. Description of the invention (U) (Please read the precautions on the back before filling out this page). After the recorder was left at 50 ° C and 30% RH for 24 hours, the bottom fogging resistance of the thermosensitive recording layer side was measured by a Macbeth densitometer visual method. This paper standard is applicable to China National Standard (CNS) A4 (210X297 mm) -24-1232812 A7B7 V. Description of the invention (22) Table 2 I Note Concentration fiscal heat preservation surviving rate (%) Moisture-resisting surviving rate (%) Anti-bottom surface fogging color rendering tone gradation 9th stage 17th stage untreated 50 ° C 30 ° / 〇RH | Example 0.29 0.81 1.75 114 108 0.08 0.14 Black Example with Less Color 0.28 0.79 1.77 120 154 0.08 0.15 Black Example with Less Color 3 3 0.25 0.77 1.77 106 91 0.08 0.14 Black Example with Less Color 0.31 0.84 1.70 120 117 0.08 0.14 Black Example with Less Color Example 5 0.24 0.79 1.71 122 119 0.08 0.12 Black with few colors Example 6 0.28 0.76 1.71 105 101 0.08 0.14 Black with few colors. Example 7 0.30 0.79 1.71 122 113 0.08 0.15 Black with few colors Example 8 0.23 0.75 1.72 109 102 0.08 0.14 Black Example with Less Color 9 0.24 0.75 1.72 109 100 0.08 0.15 Black Example with Less Color 10 0.35 0.83 1.70 127 109 0.08 0.13 Black Example with Less Color 11 0.23 0.74 1.79 100 85 0.08 0.14 Black Example with Less Color 12 0.30 0.80 1.75 117 104 0.08 0.14 Black with few colors Example 13 0.33 0.81 1.78 127 121 0.10 0.25 Black Example with Less Color 14 0.35 0.85 1.79 111 108 0.09 0.20 Black Example with Slightly Green 15 0.21 0.75 1.68 112 105 0.08 0.14 Black Example with Less Color 1 0.29 0.80 1.75 114 108 0.08 0.14 Comparative Example with Black with Green 2 0.24 0.75 1.72 108 101 0.08 0.18 Red with black comparison example 3 0.12 0.28 1.53 81 42 0.07 0.12 Black with few colors Comparative example 4 0.11 0.26 1.38 83 45 0.07 0.12 Black with few colors (please read the precautions on the back before filling (This page) The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -25- 1232812 A7 ~ " ------- B7 V. Description of the invention (23) -----— Once in the embodiment! And Record 2 of the thermal recording body application of Comparative Example 3 (applied in accordance with the 17-level hierarchical recording of the above-mentioned image printing machine (please read the precautions on the back before filling this page) :!) and the recording section records The relationship between the concentrations is shown in Figure 1. ^ Fig. 1 shows that the recording density of the thermal recording body of Che Liu 彳彳 3, which uses only one kind of coloring agent, which is different from the present invention, in the sixth stage is only 0.2, and the recording density in the sixth stage is the same. The difference between the recorded density and the unrecorded density was only 012. Also: Compared with the low recording concentration before the 9th stage, the recording / time increase sharply after the 9th stage. Therefore, when looking at the full range from the first stage to the 17th stage, it can be seen that the graph showing the relationship between the applied energy and the recording density is not a straight line but a curve, and the layering is poor. In contrast, the thermal recording body of Example 1 of the present invention has a recording density of about 0.4 in the sixth stage, and a difference between the recorded density in the sixth stage and the unrecorded part is 0.29, and the density difference is less than 0.3 ± 0. ". In addition, in the entire range from the first stage to the seventeenth stage, it can be seen that the graph showing the relationship between the applied energy and the recording density is substantially a straight line and has excellent gradation. In addition, it can be seen from the recording density item at the 17th stage of Table 2 that the saturation density (highest recording density) of the thermal recording body of Examples 1 to 15 of the present invention is also higher than that of the thermal recording body of the comparative example. [Industrial Applicability] As shown in Table 2, the color tone of the recording part of the thermal recording system of the present invention is black with few colors, and has excellent recording density (recording sensitivity), gradation, and anti-fogging properties on the bottom surface. The saturation density (highest recorded density) of the Ministry is high. The paper size is in accordance with Chinese national standard (CNS> A4 specification (210X297mm) -26-A7 B7 1232812 V. Description of the invention (24 and excellent heat resistance and humidity resistance) Therefore, it has an excellent effect of small concentration change over a long period of time. [Simplified description of the figure] FIG. 1 is a graph showing the relationship between the recording energy applied by the thermal recording body of Example 1 and Comparative Example 3 and the concentration of the recording portion. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ..............-... ....... ΤΓ ------------------ line · (Please read the precautions on the back before filling this page) -27-

