JPH0559837B2 - - Google Patents
Info
- Publication number
- JPH0559837B2 JPH0559837B2 JP60280493A JP28049385A JPH0559837B2 JP H0559837 B2 JPH0559837 B2 JP H0559837B2 JP 60280493 A JP60280493 A JP 60280493A JP 28049385 A JP28049385 A JP 28049385A JP H0559837 B2 JPH0559837 B2 JP H0559837B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive recording
- recording material
- dye precursor
- general formula
- 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 25
- 239000002243 precursor Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- QRQPUJRXMQTTLU-UHFFFAOYSA-N 2-benzylsulfanylnaphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1SCC1=CC=CC=C1 QRQPUJRXMQTTLU-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 230000004043 responsiveness Effects 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 229940037312 stearamide Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- -1 paraffin oxide Chemical compound 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DCDUWZAHMMXKRE-UHFFFAOYSA-N 1-benzylsulfanylnaphthalene Chemical compound C=1C=CC2=CC=CC=C2C=1SCC1=CC=CC=C1 DCDUWZAHMMXKRE-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000011230 binding agent 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
- 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 239000001993 wax Substances 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
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- UWPJWCBDMZHMTN-UHFFFAOYSA-N 4-(4-phenylmethoxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C(C=C1)=CC=C1OCC1=CC=CC=C1 UWPJWCBDMZHMTN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 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
- 241000254158 Lampyridae Species 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 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
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-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
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 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
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 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
- 239000004519 grease Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- XIKIUQUXDNHBFR-UHFFFAOYSA-N monobenzyl phthalate Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 XIKIUQUXDNHBFR-UHFFFAOYSA-N 0.000 description 1
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000004321 preservation Methods 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
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid 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
- 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
- 239000003232 water-soluble binding agent Substances 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
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
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
(A) 産業上の利用分野
本発明は感熱記録材料に関し、特に熱応答性、
画像保存性を向上させた感熱記録材料に関する。
(B) 従来技術
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
顕色剤と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、
記録画像が得られるもので、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、保守が容易であること、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、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材
料、すなわち低い熱エネルギーで高濃度の発色画
像が得られる熱応答性に優れている感熱記録材料
の開発が望まれている。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整髪料、ハンド
クリーム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保存性（耐脂性）等の特性
も要求されるようになり、熱応答性、画像保存性
