JPH0152198B2 - - Google Patents
Info
- Publication number
- JPH0152198B2 JPH0152198B2 JP57163650A JP16365082A JPH0152198B2 JP H0152198 B2 JPH0152198 B2 JP H0152198B2 JP 57163650 A JP57163650 A JP 57163650A JP 16365082 A JP16365082 A JP 16365082A JP H0152198 B2 JPH0152198 B2 JP H0152198B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- methyl
- sensitive recording
- diethylamino
- color
- 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
Links
- 239000000463 material Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- -1 fluoran compound Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 12
- 239000000975 dye Substances 0.000 description 11
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 9
- 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 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 125000001033 ether group Chemical group 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- HUOKHAMXPNSWBJ-UHFFFAOYSA-N 2'-chloro-6'-(diethylamino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Cl)=C(C)C=C1OC1=CC(N(CC)CC)=CC=C21 HUOKHAMXPNSWBJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DJRJYWNDMBCUSJ-UHFFFAOYSA-N 3,3-bis[4-(dibutylamino)phenyl]-2-benzofuran-1-one Chemical compound C1=CC(N(CCCC)CCCC)=CC=C1C1(C=2C=CC(=CC=2)N(CCCC)CCCC)C2=CC=CC=C2C(=O)O1 DJRJYWNDMBCUSJ-UHFFFAOYSA-N 0.000 description 1
- PGAAZCXJMPDCHO-UHFFFAOYSA-N 3-(4-chloro-2-hydroxy-5-methylphenyl)-3-[4-(dimethylamino)-2-methoxyphenyl]-2-benzofuran-1-one Chemical compound COC1=CC(N(C)C)=CC=C1C1(C=2C(=CC(Cl)=C(C)C=2)O)C2=CC=CC=C2C(=O)O1 PGAAZCXJMPDCHO-UHFFFAOYSA-N 0.000 description 1
- WMOULUHRMJQPDK-UHFFFAOYSA-N 3-[4-(diethylamino)-2-hydroxyphenyl]-3-(2-methoxy-5-methylphenyl)-2-benzofuran-1-one Chemical compound OC1=CC(N(CC)CC)=CC=C1C1(C=2C(=CC=C(C)C=2)OC)C2=CC=CC=C2C(=O)O1 WMOULUHRMJQPDK-UHFFFAOYSA-N 0.000 description 1
- LSYHVTSZEQZQNJ-UHFFFAOYSA-N 3-[4-(dimethylamino)-2-hydroxyphenyl]-3-(2-methoxy-5-nitrophenyl)-2-benzofuran-1-one Chemical compound COC1=CC=C([N+]([O-])=O)C=C1C1(C=2C(=CC(=CC=2)N(C)C)O)C2=CC=CC=C2C(=O)O1 LSYHVTSZEQZQNJ-UHFFFAOYSA-N 0.000 description 1
- QZTWMQKYDRGASN-UHFFFAOYSA-N 4-[2-[2-[2-(4-hydroxyphenyl)sulfanylethoxy]ethoxy]ethylsulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SCCOCCOCCSC1=CC=C(O)C=C1 QZTWMQKYDRGASN-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- GFGSEGIRJFDXFP-UHFFFAOYSA-N 6'-(diethylamino)-2'-(2,4-dimethylanilino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CC)CC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=C(C)C=C1C GFGSEGIRJFDXFP-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
- KCBLOCLSUSTAMW-UHFFFAOYSA-N 6-chloro-3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(Cl)C=C2C(=O)O1 KCBLOCLSUSTAMW-UHFFFAOYSA-N 0.000 description 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008542 thermal sensitivity Effects 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
本発明は感熱記録材料に関し、特に発色性その
他の記録適性にすぐれ、画像の安定性が良好な感
熱記録材料に関する。
一般の感熱記録材料は紙、フイルム等の支持体
上に発色剤としてロイコ染料のような無色又は淡
色の発色性染料及びこれを熱時発色せしめる顕色
剤としてフエノール性化合物（特にビスフエノー
