JPH0332475B2 - - Google Patents
Info
- Publication number
- JPH0332475B2 JPH0332475B2 JP58142800A JP14280083A JPH0332475B2 JP H0332475 B2 JPH0332475 B2 JP H0332475B2 JP 58142800 A JP58142800 A JP 58142800A JP 14280083 A JP14280083 A JP 14280083A JP H0332475 B2 JPH0332475 B2 JP H0332475B2
- Authority
- JP
- Japan
- Prior art keywords
- ester
- gallic acid
- heat
- sensitive recording
- 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 16
- 239000002243 precursor Substances 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N anhydrous gallic acid Natural products OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- 229940074391 gallic acid Drugs 0.000 claims description 6
- 235000004515 gallic acid Nutrition 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- -1 alkylidene bisphenols Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 2
- KBPUBCVJHFXPOC-UHFFFAOYSA-N Ethyl 3,4-dihydroxybenzoate Natural products CCOC(=O)C1=CC=C(O)C(O)=C1 KBPUBCVJHFXPOC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 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 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- VFPFQHQNJCMNBZ-UHFFFAOYSA-N ethyl gallate Chemical compound CCOC(=O)C1=CC(O)=C(O)C(O)=C1 VFPFQHQNJCMNBZ-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 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
- TYCUSKFOGZNIBO-UHFFFAOYSA-N hexadecyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 TYCUSKFOGZNIBO-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BRNPAEUKZMBRLQ-UHFFFAOYSA-N octadecyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 BRNPAEUKZMBRLQ-UHFFFAOYSA-N 0.000 description 2
- 235000010387 octyl gallate Nutrition 0.000 description 2
- NRPKURNSADTHLJ-UHFFFAOYSA-N octyl gallate Chemical compound CCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 NRPKURNSADTHLJ-UHFFFAOYSA-N 0.000 description 2
- 235000010388 propyl gallate Nutrition 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical class OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 1
- UCLHVCFKZSLALE-UHFFFAOYSA-N 2-methylpropyl 3,4,5-trihydroxybenzoate Chemical compound CC(C)COC(=O)C1=CC(O)=C(O)C(O)=C1 UCLHVCFKZSLALE-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- YBMTWYWCLVMFFD-UHFFFAOYSA-N 3-methylbutyl 3,4,5-trihydroxybenzoate Chemical compound CC(C)CCOC(=O)C1=CC(O)=C(O)C(O)=C1 YBMTWYWCLVMFFD-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical class OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- XOPOEBVTQYAOSV-UHFFFAOYSA-N butyl 3,4,5-trihydroxybenzoate Chemical compound CCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 XOPOEBVTQYAOSV-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019277 ethyl gallate Nutrition 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide 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
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
本発明は保存性を改良した感熱記録材料に関す
るものである。
感熱記録材料は一般に支持体上に電子供与性の
通常無色ないし淡色の染料前駆体と電子受容性の
顕色剤を主成分とする感熱記録層を設けたもの
で、熱ヘツド、熱ペン、レーザー光等で加熱する
ことにより染料前駆体と顕色剤とが瞬時反応し、
記録画像を得るもので、特公昭43−4160号、特公
昭45−14039号公報等に開示されている。このよ
うな感熱記録材料は比較的簡単な装置で記録が得
られ、保守が易容であること、騒音の発生がない
ことなどの利点があり、計測用記録計、フアクシ
ミリ、プリンター、コンピユーターの端末機、ラ
ベル、乗車券等自動券売機など広範囲の分野に利
用されている。
感熱記録材料に要求される基本的性能として
は、十分な発色画像濃度及び感度をもつこと、地
肌のカブリ（未発色部分の経時による発色現象）
がないこと、経時による発色画像の劣化がないこ
となどがある。また近年、印字記録の高速化が進
められ記録装置自体の高速化と共にそれに対応で
きる記録シートの開発、すなわち、画像の高濃度
化が望まれている。さらに、感熱記録材料が広く
用いられるようになるとともに、水が付着した時
の画像の安定性（画像の耐水性）、ジアゾ複写紙
と重ね合わせた時に地肌カブリしないこと、整髪
料や皮膚の汗に含まれる油脂類などの油状物の付
着による画像の安定性（耐油脂性）等、種々の特
性が要求されるようになりこれらを十分満すよう
な感熱記録材料が望まれるようになつてきた。
顕色剤からの検討も広く行なわれ、特開昭54−
155059号、同55−27253号にはアルキリデンビス
フエノール類、特開昭57−156293号にはジヒドロ
キシ安息香酸エステル、特開昭57−128594号、同
57−129787号にはモノヒドロキシ安息香酸エステ
ルが開示されている。しかしながら現在、感熱記
録材料に望まれる諸特性を完全に満足するものは
得られていない。
本発明者らは顕色剤について種々検討した結
果、通常無色ないし淡色の染料前駆体と、加熱時
反応して該染料前駆体を発色せしめる顕色剤を含
有する感熱記録材料において、顕色剤に下記一般
式で示される没食子酸アルキルエステルを用いる
こと
一般式
（Ｒ：炭素数16以上のアルキル基）
により、画像濃度、保存性等諸特性を満足しうる
感熱記録材料を得ることができた。
本発明による没食子酸アルキルエステルは、類
似構造をもつモノヒドロキシ安息香酸エステル、
ジヒドロキシ安息香酸エステルに比べ同程度の発
色濃度をもつうえにジアゾ複写紙との重ね合わせ
による地肌カブリが著しく少なく、画像の耐油脂
性が極めて高く、水による画像劣化が非常に少な
い等両者にはみられない特有の特性をもつことを
見出だした。
本発明に用いられる没食子酸アルキルエステル
の具体例としては、没食子酸メチルエステル、没
食子酸エチルエステル、没食子酸プロピルエステ
ル、没食子酸ブチルエステル、没食子酸イソブチ
ルエステル、没食子酸イソアミルエステル、没食
子酸オクチルエステル、没食子酸ラウリルエステ
ル、没食子酸セチルエステル、没食子酸ステアリ
ルエステル、没食子酸ベヘニルエステル等が挙げ
られる。
本発明に用いられる主な成分を具体的に説明す
るが、本発明の要旨を越えない限り、本発明を限
定するものではない。染料前駆体としては、一般
に感熱紙に使用される染料前駆体が使用でき、例
えばクリスタルバイオレツトラクトン、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−６−クロロ−７−メチルフルオラン、
３−ジエチルアミノ−６−メチル−７−クロロフ
ルオラン、３−ジエチルアミノ−７−アニリノフ
ルオラン、３−ジエチルアミノ−７−（２−クロ
ロアニリノ）フルオラン、３−ジブチルアミノ−
７−（２−クロロアニリノ）フルオラン、３−ジ
エチルアミノ−７−（３−クロロアニリノ）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−（Ｎ−エチル−Ｐ−ト
ルイジノ）−６−メチル−７−アニリノフルオラ
ン、３−（Ｎ−メチルシタロヘキシルアミノ）−３
−メチル−７−アニリノフルオラン、３−ピペリ
ジノ−３−メチル−７−アニリノフルオラン、な
ど。
結着剤としては例えば、でん粉類、ヒドロキシ
エチルセルロース、メチルセルロース、ポリビニ
ルアルコール、スチレン−無水マレイン酸共重合
