JPH025199B2 - - Google Patents
Info
- Publication number
- JPH025199B2 JPH025199B2 JP57075886A JP7588682A JPH025199B2 JP H025199 B2 JPH025199 B2 JP H025199B2 JP 57075886 A JP57075886 A JP 57075886A JP 7588682 A JP7588682 A JP 7588682A JP H025199 B2 JPH025199 B2 JP H025199B2
- Authority
- JP
- Japan
- Prior art keywords
- color
- thiourea
- heat
- parts
- recording material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- -1 ethyl phenyl Chemical group 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ABJAMKKUHBSXDS-UHFFFAOYSA-N 3,3-bis(6-amino-1,4-dimethylcyclohexa-2,4-dien-1-yl)-2-benzofuran-1-one Chemical compound C1=CC(C)=CC(N)C1(C)C1(C2(C)C(C=C(C)C=C2)N)C2=CC=CC=C2C(=O)O1 ABJAMKKUHBSXDS-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- GSCLSACFHWKTQU-UHFFFAOYSA-N 2'-chloro-6'-(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Cl)=CC=C1OC1=CC(N(CC)CC)=CC=C21 GSCLSACFHWKTQU-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- LYCCNHVQBSOODL-UHFFFAOYSA-N 6-(diethylamino)-3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C=1C(N(CC)CC)=CC=C2C=1C(=O)OC2(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 LYCCNHVQBSOODL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
Description
本発明は発色剤としてロイコ染料を含む感熱記
録材料の改良に関する。
感熱記録材料は一般に紙、合成紙、プラスチツ
クフイルム等の支持体上に熱発色性組成物を主成
分とする感熱発色層を設けたもので、熱ヘツド、
熱ペン、レーザー光等で加熱することにより発色
画像が得られる。この種の記録材料は他の記録材
料に比べて現像、定着等の煩雑な処理を施すこと
なく、比較的簡単な装置で短時間に記録が得られ
ること、騒音の発生及び環境汚染が少ないこと、
コストが安いことなどの利点により、図書、文書
などの複写に用いられる他、電子計算機、フアク
シミリ、券売機、ラベル、レコーダーなど多方面
に亘る記録材料として広く利用されている。この
ような感熱記録材料に用いられる熱発色性組成物
は一般に発色剤と、この発色剤を熱時発色せしめ
る顕色剤とからなり、発色剤としては例えばラク
トン、ラクタム又はスピロピラン環を有する無色
又は淡色のロイコ染料が、また顕色剤としては各
種の酸性物質、例えば有機酸やフエノール性物質
が用いられている。この発色剤の顕色剤とを組合
せた記録材料は特に得られる画像の色調が鮮明で
あり、且つ地肌の白色度が高く、しかも画像（染
料画像）の耐候性が優れているという利点を有
し、広く利用されている。
しかし、近年、感熱記録方式が従来の他の記録
方式にとつて代り、需要が増大するにつれて、こ
の方式に用いられる感熱記録材料の品質向上に対
する要求も高まつて来ており、特に普通紙に近い
品質、即ち白色度、保存安定性等を改良する要望
が大きい。ところで前述のような感熱記録材料の
品質に影響を及ぼす材料としては発色剤、顕色
剤、及びこれらを結着又は保護する結着剤、その
他の助剤（例えば分散剤、顔料）が挙げられる
が、中でも影響が大きいのは顕色剤である。従
来、顕色剤としては発色性の優れているものとし
てビスフエノールＡが一般に使用されて来たが、
ビスフエノールＡは反面、地肌部にかぶりを起こ
させる他、耐水性が劣る等の欠点があり、その結
果としてコントラストの低下をきたすことは当業
者間ではよく知られていることである。
本発明者らは優れた発色性を維持し、しかし前
述のような欠点も殆どなく、地肌を白く維持でき
る顕色剤について種々検討した結果、本発明に到
達した。
即ち本発明の感熱記録材料は支持体上に無色又
は淡色のロイコ染料と顕色性物質とを含む感熱発
色層を設けた感熱記録材料において、顕色性物質
として一般式（）
（式中、R1，R2は、水素、アルキル、芳香族基、
アシル又はハロゲンを表わす）
で示される化合物を用いたことを特徴とするもの
である。上記一般式（）におけるアルキルとし