ルＡ）、有機酸等の酸性物質からなる発色系に更
に結合剤、充填剤、感度向上剤、滑剤、その他の
助剤を分散した感熱発色層を設けたもので、例え
ば特公昭43−4160号、特公昭45−14039号、特開
昭48−27736号等に紹介され、広く実用に供され
ている。この種の感熱記録シートは加熱時（加熱
には熱ヘツドを内蔵したサーマルプリンターやフ
アクシミリ等が利用される）の発色剤と顕色剤と
の瞬間的な化学反応により発色画像を得るもので
あるから、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、テレツクス、医
療計測機等の種々の情報並びに計測機器の記録材
料として有用である。一方、近年、社会の発展と
共に記録の高速化及び高密度化に対する要求が高
まつてきた。このため記録装置自体の高速化は勿
論、これに対応し得る記録材料の開発が強く望ま
れている。そこでこのような観点から特開昭53−
39139号、特開昭53−26139号、特開昭53−5636
号、特開昭53−11036号等には前述のような感熱
発色層に更に各種ワツクス類、脂肪酸アミド、ア
ルキル化ビフエニル、置換ビフエニルアルカン、
クマリン類、ジフエニルアミン類等の低融点の熱
溶融性物質を増感剤（あるいは融点降下剤）とし
て添加したものが提案されている。しかし増感剤
を添加する方式は発色反応に先立つてまず増感剤
を溶融する必要があるため、短時間のパルスで微
小な熱量しか供給されない高速記録において充分
な熱応答性が得られないばかりでなく、発色層中
の増感剤が溶融するため、サーマルヘツドへのカ
ス付着やにじみ、尾引き、ゴースト等のトラブル
が発生し易いという記録適性上の問題がある。ま
た高温及び／又は多湿下で保存した場合は経時と
共にかぶりを生じる上、記録画像のコントラスト
を低下させることが多い。従つて高速記録用感熱
記録シートとしては増感剤を添加しない構成のも
のが望ましい。しかし感熱記録シートに使用され
る無色又は淡色の発色性染料は通常160〜240℃と
高いので、増感剤を添加しないで高速記録用とし
て適した感熱発色層を構成するには低融点で、し
かも前記発色剤を発色させる能力の大きな顕色剤
の使用が不可欠である。ところで、無色又は淡色
の発色性染料と組合せる酸性物質、特にフエノー
ル性化合物については特公昭45−14039号を初め
として各種文献に数多く記載されているが、この
うちビスフエノールＡが品質の安定性、低価格、
入手のし易さ等の点から汎用されている。しか
し、このビスフエノールＡは融点が156〜158℃と
高いため、熱感度が低い（従つて熱発色温度が高
い）という欠点がある。これに対し、融点の低い
フエノール性化合物、例えば４−ｔ−ブチルフエ
ノール（融点94〜99℃）、α−ナフトール（融点
95〜96℃）、β−ナフトール（融点119〜122℃）
等のモノフエノール類を使用した場合には感熱記
録シートの保存安定性が劣り、室温でも次第にか
ぶりを生じるばかりでなく、いわゆるフエノール
臭が強く、実用的ではない。また特公昭54−
12819号には、２，２−ビス（4′−ヒドロキシフ
エニル）ノルマルヘキサン（融点99〜103℃）を、
特開昭55−27253号には１，１−ビス（4′−ヒド
ロキシフエニル）アルカン（アルカンの炭素数は
３〜13）をそれぞれ用いて熱感度が高く、且つ保
存安定性及び発色性の良い感熱記録シートを作り
得ることが記載されているが、これらの物質はい
ずれも合成が困難で入手性に問題がある。更に特
開昭56−144193号には、ｐ−ヒドロキシ安息香酸
の低級アルキルエステル又はベンジルエステルは
合成が容易であり、またこれを用いて高感度の感
熱記録シートを作り得ることが記載されている
が、このものは発色部が経時と共に消色し易く、
しかも前記フエノール性化合物の結晶が析出する
（いわゆる白粉現象）という保存上の欠点を有し
ている。
以上のように、従来の高速記録用感熱記録シー
トは増感剤又は融点降下剤を使用したものも使用
しないものもそれぞれ一長一短があり、実用的と
いえるものはなかつた。
本発明の第１の目的は、増感剤又は融点降下剤
を使用する必要がなく、従つて熱応答性、記録適
性に優れ、さらに高温及び又は多湿下でも保存安
定性及び画像コントラストに優れた感熱記録材料
を提供することである。
本発明の第２の目的は、高熱感度のフエノール
性化合物を使用するにも拘わらず、室温での保存
安定性に優れ、フエノール臭もなく、入手性の問
題もない、極めて実用的な感熱記録材料を提供す
ることである。
即ち、本発明の感熱記録材料は、ロイコ染料に
対する顕色剤として、一般式
（式中、Ｒはエーテル結合を１〜５個含有するア
ルキレン基を表わす）
で表わされるフエノール性物質を用いることを特
徴とする。
本発明で使用される前記一般式のフエノール性
物質はモノチオハイドロキノンと相当するジハロ
ゲノアルキルエーテルとをアルカリ性条件下で反
応させることにより、容易に高収率、高純度で、
且つ比較的安価に合成できる。
本発明において用いられるロイコ染料は、単独
又は２種以上混合して適用されるが、このような
ロイコ染料としては、この種の感熱記録材料に適
用されているものが任意に適用され、例えば、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
のロイコ化合物が好ましく用いられる。このよう
なロイコ染料の具体例としては、例えば、以下に
示すようなものが挙げられる。
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−ジメチルアミノフタリド（別名クリスタル
バイオレツトラクトン）、
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−ジメチルアミノフエニル）
−６−クロルフタリド、
３，３−ビス（ｐ−ジブチルアミノフエニル）
フタリド、
３−シクロヘキシルアミノ−６−クロルフルオ
ラン、
３−ジメチルアミノ−５，７−ジメチルフルオ
ラン、
３−Ｎ−メチル−Ｎ−イソブチルアミノ−６−
メチル−７−アニリノフルオラン、
３−Ｎ−エチル−Ｎ−アミル−６−メチル−７
−アニリノフルオラン、
３−ジエチルアミノ−７−クロロフルオラン、
３−ジエチルアミノ−７−メチルフルオラン、
３−ジエチルアミノ−７，８−ベンズフルオラ
ン、
３−ジエチルアミノ−６−メチル−７−クロル
フルオラン、
３−（Ｎ−ｐ−トリル−Ｎ−エチルアミノ）−６
−メチル−７−アニリノフルオラン、
３−ピロリジノ−６−メチル−７−アニリノフ
ルオラン、
２−｛Ｎ−（3′−トリフルオルメチルフエニル）
アミノ｝−６−ジエチルアミノフルオラン、
２−｛３，６−ビス（ジエチルアミノ）−９−
（ｏ−クロルアニリノ）キサンチル安息香酸ラク
タム｝、
３−ジエチルアミノ−６−メチル−７−（ｍ−
トリクロロメチルアニリノ）フルオラン、
３−ジエチルアミノ−７−（ｏ−クロルアニリ