を十分満たすように感熱記録材料が望まれるよう
になつてきた。
従来より高濃度の発色画像を得るために各種添
加剤を記録層中に含有させる方法が知られてい
る。例えば、特公昭43−4160号には尿素、無水フ
タル酸、アセトアニリド等を、特公昭48−19231
号には密ろう、カルナウバろう、パラフインワツ
クス等の天然及び合成ワツクス類を、特公昭49−
17748号にはサリチル酸、フタル酸モノベンジル
エステル等を添加する方法が開示されている。
また、画像保存性を向上させるために、ビス
（４−ヒドロキシフエニル）スルホンを顕色剤と
して用いる事が特開昭58−119893号に記載されて
いる。
しかしながら、熱応答性が悪く十分な濃度が得
られなかつたり、高濃度の画像が得られても保存
性が悪く、経時的に劣化する等の欠点があり満足
できるものは得られていない。
(C) 発明の目的
本発明の目的は、さらに熱応答性、画像保存性
に優れた感熱記録材料を得る事にある。
(D) 発明の構成
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とを
含有する感熱記録材料において、該顕色剤として
一般式(1)で示される化合物を含有させ、さらに２
−ベンジルチオナフタレンを含有する事により、
熱応答性、画像保存性に優れた感熱記録材料を得
ることができた。
一般式(1)
（式中Ｒはアルキル基、アルコキシ基、アラルキ
ルオキシ基又はハロゲン原子を表わす）
顕色剤として、一般式(1)で示される化合物を使
用する事により、画像保存性の良好な感熱記録材
料を得ることができるが、熱応答性が満足できる
ものでなく、添加剤を種々検討したところ、２−
ベンジルチオナフタレンを添加する事により、熱
応答性が向上した。一般式(1)で示される化合物の
具体例としては、４−ヒドロキシ−4′−メチルジ
フエニルスルホン、４−ヒドロキシ−4′−イソプ
ルピルオキシジフエニルスルホン、４−クロロ−
4′−ヒドロキシジフエニルスルホン、４−ベンジ
ルオキシ−4′−ヒドロキシジフエニルスルホン等
が挙げられる。
本発明による一般式(1)で示される化合物及び２
−ベンジルチオナフタレンは、通常染料前駆体に
体して各々５重量％以上添加される。
好ましい量は10−600重量％であり、特に20−
500重量％が好ましい。添加量が５重量％未満で
は、熱応答性、画像保存性が十分でなく、600重
量％より多い添加では熱ヘツド等への熱可融物付
着が増加し、印字障害が生じる場合もある。
また、ステアリン酸アミド、Ｎ−ヒドロキシメ
チルステアリン酸アミド等の融点80℃〜160℃の
熱可融物を添加する事により熱応答性がさらに向
上する。
本発明の感熱記録材料に用いられる主な成分を
以下に具体的に説明する。
染料前駆体としては、トリフエニルメタン系、
フルオラン系、ジフエニルメタン系、チアジン
系、スピロピラン系化合物などが挙げられる。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−メチルシクロヘキシルアミノ）
−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
等がある。
バインダーとしては、デンプン類、ヒドロキシ
エチルセルロース、メチルセルロース、カルボキ
シメチルセルロース、ゼラチン、カゼイン、ポリ
ビニルアルコール、変性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、エチレン−
無水マレイン酸共重合体などの水溶性バインダ
ー、スチレン−ブタジエン共重合体、アクリロニ
トリル−ブタジエン共重合体、アクリル酸メチル
−ブタジエン共重合体などのラテツクス系水不溶
性バインダーなどが挙げられる。
顔料としては、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が
挙げられる。
その他に、ヘツド摩耗防止、ステイツキング防
止などの目的でステアリン酸亜鉛、ステアリン酸
カルシウム等の高級脂肪酸金属塩、パラフイン、
酸化パラフイン、ポリエチレン、酸化ポリエチレ
ン、ステアリン酸アミド、カスタ−ワツクス等の
ワツクス類を、また、ジオクチルスルホコハク酸
ナトリウム等の分散剤、ベンゾフエノン系、ベン
ゾトリアゾール系などの紫外線吸収剤、さらに界
面活性剤、螢光染料などが挙げられる。
本発明による感熱記録材に用いられる支持体と
しては紙が主として用いられるが、各種不織布、
プラスチツクフイルム、合成紙、金属箔等あるい
はこれらを組合わせた複合シートを任意に用いる
ことができる。
(E) 実施例
実施例によつて本発明をさらに詳しく説明す
る。
実施例 １
３−ジエチルアミノ−６−メチル−７−アニリ
ノフルオラン10ｇを２％ポリビニルアルコール水
溶液30ｇと共にボールミルで24時間分散した。
一方、４−ヒドロキシ−4′−メチルジフエニル
スルホン25ｇを２％ポリビニルアルコール水溶液
75ｇと共に、ボールミルで24時間分散し、また別
に２−ベンジルチオナフタレン25ｇを２％ポリビ
ニルアルコール水溶液75ｇと共にボールミルで24
時間分散した。これら３種の分散液を混合した
後、炭酸カルシウムの50％分散液80ｇを加え、さ
らに、ステアリン酸亜鉛の20％分散液25ｇ、10％
ポリビニルアルコール水溶液200ｇを加え、十分
撹拌して塗液とした。
塗液を坪量50ｇ／m2の原紙に固形分塗布量4.0
ｇ／m2になるように、塗布乾燥し、スーパーカレ
ンダーで処理した感熱記録材料を得た。
実施例 ２
実施例１の４−ヒドロキシ−4′−メチルジフエ
ニルスルホンのかわりに、４−ヒドロキシ−4′−
イソプロピルオキシジフエニルスルホンを使用す
る以外は実施例１と同様にして感熱記録材料を得
た。
比較例 １
実施例１の４−ヒドロキシ−4′−メチルジフエ
ニルスルホンのかわりに、２，２−ビス（４−ヒ
ドロキシフエニル）プロパンを使用し、２−ベン
ジルチオナフタレンのかわりにステアリン酸アミ
ドを使用する以外は実施例１と同様にして感熱記
録材料を得た。
比較例 ２
実施例１の２−ベンジルチオナフタレンのかわ
りに、ステアリン酸アマイドを使用する以外は実
施例１と同様にして感熱記録材料を得た。
比較例 ３
実施例１の２−ベンジルチオナフタレンを除く
以外は、実施例１と同様にして感熱記録材料を得
た。
実施例１の４−ヒドロキシ−4′−メチルジフエ
ニルスルホンのかわりに４，4′−ジフエノールス
ルホンを使用する以外は、実施例１と同様にして
感熱記録材料を得た。
以上のようにして得られた感熱記録材料を松下
電子部品(株)製、感熱紙長距離摩耗試験機にて記録
し、発色濃度をマクベス濃度計にて測定した。ま
た、記録部について耐可塑剤性についてテストし
た。結果を表−１に示す。
(A) Industrial Application Field The present invention relates to a heat-sensitive recording material, and in particular, heat-responsive, heat-responsive,
This invention relates to a heat-sensitive recording material with improved image storage properties. (B) Prior art A heat-sensitive recording material generally has 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 color developer. By heating with a head, hot pen, laser light, etc., the dye precursor and developer react instantly.