ては炭素数１〜30、好ましくは１〜18、更に好ま
しくは１〜４のものがあげられ、またハロゲンと
しては塩素、臭素、フツ素などがあげられ、芳香
族基としては、フエニル、メチルフエニル、エチ
ルフエニル、プロピルフエニル、イソプロピルフ
エニル等のアリール基があげられる。
本発明化合物を用いることによつてビスフエノ
ール等の従来の顕色剤と較べて、画像濃度は同等
もしくはそれ以上であり、しかも地肌の白さは格
段に改良され、むしろ、より白くする傾向を示
す。
上記一般式で示される化合物の具体例をあげる
と、
１，３―ジフエニルチオ尿素
１，３―ジ―（ｐ―メチルフエニル）チオ尿素
１，３―ジ（ｐ―クロロフエニル）チオ尿素
１，３―ジ（ｍ―クロロフエニル）チオ尿素
１，３―ジ（ｏ―メチルフエニル）チオ尿素
１，３―ジ（ｍ―メチルフエニル）チオ尿素
１，３―ジ（ｏ―クロロフエニル）チオ尿素
１，３―ジ（ｐ―ブロモフエニル）チオ尿素
１，３―ジ（ｍ―ブロモフエニル）チオ尿素
１，３―ジ（ｏ―ブロモフエニル）チオ尿素
１，３―ジ（ｐ―エチルフエニル）チオ尿素
１，３―ジ（ｍ―エチルフエニル）チオ尿素
１，３―ジ（ｏ―エチルフエニル）チオ尿素
１，３―ジ（ｐ―イソプロピルフエニル）チオ
尿素
１，３―ジ（ｐ―イソブチルフエニル）チオ尿
素
１，３―ジ（ｐ―イソアミルフエニル）チオ尿
素
１，３―ジ（ｐ―オクチルフエニル）チオ尿素
１，３―ジ（ｐ―ラウリルフエニル）チオ尿素
１，３―ジ（ｐ―ステアリルフエニル）チオ尿
素
１，３―ジ（ｐ―メチルカルボニルフエニル）
チオ尿素
１，３―（（ｐ―イソプロピルカルボニルフエ
ニル）チオ尿素
１，３―ジ（ｐ―ジフエニル）チオ尿素
等が挙げられるが、この限りではない。
本発明化合物が強い顕色能を示すことについて
はアミノ基の活性水素によるものと考えられる。
また、地肌が格段に白いことについては、常温
で、アミノ基の活性水素が弱くむしろ塩基性を示
し、染料を無色化する効果があると考えられる。
本発明化合物の合成は、例えば、実験有機化学
書（Gatterman，Wieland p.151）等に記載され
ている。
本発明で用いられる無色又は淡色のロイコ染料
は発色剤として単独又は２種以上混合して使用さ
れる。その具体例はトリフエニルメタン系、フル
オラン系、フエノチアジン系、オーラミン系、ス
ピロピラン系等の染料のロイコ体であり、更に詳
しくは
３，3′―ビス（ｐ―ジメチルアミノフエニル）
―６―ジメチルアミノフタリド（別名クリスタル
バイオレツト）、
３，３―ビス（ｐ―ジメチルアミノフエニル）
フタリド、
３，３―ビス（ｐ―ジメチルアミノフエニル）
フタリド、
３，３―ビス（ｐ―ジメチルアミノフエニル）
―６―ジエチルアミノフタリド、
３，３―ビス（ｐ―ジメチルアミノフタリド）
―６―クロロフタリド、
３―（Ｎ―ｐ―トリル―Ｎ―エチルアミノ）―
６―メチル―７―（Ｎ―フエニルアミノ）フルオ
ラン、
３―ジエチルアミノ―７―クロロフルオラン、
ベンゾイルロイコメチレンブルー、
6′―クロロ―8′―メトキシ―ベンゾインドリノ
―ピリロスピラン、
6′―ブロモ―3′―メトキシ―ベンゾインドリノ
―ピリロスピラン、
２―〔３，６―ビス（ジエチルアミノ）―９―
（ｏ―クロロアニリノ）〕キサンチル安息香酸ラク
タム、
等が挙げられる。
感熱発色層には以上の素材の他、通常、結着剤
も含まれる。結着剤としては感熱記録の分野で公
知のものが全て使用でき、例えばゼラチン、澱
粉、ヒドロキシエチルセルロース、ポリアクリル
酸、カルボキシエチルセルロース、メトキシセル
ロース、ポリビニルアルコール、ポリビニルピロ
リドン等が挙げられる。
本発明の感熱記録材料を作るには紙、合成紙等
の支持体上にロイコ染料、前記一般式の化合物及
び結着剤を主成分とする水溶液を塗布乾燥すれば
よい。ここでロイコ染料、前記一般式の化合物及
び結着剤の使用量は夫々、５〜30重量％、40〜80
重量％、２〜20重量％が適当である。また形成さ
れる感熱発色層の付着量は、２〜10ｇ／m2程度で
ある。なお塗布液中には塗布状態又は熱記録状態
を良くするため、タルク、ワツクス、界面活性
剤、消泡剤等の助剤を添加することができる。
以下に実施例を示す。なお部、％は夫々、重量
部、重量％である。
実施例 １〜５
〔Ａ液〕
３―（Ｎ―メチル―Ｎ―シクロヘキシルアミ
ノ）―６―メチル―７―アニリノフルオラン
10部
ヒドロキシエチルセルロースの10％水溶液 10部
水 30部
ボールミルで20時間分散する。
〔Ｂ液〕
表記の顕色剤成分 30部
ヒドロキシエチルセルロースの10％水溶液 30部
水 90部
ボールミルで20時間分散する。
〔Ｃ液〕
炭酸カルシウム 40部
ステアリン酸アミド 15部
ステアリン酸亜鉛 ５部
ポリビニルアルコール10％水溶液 60部
水 180部
ボールミルで10時間分散する。
以上のようにして得られたＡ液、Ｂ液及びＣ液
を混合し、坪量50ｇ／m2の上質紙上に乾燥付着量
が６ｇ／m2となるよう塗布乾燥して感熱発色層を
設け、感熱記録紙を得た。その評価結果を下記表
に示す。なお最高濃度とは市販の熱傾斜試験機を
用いて140℃で印字した時の画像濃度で、またそ
の時の地肌濃度も併記した。濃度はマクベス濃度
計を用いて測定した。