ノ）フルオラン、
３−ジブチルアミノ−７−（ｏ−クロルアニリ
ノ）フルオラン、
３−Ｎ−メチル−Ｎ−アミルアミノ−６−メチ
ル−７−アニリノフルオラン、
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、
３−ジエチルアミノ−６−メチル−７−アニリ
ノフルオラン、
３−ジエチルアミノ−６−メチル−７−（2′，
4′−ジメチルアニリノ）フルオラン、
３−（Ｎ，Ｎ−ジエチルアミノ）−５−メチル−
７−（Ｎ，Ｎ−ジベンジルアミノ）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、
３−（2′−ヒドロキシ−4′−ジメチルアミノフ
エニル）−３−（2′−メトキシ−5′−クロルフエニ
ル）フタリド、
３−（2′−ヒドロキシ−4′−ジメチルアミノフ
エニル）−３−（2′−メトキシ−5′−ニトロフエニ
ル）フタリド、
３−（2′−ヒドロキシ−4′−ジエチルアミノフ
エニル）−３−（2′−メトキシ−5′−メチルフエニ
ル）フタリド、
３−（2′−メトキシ−4′−ジメチルアミノフエ
ニル）−３−（2′−ヒドロキシ−4′−クロル−5′−
メチルフエニル）フタリド、
３−モルホリノ−７−（Ｎ−プロピル−トリフ
ルオロメチルアニリノ）フルオラン、
３−ピロリジノ−７−トリフルオロメチルアニ
リノフルオラン、
３−ジエチルアミノ−５−クロロ−７−（Ｎ−
ベンジル−トリフルオロメチルアニリノ）フルオ
ラン、
３−ピロリジノ−７−（ジ−ｐ−クロルフエニ
ル）メチルアミノフルオラン、
３−ジエチルアミノ−５−クロル−７−（α−
フエニルエチルアミノ）フルオラン、
３−（Ｎ−エチル−ｐ−トルイジノ）−７−（α
−フエニルエチルアミノ）フルオラン、
３−ジエチルアミノ−７−（ｏ−メトキシカル
ボニルフエニルアミノ）フルオラン、
３−ジエチルアミノ−５−メチル−７−（α−
フエニルエチルアミノ）フルオラン、
３−ジエチルアミノ−７−ピペリジノフルオラ
ン、
２−クロロ−３−（Ｎ−メチルトルイジノ）−７
−（ｐ−ｎ−ブチルアニリノ）フルオラン、
３−（Ｎ−メチル−Ｎ−イソプロピルアミノ）−
６−メチル−７−アニリノフルオラン、
３−ジブチルアミノ−６−メチル−７−アニリ
ノフルオラン、
３，６−ビス（ジメチルアミノ）フルオレンス
ピロ（９，3′）−６−ジメチルアミノフタリド、
３−（Ｎ−ベンジル−Ｎ−シクロヘキシルアミ
ノ）−５，６−ベンゾ−７−α−ナフチルアミノ
−4′−ブロモフルオラン、
３−ジエチルアミノ−６−クロル−７−アニリ
ノフルオラン、
３−Ｎ−エチル−Ｎ−（２−エトキシプロピル）
アミノ−６−メチル−７−アニリノフルオラン、
３−Ｎ−エチル−Ｎ−テトラヒドロフルフリル
アミノ−６−メチル−７−アニリノフルオラン、
３−ジエチルアミノ−６−メチル−７−メシチ
ジノ−4′，5′−ベンゾフルオラン等。
本発明において好ましく使用されるロイコ染料
は前記一般式
（式中、R1及びR2はそれぞれ炭素数１〜６のア
ルキル基又はシクロヘキシル基、及びR3は炭素
数１〜２のアルキル基であり、ｎは０又は１の数
を示す）
で表わされるフルオラン化合物である。
このようなフルオラン化合物の具体例として
は、例えば、３−ジエチルアミノ−６−メチル−
７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ
−イソアミルアミノ）−６−メチル−７−アニリ
ノフルオラン、３−（Ｎ−メチル−Ｎ−ノルマル
ヘキシルアミノ）−６−メチル−７−アニリノフ
ルオラン、３−（Ｎ−シクロヘキシル−Ｎ−メチ
ルアミノ）−６−メチル−７−アニリノフルオラ
ンなどが挙げられ、これらのものは単独又は２種
以上の混合物の形で適用される。
ここでロイコ染料と前記式のフエノール性化合
物との比率は１：１〜６（重量）程度が適当であ
る。
前記一般式で表わされるフエノール性物質にお
いて、Ｒはエーテル基を１〜５個含有するアルキ
レン基であるが、この場合、エーテル基はアルキ
レン基の主鎖中にあつてもよく、また側鎖にあつ
てもよい。このエーテル基含有アルキレン基中に
含まれる炭素数は通常２〜15個の範囲である。本
発明において採用する好ましいエーテル基含有ア
ルキレン基は、エーテル結合１〜３個を含有し、
かつ炭素数２〜７個を有するものである。前記一
般式で表わされるフエノール性物質の具体例とし
ては以下に示すものが挙げられる。また、本発明
においては、必要に応じ、慣用の顕色剤の併用を
妨げるものではない。
The present invention relates to a heat-sensitive recording material, and particularly to a heat-sensitive recording material that has excellent color development and other recording suitability, and has good image stability. General heat-sensitive recording materials are coated on a support such as paper or film, and contain a colorless or light-colored color-forming dye such as a leuco dye as a color-forming agent, and a phenolic compound (especially bisphenol A) as a color-developing agent that causes the dye to develop color when heated. , a coloring system consisting of an acidic substance such as an organic acid, further provided with a heat-sensitive coloring layer in which binders, fillers, sensitivity improvers, lubricants, and other auxiliary agents are dispersed. It was introduced in Publication No. 45-14039, Japanese Patent Application Laid-open No. 48-27736, etc., and has been widely put into practical use. This type of thermal recording sheet produces colored images through an instantaneous chemical reaction between a coloring agent and