Claims

1232812 A8 B8 C8 D8 6. Scope of patent application 1. A thermal recording body, which has (a) a support and (b) a thermal recording formed on the support and containing #color dye, I color agent and adhesive: And the thermosensitive recording layer contains two or more hydroxydiphenylhydrazone compounds as the color former, and one containing a black chromogenic leuco dye and a red chromogenic leuco dye as the leuco dye, The red color-developing leuco dye is present in an amount of 0.5 to 3.5% by weight based on the black color-developing leuco dye. 2. (Please read the precautions on the back before filling this page) If the thermal recording body of item 1 of the scope of patent application, the hydroxydiphenylhydrazone compound is composed of 2,4, dihydroxydiphenylhydrazone and 4 At least one selected from the group consisting of 4,4,2-dihydroxydiphenylhydrazone, and 4-hydroxy-1,4-isopropyloxydiphenyl. 3. The thermal recording body according to item 2 of the scope of patent application, in which 4-hydroxyl-4'-isopropyloxydiphenyl maple is composed of 2,4,1-dihydroxydiphenylhydrazone and 4,4 with respect to the weight of i. At least one selected from the group consisting of 'dihydroxydiphenylhydrazone' uses 0.5 to 2.0 parts by weight. 4. The thermal recording body according to item 1 of the scope of patent application, wherein the aforementioned black color-developing leuco dye is composed of 3-bis (n-butyl) amino-6-methyl-7-aniline fluoranine, 3- In the group consisting of bis (η-pentyl) amino-6-methyl-7 aniline fluoranil and 3-bis (η-butyl) amino-7- (0-gas aniline) fluorine Pick at least one. 5. The thermal recording body according to item 4 of the application, wherein the black color-developing leuco dye is composed of 3-bis (η-butyl) amino-6-fluorenyl-7-aniline fluoran and 3- At least one selected from the group consisting of bis (η-pentyl) amino-6-methyl-7-aniline fluorescein, and 3 paper sizes are applicable to China National Standard (CNS) A4 specifications (210X297 mm) ) -28- 1232812 A8 B8 C8 D8 Six, the scope of application for patents is a mixture of di (n-butyl) amino-7- (0-chloroaniline) fluorane. 6. The thermal recording body according to item 5 of the scope of patent application, in which, relative to (please read the precautions on the back before filling in this page), it consists of 3 ~ bis (η-butyl) amino-6-fluorenyl-7 —Styrylamine fluorescein and at least one selected from the group consisting of 3 ~ di-U-pentyl) amino-6-fluorenyl-7-anilinefluorane, 3-bis (η-butyl) amine A 7 — (0 ~ air amine group) fluorescent system is used at a ratio of 30 to 300% by weight. 7. The thermal recording body according to item 丨 of the patent application scope, wherein the aforementioned red color-developing leuco dye is 3-diethylamino-7-aerofluorane. 8. Rushen black contains 9. Russian record weight 10. Russian record 11. Russian record 12 Russin remembers the thermal recording body of the patent scope item 1, which is a colorless leuco dye relative to the front color, The red color-developing leuco dye is 0.8 to 3.0% by weight. The thermosensitive recording material according to the first item of the patent application, wherein the thermosensitive layer contains 0.5 to 5% of the blue color-developing leuco dye relative to the black color-developing leuco dye. : Line_ Please refer to the thermal recording body of the first item of the patent scope, wherein the adhesive in the thermal layer is a water-dispersible resin. The thermosensitive recording material according to claim 1, wherein the thermosensitive layer further contains a sensitizer or a preservative improver or a mixture thereof. The thermal recording body of item 1 of the monthly patent range further has a protective layer on the aforementioned sensing layer.

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