The present invention relates to improvements in heat-sensitive recording materials containing leuco dyes as color formers. Thermosensitive recording materials generally have a thermosensitive coloring layer containing a thermochromic composition as a main component on a support such as paper, synthetic paper, or plastic film.
Colored images can be obtained by heating with a thermal pen, laser light, etc. Compared to other recording materials, this type of recording material does not require complicated processing such as development and fixing, can produce records in a short time using relatively simple equipment, and generates less noise and pollutes the environment. ,
Due to its low cost and other advantages, it is used not only for copying books and documents, but also as a recording material in a wide range of applications such as electronic computers, facsimile machines, ticket vending machines, labels, and recorders. Thermochromic compositions used in such heat-sensitive recording materials generally consist of a color former and a color developer that causes the color former to develop color when heated. Examples of the color former include lactone, lactam, or colorless or spiropyran ring-containing compositions. Light-colored leuco dyes are used, and various acidic substances such as organic acids and phenolic substances are used as color developers. Recording materials in which this color forming agent is combined with a color developer have the advantage that the obtained image has a particularly clear color tone, has a high background whiteness, and has excellent weather resistance of the image (dye image). and is widely used. However, in recent years, heat-sensitive recording methods have replaced other conventional recording methods, and as demand has increased, there has also been an increasing demand for improved quality of the heat-sensitive recording materials used in this method, especially for plain paper. There is a strong desire to improve similar quality, ie, whiteness, storage stability, etc. By the way, materials that affect the quality of the heat-sensitive recording material as mentioned above include color formers, color developers, binders that bind or protect these, and other auxiliary agents (such as dispersants and pigments). However, the color developer has the greatest influence. Conventionally, bisphenol A has been generally used as a color developer due to its excellent color development properties.