a color developer during heating (a thermal printer or facsimile machine with a built-in thermal head is used for heating). Therefore, compared to other recording materials, recording can be obtained in a short time using relatively simple equipment without complicated processing such as development and fixing, there is less noise generation and environmental pollution, and the cost is low. Due to these advantages, it is useful not only for copying books, documents, etc., but also as a recording material for various information and measuring instruments such as electronic computers, facsimile machines, telex machines, and medical measuring instruments. On the other hand, in recent years, along with the development of society, there has been an increasing demand for higher speed and higher density recording. For this reason, there is a strong desire not only to increase the speed of the recording apparatus itself, but also to develop recording materials that can support this speed. Therefore, from this point of view, Japanese Patent Application Laid-open No.
No. 39139, JP-A-53-26139, JP-A-53-5636
No. 53-11036, etc., in addition to the above-mentioned heat-sensitive coloring layer, various waxes, fatty acid amides, alkylated biphenyl, substituted biphenyl alkanes,
It has been proposed that heat-melting substances with low melting points such as coumarins and diphenylamines are added as sensitizers (or melting point depressants). However, in the method of adding a sensitizer, it is necessary to melt the sensitizer before the color reaction occurs, so it is difficult to obtain sufficient thermal response in high-speed recording where only a small amount of heat is supplied in a short pulse. However, since the sensitizer in the coloring layer melts, there are problems in recording suitability, such as adhesion of residue to the thermal head, smearing, trailing, ghosting, and other problems. Furthermore, when stored at high temperatures and/or high humidity, fogging occurs over time and often reduces the contrast of recorded images. Therefore, it is desirable that a heat-sensitive recording sheet for high-speed recording has a structure in which no sensitizer is added. However, colorless or light-colored color-forming dyes used in heat-sensitive recording sheets usually have a high temperature of 160 to 240°C, so in order to construct a heat-sensitive color-forming layer suitable for high-speed recording without adding a sensitizer, it is necessary to have a low melting point. Moreover, it is essential to use a color developer that has a large ability to develop color from the color former. By the way, acidic substances, especially phenolic compounds, that can be combined with colorless or light-colored dyes are described in various documents, including Japanese Patent Publication No. 45-14039, but among these, bisphenol A has a stable quality. ,Low price,