体、スチレン−ブタジエン共重合体、ポリアクリ
ルアミド、など。
その他の添加剤として例えばケイソウ土、タル
ク、カオリン、焼成カオリン、炭酸カルシウム、
炭酸マグネシウム、酸化チタン、酸化亜鉛、酸化
ケイ素、水酸化アルミニウム、尿素−ホルマリン
樹脂などの顔料、ステアリン酸亜鉛、ステアリン
酸アルミニウム、ステアリン酸カルシウムなどの
高級脂肪酸金属塩、その他、必要に応じて感度向
上剤、紫外線吸収剤、界面活性剤、消泡剤などが
あげられる。
以下実施例を示し、更に詳細に説明するが、本
発明はこの実施例のみに限定されるものではな
い。
参考例 １
３−ジエチルアミノ−６−メチル−７−アニリ
ノフルオラン20ｇを２％ポリビニルアルコール水
溶液60ｇとともにボールミルで24時間分散した。
一方没食子酸メチルエステル40ｇを２％ポリビニ
ルアルコール水溶液120ｇとともにボールミルで
24時間分散した。これらの分散液を混合し、炭酸
カルシウムの50％分散液100ｇを加え、さらにス
テアリン酸亜鉛の20％分散液100ｇ、15％ポリビ
ニルアルコール水溶液220ｇ、水155ｇを加えて塗
液とした。塗液を坪量50ｇ／m2の原紙に乾燥後の
塗布量が4.5ｇ／m2になるように塗布し、スーパ
ーカレンダーで処理し感熱記録材料を作成した。
参考例２〜４及び実施例１〜２
参考例１の没食子酸メチルエステルのかわり
に、それぞれ没食子酸プロピルエステル、没食子
酸オクチルエステル、没食子酸ラウリルエステ
ル、没食子酸セチルエステル、没食子酸ステアリ
ルエステルを用いる以外は参考例１と同様にして
感熱記録材料を作製した。
比較例 １〜３
参考例１の没食子酸メチルエステルのかわりに
それぞれ２，２−ビス（４−ヒドロキシフエニ
ル）プロパン、４−ヒドロキシ安息香酸ベンジル
エステル、３，４−ジヒドロキシ安息香酸エチル
エステルを用いる以外は参考例１と同様にして感
熱記録材料を作製した。
参考例１〜４及び実施例１〜２及び比較例１〜
３で作製した感熱記録材料について以下に記す試
験を行ない評価した。
試 験
感熱フアクシミリ試験機を用いて印加パルス巾
3.0ミリ秒、印加電圧15.97ボルトの条件で印字
し、発色画像を得たのち、下記に示す保存試験を
行つた。結果を表１に示した。なお地肌及び発色
画像の濃度はマクベス濃度計を用いて測定した。
ａ 発色濃度を測定した。
ｂ 耐水性試験；３リツトルの水に24時間浸漬し
たのちの画像濃度を測定し画像残存率をもとめ
た。
画像残存率（％）＝試験後の画像濃度／試験前の画像
濃度×100
ｃ 耐油脂性試験；整髪剤、バイタリス（ライオ
ン株式会社製）を充填したフエルトペンにて画
像部を筆記し、画像部上にバイタリスの薄層を
ひいて20分放置したのち画像濃度を測定し画像
残存率をもとめた。
ｄ ジアゾ複写紙による地肌カブリ；ジアゾ複写
紙と未発色の感熱記録材料と各々の表面を重ね
合わせたのち24時間保存し、地肌の濃度を測定
した。値が大きい程地肌のカブリが大きく商品
価値は著しく低下する。
The present invention relates to a heat-sensitive recording material with improved storage stability. Heat-sensitive recording materials generally have a heat-sensitive recording layer on a support, the main components of which are an electron-donating, usually colorless or light-colored dye precursor and an electron-accepting developer. By heating with light etc., the dye precursor and developer react instantly,
This method is used to obtain a recorded image, and is disclosed in Japanese Patent Publication No. 43-4160, Japanese Patent Publication No. 14039-1974, etc. These heat-sensitive recording materials have the advantages of being able to record with relatively simple equipment, being easy to maintain, and producing no noise. It is used in a wide range of fields such as automatic ticket vending machines, labels, and ticket vending machines. The basic performance required of heat-sensitive recording materials is to have sufficient color image density and sensitivity, and to prevent fogging on the background (a phenomenon in which uncolored areas develop color over time).