On the other hand, it is well known among those skilled in the art that bisphenol A causes fogging on the background and has drawbacks such as poor water resistance, resulting in a decrease in contrast. The present inventors have arrived at the present invention after conducting various studies on a color developer that maintains excellent color development, has almost no drawbacks as mentioned above, and can maintain a white background. That is, the heat-sensitive recording material of the present invention is a heat-sensitive recording material in which a heat-sensitive coloring layer containing a colorless or light-colored leuco dye and a color-developing substance is provided on a support, and the color-developing substance has the general formula (). (In the formula, R 1 and R 2 are hydrogen, alkyl, aromatic group,
It is characterized by using a compound represented by (representing acyl or halogen). The alkyl in the above general formula () includes those having 1 to 30 carbon atoms, preferably 1 to 18 carbon atoms, and more preferably 1 to 4 carbon atoms, and the halogen includes chlorine, bromine, fluorine, etc. Examples of the group include aryl groups such as phenyl, methylphenyl, ethyl phenyl, propylphenyl, and isopropylphenyl. By using the compound of the present invention, compared to conventional color developers such as bisphenols, the image density is the same or higher, and the whiteness of the background is significantly improved, and in fact, it tends to become whiter. show. Specific examples of compounds represented by the above general formula are: 1,3-diphenylthiourea 1,3-di-(p-methylphenyl)thiourea 1,3-di(p-chlorophenyl)thiourea 1,3-di- (m-chlorophenyl)thiourea 1,3-di(o-methylphenyl)thiourea 1,3-di(m-methylphenyl)thiourea 1,3-di(o-chlorophenyl)thiourea 1,3-di(p -bromophenyl)thiourea 1,3-di(m-bromophenyl)thiourea 1,3-di(o-bromophenyl)thiourea 1,3-di(p-ethylphenyl)thiourea 1,3-di(m-ethylphenyl) ) Thiourea 1,3-di(o-ethylphenyl)thiourea 1,3-di(p-isopropylphenyl)thiourea 1,3-di(p-isobutylphenyl)thiourea 1,3-di(p -isoamylphenyl)thiourea 1,3-di(p-octylphenyl)thiourea 1,3-di(p-laurylphenyl)thiourea 1,3-di(p-stearylphenyl)thiourea 1 ,3-di(p-methylcarbonylphenyl)
Examples include, but are not limited to, thiourea, 1,3-((p-isopropylcarbonylphenyl)thiourea, 1,3-di(p-diphenyl)thiourea, etc. The compounds of the present invention exhibit strong color developing ability. This is thought to be due to the active hydrogen of the amino group.
Furthermore, the reason why the background is so white is thought to be that at room temperature, the active hydrogen of the amino group is weak and rather basic, which has the effect of making the dye colorless. The synthesis of the compounds of the present invention is described, for example, in Experimental Organic Chemistry (Gatterman, Wieland p. 151). The colorless or light-colored leuco dye used in the present invention may be used alone or in combination as a coloring agent. Specific examples include leuco dyes such as triphenylmethane, fluoran, phenothiazine, auramine, and spiropyran dyes, and more specifically 3,3'-bis(p-dimethylaminophenyl).
-6-dimethylaminophthalide (also known as crystal violet), 3,3-bis(p-dimethylaminophenyl)
Phthalide, 3,3-bis(p-dimethylaminophenyl)
Phthalide, 3,3-bis(p-dimethylaminophenyl)
-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophthalide)
-6-chlorophthalide, 3-(N-p-tolyl-N-ethylamino)-
6-methyl-7-(N-phenylamino)fluoran, 3-diethylamino-7-chlorofluoran,
Benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolino-pyrylospirane, 6'-bromo-3'-methoxy-benzoindolino-pyrylospirane, 2-[3,6-bis(diethylamino)-9-
(o-chloroanilino)]xantylbenzoic acid lactam, and the like. In addition to the above-mentioned materials, the thermosensitive coloring layer usually also contains a binder. As the binder, all known binders in the field of thermosensitive recording can be used, such as gelatin, starch, hydroxyethyl cellulose, polyacrylic acid, carboxyethyl cellulose, methoxy cellulose, polyvinyl alcohol, polyvinylpyrrolidone, and the like. To produce the heat-sensitive recording material of the present invention, an aqueous solution containing a leuco dye, a compound of the above general formula, and a binder as main components may be coated on a support such as paper or synthetic paper and dried. Here, the amounts of the leuco dye, the compound of the above general formula, and the binder used are 5 to 30% by weight and 40 to 80% by weight, respectively.