It is widely used due to its ease of acquisition. However, since this bisphenol A has a high melting point of 156 to 158° C., it has the disadvantage of low thermal sensitivity (therefore, a high thermal coloring temperature). In contrast, phenolic compounds with low melting points, such as 4-t-butylphenol (melting point 94-99°C), α-naphthol (melting point
95-96℃), β-naphthol (melting point 119-122℃)
When such monophenols are used, the storage stability of the heat-sensitive recording sheet is poor, fogging gradually occurs even at room temperature, and a so-called phenol odor is strong, making it impractical. Also, special public service in 1977-
No. 12819 contains 2,2-bis(4'-hydroxyphenyl) normal hexane (melting point 99-103℃),
In JP-A No. 55-27253, 1,1-bis(4'-hydroxyphenyl)alkane (alkane has 3 to 13 carbon atoms) is used to provide a material with high heat sensitivity, storage stability, and color development. Although it has been described that good heat-sensitive recording sheets can be made, all of these materials are difficult to synthesize and have problems in availability. Furthermore, JP-A-56-144193 describes that lower alkyl esters or benzyl esters of p-hydroxybenzoic acid are easy to synthesize, and that high-sensitivity heat-sensitive recording sheets can be made using them. However, the colored part of this product tends to fade over time,
Moreover, it has a storage disadvantage in that crystals of the phenolic compound precipitate (so-called white powder phenomenon). As mentioned above, conventional heat-sensitive recording sheets for high-speed recording, those using sensitizers or melting point depressants, and those without, each have their own advantages and disadvantages, and none of them can be said to be practical. The first object of the present invention is to provide a film that does not require the use of sensitizers or melting point depressants, has excellent thermal responsiveness and recording suitability, and has excellent storage stability and image contrast even under high temperature and/or high humidity conditions. An object of the present invention is to provide a heat-sensitive recording material. The second object of the present invention is to provide an extremely practical thermosensitive record that has excellent storage stability at room temperature, no phenol odor, and no problems in availability despite the use of a highly heat-sensitive phenolic compound. The goal is to provide materials. That is, the heat-sensitive recording material of the present invention uses the general formula (In the formula, R represents an alkylene group containing 1 to 5 ether bonds.) It is characterized by using a phenolic substance represented by the following formula. The phenolic substance of the general formula used in the present invention can be easily obtained in high yield and with high purity by reacting monothiohydroquinone with the corresponding dihalogenoalkyl ether under alkaline conditions.