In some cases, there is no deterioration of colored images over time. In addition, in recent years, the speed of printing and recording has been increasing, and as the speed of the recording apparatus itself has increased, there has been a demand for the development of recording sheets that can cope with the speed increase, that is, higher image density. Furthermore, with the widespread use of heat-sensitive recording materials, the stability of images when exposed to water (image water resistance), the fact that the skin does not fog when layered with diazo copy paper, hair products and skin sweat, etc. Various properties have become required, such as image stability (oil resistance) due to the adhesion of oils and fats contained in . A wide range of studies were also conducted on color developers, and
No. 155059 and No. 55-27253 contain alkylidene bisphenols, JP-A No. 57-156293 contains dihydroxybenzoic acid esters, JP-A No. 57-128594 and No. 128-594 contain alkylidene bisphenols;
No. 57-129787 discloses monohydroxybenzoic acid esters. However, at present, no heat-sensitive recording material has been obtained that completely satisfies the various properties desired for a heat-sensitive recording material. As a result of various studies on color developers, the inventors of the present invention found that in heat-sensitive recording materials containing a normally colorless or light-colored dye precursor and a color developer that reacts with the dye precursor when heated to develop a color, the color developer Using a gallic acid alkyl ester represented by the general formula below.General formula (R: alkyl group having 16 or more carbon atoms) It was possible to obtain a heat-sensitive recording material that can satisfy various properties such as image density and storage stability. The gallic acid alkyl ester according to the present invention is a monohydroxybenzoic acid ester having a similar structure,
It has the same color density as dihydroxybenzoic acid ester, has significantly less background fog when overlaid with diazo copy paper, has extremely high oil and fat resistance, and has very little image deterioration due to water, etc. We have discovered that it has unique characteristics that make it difficult to use. Specific examples of gallic acid alkyl esters used in the present invention include gallic acid methyl ester, gallic acid ethyl ester, gallic acid propyl ester, gallic acid butyl ester, gallic acid isobutyl ester, gallic acid isoamyl ester, gallic acid octyl ester, Examples include gallic acid lauryl ester, gallic acid cetyl ester, gallic acid stearyl ester, gallic acid behenyl ester, and the like. The main components used in the present invention will be specifically explained, but the present invention is not limited thereto unless it exceeds the gist of the present invention. As the dye precursor, dye precursors generally used for thermal paper can be used, such as crystal violet lactone, 3-diethylamino-7-methylfluoran, 3-diethylamino-6-chloro-7-methylfluoran,
3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-7-(2-chloroanilino)fluorane, 3-dibutylamino-
7-(2-chloroanilino)fluoran, 3-diethylamino-7-(3-chloroanilino)fluoran, 3-diethylamino-6-methyl-7-
Anilinofluorane, 3-(N-ethyl-P-toluidino)-6-methyl-7-anilinofluorane, 3-(N-methylcitalohexylamino)-3
-Methyl-7-anilinofluorane, 3-piperidino-3-methyl-7-anilinofluorane, etc. Examples of the binder include starch, hydroxyethylcellulose, methylcellulose, polyvinyl alcohol, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, polyacrylamide, and the like. Other additives include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate,
Pigments such as magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin, higher fatty acid metal salts such as zinc stearate, aluminum stearate, calcium stearate, and other sensitivity improvers as necessary. , ultraviolet absorbers, surfactants, antifoaming agents, etc. Examples will be shown below and explained in more detail, but the present invention is not limited only to these examples. Reference Example 1 20 g of 3-diethylamino-6-methyl-7-anilinofluorane and 60 g of a 2% polyvinyl alcohol aqueous solution were dispersed in a ball mill for 24 hours.
On the other hand, 40 g of gallic acid methyl ester was mixed with 120 g of a 2% polyvinyl alcohol aqueous solution in a ball mill.
Dispersed for 24 hours. These dispersions were mixed, 100 g of a 50% dispersion of calcium carbonate was added, 100 g of a 20% dispersion of zinc stearate, 220 g of a 15% aqueous polyvinyl alcohol solution, and 155 g of water were added to prepare a coating liquid. The coating liquid was applied to a base paper having a basis weight of 50 g/m 2 so that the coated amount after drying was 4.5 g/m 2 and treated with a supercalender to prepare a heat-sensitive recording material. Reference Examples 2 to 4 and Examples 1 to 2 Instead of gallic acid methyl ester in Reference Example 1, gallic acid propyl ester, gallic acid octyl ester, gallic acid lauryl ester, gallic acid cetyl ester, and gallic acid stearyl ester are used, respectively. A heat-sensitive recording material was produced in the same manner as in Reference Example 1 except for this. Comparative Examples 1 to 3 2,2-bis(4-hydroxyphenyl)propane, 4-hydroxybenzoic acid benzyl ester, and 3,4-dihydroxybenzoic acid ethyl ester are used instead of gallic acid methyl ester in Reference Example 1, respectively. A heat-sensitive recording material was produced in the same manner as in Reference Example 1 except for this. Reference Examples 1-4, Examples 1-2, and Comparative Examples 1-
The heat-sensitive recording material prepared in step 3 was evaluated by conducting the following tests. Test The applied pulse width was measured using a heat-sensitive facsimile tester.