% by weight, 2 to 20% by weight is suitable. The amount of the heat-sensitive coloring layer formed is about 2 to 10 g/m 2 . In order to improve the coating state or thermal recording state, auxiliary agents such as talc, wax, surfactant, antifoaming agent, etc. can be added to the coating liquid. Examples are shown below. Note that parts and % are parts by weight and % by weight, respectively. Examples 1 to 5 [Liquid A] 3-(N-methyl-N-cyclohexylamino)-6-methyl-7-anilinofluorane
10 parts 10% aqueous solution of hydroxyethyl cellulose 10 parts water 30 parts Disperse in a ball mill for 20 hours. [Liquid B] 30 parts of the developer component listed above 30 parts of a 10% aqueous solution of hydroxyethyl cellulose 90 parts of water Disperse in a ball mill for 20 hours. [Liquid C] Calcium carbonate 40 parts Stearamide 15 parts Zinc stearate 5 parts Polyvinyl alcohol 10% aqueous solution 60 parts Water 180 parts Disperse in a ball mill for 10 hours. The A, B, and C solutions obtained as above were mixed and coated and dried on a high-quality paper with a basis weight of 50 g/m 2 to a dry adhesion of 6 g/m 2 to form a heat-sensitive coloring layer. , thermal recording paper was obtained. The evaluation results are shown in the table below. The maximum density is the image density when printed at 140°C using a commercially available thermal gradient tester, and the background density at that time is also recorded. Concentrations were measured using a Macbeth densitometer.
【表】
以上の結果から本発明の前記一般式化合物を用
いた記録材料は優れた発色性を維持し、しかも地
肌が格段に白いことがわかる。[Table] From the above results, it can be seen that the recording material using the compound of the general formula of the present invention maintains excellent color development and has a significantly whiter background.
Claims (1)
時発色せしめる顕色性物質を支持させた感熱記録
材料において、該顕色性物質が下記一般式（）
で示される化合物であることを特徴とする感熱記
録材料。 一般式（） （式中、R1，R2は、Ｈ、アルキル、芳香族基、
アシル又はハロゲンを表わす）[Scope of Claims] 1. A heat-sensitive recording material in which a leuco dye and a color-developing substance that causes the leuco dye to develop color when heated are supported on a support, wherein the color-developing substance has the following general formula ().
A heat-sensitive recording material characterized by being a compound represented by: General formula () (In the formula, R 1 and R 2 are H, alkyl, aromatic group,
(represents acyl or halogen)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57075886A JPS58193190A (en) | 1982-05-06 | 1982-05-06 | Thermosensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57075886A JPS58193190A (en) | 1982-05-06 | 1982-05-06 | Thermosensitive recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58193190A JPS58193190A (en) | 1983-11-10 |
| JPH025199B2 true JPH025199B2 (en) | 1990-01-31 |
Family
ID=13589220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57075886A Granted JPS58193190A (en) | 1982-05-06 | 1982-05-06 | Thermosensitive recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58193190A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4599630A (en) * | 1983-11-15 | 1986-07-08 | Ricoh Company, Ltd. | Two-color thermosensitive recording material |
| JPH0679870B2 (en) * | 1984-04-19 | 1994-10-12 | 株式会社リコー | Two-color thermal recording material |
| JPS6127287A (en) * | 1984-07-17 | 1986-02-06 | Ricoh Co Ltd | Thermal recording material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55139290A (en) * | 1979-04-19 | 1980-10-30 | Ricoh Co Ltd | Multicolor thermosensitive recording material |
| JPS5670985A (en) * | 1979-11-09 | 1981-06-13 | Ciba Geigy Ag | Pressure sensitive or heat sensitive recording material |
| JPS56148587A (en) * | 1980-04-21 | 1981-11-18 | Honshu Paper Co Ltd | Heat-sensitive recording material |
-
1982
- 1982-05-06 JP JP57075886A patent/JPS58193190A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55139290A (en) * | 1979-04-19 | 1980-10-30 | Ricoh Co Ltd | Multicolor thermosensitive recording material |
| JPS5670985A (en) * | 1979-11-09 | 1981-06-13 | Ciba Geigy Ag | Pressure sensitive or heat sensitive recording material |
| JPS56148587A (en) * | 1980-04-21 | 1981-11-18 | Honshu Paper Co Ltd | Heat-sensitive recording material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58193190A (en) | 1983-11-10 |
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