Moreover, it can be synthesized at relatively low cost. The leuco dyes used in the present invention may be applied singly or in a mixture of two or more types, and as such leuco dyes, those applied to this type of heat-sensitive recording material can be arbitrarily applied, for example, Leuco compounds of triphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based, and spiropyran-based dyes are preferably used. Specific examples of such leuco dyes include those shown below. 3,3-bis(p-dimethylaminophenyl)
-phthalide, 3,3-bis(p-dimethylaminophenyl)
-6-dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis(p-dimethylaminophenyl)
-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)
-6-chlorphthalide, 3,3-bis(p-dibutylaminophenyl)
Phthalide, 3-cyclohexylamino-6-chlorofluoran, 3-dimethylamino-5,7-dimethylfluoran, 3-N-methyl-N-isobutylamino-6-
Methyl-7-anilinofluorane, 3-N-ethyl-N-amyl-6-methyl-7
-anilinofluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7,8-benzfluorane, 3-diethylamino-6-methyl-7-chlorofluoran Oran, 3-(N-p-tolyl-N-ethylamino)-6
-Methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2-{N-(3'-trifluoromethylphenyl)
amino}-6-diethylaminofluorane, 2-{3,6-bis(diethylamino)-9-
(o-chloroanilino)xantylbenzoic acid lactam}, 3-diethylamino-6-methyl-7-(m-
trichloromethylanilino)fluoran, 3-diethylamino-7-(o-chloroanilino)fluoran, 3-dibutylamino-7-(o-chloroanilino)fluoran, 3-N-methyl-N-amylamino-6-methyl-7- Anilinofluorane, 3-N-methyl-N-cyclohexylamino-
6-Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-(2',
4'-dimethylanilino)fluoran, 3-(N,N-diethylamino)-5-methyl-
3 -(2'-Hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-chlorophenyl)phthalide, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3- (2'-Methoxy-5'-nitrophenyl)phthalide, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenyl)phthalide, 3-(2'- Methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chloro-5'-
methylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7-(N-
benzyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluorane, 3-diethylamino-5-chloro-7-(α-
phenylethylamino)fluoran, 3-(N-ethyl-p-toluidino)-7-(α
-phenylethylamino)fluoran, 3-diethylamino-7-(o-methoxycarbonylphenylamino)fluoran, 3-diethylamino-5-methyl-7-(α-
phenylethylamino)fluorane, 3-diethylamino-7-piperidinofluorane, 2-chloro-3-(N-methyltoluidino)-7
-(p-n-butylanilino)fluoran, 3-(N-methyl-N-isopropylamino)-
6-Methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3,6-bis(dimethylamino)fluorenespiro(9,3')-6-dimethylaminophthari 3-(N-benzyl-N-cyclohexylamino)-5,6-benzo-7-α-naphthylamino-4'-bromofluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-N-ethyl-N-(2-ethoxypropyl)
Amino-6-methyl-7-anilinofluorane, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-mesitidino-4 ′,5′-benzofluorane etc. The leuco dye preferably used in the present invention has the general formula (In the formula, R 1 and R 2 are each an alkyl group or a cyclohexyl group having 1 to 6 carbon atoms, R 3 is an alkyl group having 1 to 2 carbon atoms, and n represents the number 0 or 1.) It is a fluoran compound. Specific examples of such fluoran compounds include, for example, 3-diethylamino-6-methyl-
7-anilinofluorane, 3-(N-ethyl-N