After printing under the conditions of 3.0 milliseconds and an applied voltage of 15.97 volts to obtain a colored image, the following storage test was conducted. The results are shown in Table 1. The densities of the background and colored images were measured using a Macbeth densitometer. a Color density was measured. b Water resistance test: After immersing in 3 liters of water for 24 hours, the image density was measured to determine the image survival rate. Image survival rate (%) = Image density after test / Image density before test x 100c Oil and fat resistance test: Write down the image area with a felt tip pen filled with hair conditioner, Vitalis (manufactured by Lion Corporation), and write down the image area. A thin layer of Vitalis was placed on top and left for 20 minutes, then the image density was measured and the image survival rate was determined. d. Background fog due to diazo copying paper; After the surfaces of the diazo copying paper and the uncolored heat-sensitive recording material were superimposed, they were stored for 24 hours, and the density of the background was measured. The larger the value, the greater the fogging on the background, and the greater the product value.
【表】
表１の結果より、本発明による没食子酸アルキ
ルエステルは十分な発色濃度をもつと共に画像の
耐水性、耐油脂性に優れ、地肌の保存性にも優れ
ていることがわかる。[Table] From the results in Table 1, it can be seen that the gallic acid alkyl ester according to the present invention has sufficient color density, and has excellent water resistance and oil resistance of images, as well as excellent preservability of the background.
Claims (1)
反応して該染料前駆体を発色せしめる顕色剤を含
有する感熱記録材料において、該顕色剤が下記一
般式で示される没食子酸アルキルエステルである
ことを特徴とする感熱記録材料。 一般式 （Ｒ：炭素数16以上のアルキル基）[Scope of Claims] 1. A heat-sensitive recording material containing a normally colorless or light-colored dye precursor and a color developer that reacts with the dye precursor when heated to develop a color, wherein the color developer is represented by the following general formula. A heat-sensitive recording material characterized by being a gallic acid alkyl ester. general formula (R: alkyl group having 16 or more carbon atoms)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58142800A JPS6032697A (en) | 1983-08-04 | 1983-08-04 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58142800A JPS6032697A (en) | 1983-08-04 | 1983-08-04 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6032697A JPS6032697A (en) | 1985-02-19 |
| JPH0332475B2 true JPH0332475B2 (en) | 1991-05-13 |
Family
ID=15323920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58142800A Granted JPS6032697A (en) | 1983-08-04 | 1983-08-04 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6032697A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55152135A (en) * | 1979-05-11 | 1980-11-27 | Fuji Photo Film Co Ltd | Recovering method and apparatus for silver from photographic treating procedure |
| JPS61211087A (en) * | 1985-03-15 | 1986-09-19 | Ricoh Co Ltd | Thermal recording material |
| JPH0710628B2 (en) * | 1985-05-17 | 1995-02-08 | 株式会社リコー | Thermal recording material |
| JPS62105688A (en) * | 1985-11-01 | 1987-05-16 | Jujo Paper Co Ltd | Thermosensitive recording medium |
| JPS6398488A (en) * | 1986-10-15 | 1988-04-28 | Honshu Paper Co Ltd | Thermal recording material |
| EP0520404B1 (en) * | 1991-06-24 | 1996-09-11 | Nippon Paper Industries Co., Ltd. | Transparent recording medium |
| DE102015119428B3 (en) | 2015-11-11 | 2016-03-24 | Papierfabrik August Koehler Se | Heat-sensitive recording material and method for its production |
-
1983
- 1983-08-04 JP JP58142800A patent/JPS6032697A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6032697A (en) | 1985-02-19 |
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