-isoamylamino)-6-methyl-7-anilinofluorane, 3-(N-methyl-N-n-n-hexylamino)-6-methyl-7-anilinofluorane, 3-(N-cyclohexyl-N- Examples include methylamino)-6-methyl-7-anilinofluorane, which may be used alone or in the form of a mixture of two or more. Here, the ratio of the leuco dye to the phenolic compound of the above formula is suitably about 1:1 to 6 (by weight). In the phenolic substance represented by the above general formula, R is an alkylene group containing 1 to 5 ether groups; in this case, the ether group may be present in the main chain of the alkylene group, or may be present in the side chain. It may be hot. The number of carbon atoms contained in this ether group-containing alkylene group is usually in the range of 2 to 15. Preferred ether group-containing alkylene groups employed in the present invention contain 1 to 3 ether bonds,
and has 2 to 7 carbon atoms. Specific examples of the phenolic substance represented by the above general formula include those shown below. Furthermore, in the present invention, a conventional color developer may be used in combination, if necessary.
【表】【table】
１，８−ジ（４−ヒドロキシフエニルチオ）−３，
６−ジオキサオクタン（前記No.６の化合物、融点
100〜101℃） 20部
比較例 １
実施例１の〔Ｂ〕液の代りに下記〔Ｅ〕液を使
用する以外はすべて実施例１と同様にして感熱記
録シート(c)を作つた。
〔Ｅ液〕
ビスフエノールＡ 20部
ヒドロキシエチルセルロースの10％水溶液 20部
水 60部
比較例 ２
実施例１の〔Ｂ〕液の代りに下記〔Ｆ〕液を使
用する以外はすべて実施例１と同様にして感熱記
録シート(d)を作つた。
〔Ｆ液〕
ｐ−ヒドロキシ安息香酸ベンジルエステル 20部
ヒドロキシエチルセルロースの10％水溶液 20部
水 60部
以上のようにして得た感熱記録シート(a)〜(d)を
Ｇ−フアクシミリ装置（リフアツクス3300(株)リ
コー製）で高速で印字（印字速度：0.94ｍsec、
印加電圧：16V、18V、20V）し、その発色濃度
をマクベス濃度計RD−514（マクベス社製）で測
定した。その結果を表−１に示す。
また、上記印字物（印字速度：0.94ｍsec、印
加電圧：20Vのもの）を１週間放置後、再度発色
濃度をマクベス濃度計RD−514で測定した。ま
た、その時の発色部の白粉現象も観察した。その
結果を表−２に示す。
1,8-di(4-hydroxyphenylthio)-3,
6-dioxaoctane (compound No. 6 above, melting point
100-101°C) 20 parts Comparative Example 1 A thermosensitive recording sheet (c) was prepared in the same manner as in Example 1 except that the following liquid [E] was used instead of liquid [B] in Example 1. [Liquid E] Bisphenol A 20 parts 10% aqueous solution of hydroxyethyl cellulose 20 parts Water 60 parts Comparative Example 2 Everything is the same as Example 1 except that the following liquid [F] is used instead of liquid [B] of Example 1. I made a thermosensitive recording sheet (d). [Liquid F] 20 parts of p-hydroxybenzoic acid benzyl ester 20 parts of 10% aqueous solution of hydroxyethyl cellulose 60 parts of water The heat-sensitive recording sheets (a) to (d) obtained as above were transferred to a G-fax machine (Refax 3300 ( Ricoh Co., Ltd.) for high-speed printing (printing speed: 0.94 msec,
Applied voltage: 16 V, 18 V, 20 V), and the color density was measured using Macbeth Densitometer RD-514 (manufactured by Macbeth). The results are shown in Table-1. Further, after the above printed matter (printing speed: 0.94 msec, applied voltage: 20 V) was left for one week, the color density was measured again using a Macbeth densitometer RD-514. In addition, white powder phenomenon in the colored area was also observed at that time. The results are shown in Table-2.
【表】【table】
【表】
表−１、表−２より明らかなように、本発明の
感熱記録材料は高速記録時の発色性にすぐれ、発
色画像の極めて安定した感熱記録材料であること
が判る。[Table] As is clear from Tables 1 and 2, the heat-sensitive recording material of the present invention has excellent color development during high-speed recording and is a heat-sensitive recording material that produces extremely stable colored images.
Claims (1)
利用した感熱記録材料において、該顕色剤とし
て、一般式 （式中、Ｒはエーテル結合を１〜５個含有するア
ルキレン基である。） で表わされるフエノール性化合物を用いることを
特徴とする感熱記録材料。 ２ ロイコ染料が下記一般式で表わされるフルオ
ラン化合物である特許請求の範囲第１項記載の感
熱記録材料。 （式中、R1及びR2はそれぞれ炭素数１〜６のア
ルキル基又はシクロヘキシル基、及びR3は炭素
数１〜２のアルキル基であり、ｎは０又は１の数
を示す）[Scope of Claims] 1. In a heat-sensitive recording material that utilizes a color-forming reaction between a leuco dye and its color developer, as the color developer, the general formula (In the formula, R is an alkylene group containing 1 to 5 ether bonds.) A heat-sensitive recording material characterized by using a phenolic compound represented by the following formula. 2. The heat-sensitive recording material according to claim 1, wherein the leuco dye is a fluoran compound represented by the following general formula. (In the formula, R 1 and R 2 are each an alkyl group or a cyclohexyl group having 1 to 6 carbon atoms, and R 3 is an alkyl group having 1 to 2 carbon atoms, and n represents a number of 0 or 1.)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57163650A JPS5952694A (en) | 1982-09-20 | 1982-09-20 | Heat sensitive recording material |
| US06/527,899 US4502068A (en) | 1982-09-20 | 1983-08-30 | Thermosensitive recording material |
| GB08325134A GB2127985B (en) | 1982-09-20 | 1983-09-20 | Thermosensitive recording materials |
| FR8314923A FR2533167B1 (en) | 1982-09-20 | 1983-09-20 | THERMOSENSITIVE RECORDING MATERIAL |
| DE3333987A DE3333987C2 (en) | 1982-09-20 | 1983-09-20 | Thermosensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57163650A JPS5952694A (en) | 1982-09-20 | 1982-09-20 | Heat sensitive recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5952694A JPS5952694A (en) | 1984-03-27 |
| JPH0152198B2 true JPH0152198B2 (en) | 1989-11-08 |
Family
ID=15777965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57163650A Granted JPS5952694A (en) | 1982-09-20 | 1982-09-20 | Heat sensitive recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5952694A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2632717B2 (en) * | 1988-06-23 | 1997-07-23 | 株式会社リコー | Novel phenolic compound and recording material using the compound |
| US5702850A (en) | 1994-09-14 | 1997-12-30 | New Oji Paper Co., Ltd. | Thermosensitive reversible color-developing and disappearing agent |
-
1982
- 1982-09-20 JP JP57163650A patent/JPS5952694A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5952694A (en) | 1984-03-27 |
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| JPS60248395A (en) | Thermal recording material | |
| JPS6211676A (en) | Thermal recording material |