This allows recorded images to be obtained, and is designated as Special Publication No. 43-4160.
It is disclosed in Japanese Patent Publication No. 14039/1983. 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 , labels, and automatic ticket vending machines. The basic performances required of a heat-sensitive recording material include sufficient color image density and sensitivity, and no deterioration of color images over time.
In addition, in recent years, the speed of print recording has been increasing, and as the speed of recording devices themselves has increased, we have also developed recording materials that can cope with this, that is, heat-sensitive recording materials with excellent thermal responsiveness that can produce high-density colored images with low thermal energy. is desired. Furthermore, as heat-sensitive recording materials became widely used, properties such as image preservation (grease resistance) due to the adhesion of oily substances such as hair products, hand creams, and oils and fats contained in skin sweat were also required. As a result, heat-sensitive recording materials that satisfactorily satisfy thermal responsiveness and image storage stability have become desirable. Conventionally, methods have been known in which various additives are incorporated into the recording layer in order to obtain colored images with high density. For example, urea, phthalic anhydride, acetanilide, etc. are listed in Japanese Patent Publication No. 43-4160;
The issue includes natural and synthetic waxes such as beeswax, carnauba wax, and paraffin wax.
No. 17748 discloses a method of adding salicylic acid, phthalic acid monobenzyl ester, etc. Further, in order to improve image storage stability, the use of bis(4-hydroxyphenyl) sulfone as a color developer is described in JP-A-58-119893. However, they have disadvantages such as poor thermal response, making it impossible to obtain sufficient density, and even if high-density images are obtained, they have poor storage stability and deteriorate over time, so that no satisfactory product has been obtained. (C) Object of the invention The object of the invention is to obtain a heat-sensitive recording material that is further excellent in thermal response and image storage stability. (D) Structure of the Invention In 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, the color developer is a compound of the general formula (1). ), and further contains 2
-By containing benzylthionaphthalene,
A heat-sensitive recording material with excellent heat responsiveness and image storage stability could be obtained. General formula (1) (In the formula, R represents an alkyl group, an alkoxy group, an aralkyloxy group, or a halogen atom) By using a compound represented by the general formula (1) as a color developer, a heat-sensitive recording material with good image storage stability can be obtained. However, the thermal response was not satisfactory, and after examining various additives, we found that 2-
Thermal response was improved by adding benzylthionaphthalene. Specific examples of the compound represented by general formula (1) include 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4'-isopropyloxydiphenylsulfone, 4-chloro-
Examples include 4'-hydroxydiphenylsulfone and 4-benzyloxy-4'-hydroxydiphenylsulfone. Compounds represented by general formula (1) and 2 according to the present invention
- Benzylthionaphthalene is usually added in an amount of 5% by weight or more based on the dye precursor. Preferred amounts are 10-600% by weight, especially 20-600% by weight.
500% by weight is preferred. If the amount added is less than 5% by weight, thermal responsiveness and image storage stability will not be sufficient, and if the amount added is more than 600% by weight, adhesion of thermofusible substances to the thermal head etc. will increase and printing problems may occur. Further, by adding a thermofusible substance having a melting point of 80°C to 160°C, such as stearamide or N-hydroxymethylstearamide, the thermal responsiveness can be further improved. The main components used in the heat-sensitive recording material of the present invention will be specifically explained below. As a dye precursor, triphenylmethane type,
Examples include fluoran-based, diphenylmethane-based, thiazine-based, and spiropyran-based compounds. For example, crystal violet lactone, 3-diethylamino-7-methylfluorane, 3-diethylamino-6-chloro-7-methylfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7 -anilinofluorane, 3-diethylamino-7-(2-
chloroanilino)fluoran, 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-methylcyclohexylamino)
-3-methyl-7-anilinofluorane, 3-piperidino-3-methyl-7-anilinofluorane, and the like. As binders, starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol,
Styrene-maleic anhydride copolymer, ethylene-
Examples include water-soluble binders such as maleic anhydride copolymers, and latex-based water-insoluble binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, and methyl acrylate-butadiene copolymers. Examples of pigments include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin, and the like. In addition, higher fatty acid metal salts such as zinc stearate and calcium stearate, paraffin,
Waxes such as paraffin oxide, polyethylene, polyethylene oxide, stearamide, and castor wax, dispersants such as sodium dioctyl sulfosuccinate, ultraviolet absorbers such as benzophenone and benzotriazole, and surfactants and fireflies. Examples include photodyes. Paper is mainly used as the support for the heat-sensitive recording material according to the present invention, but various non-woven fabrics,
Plastic film, synthetic paper, metal foil, etc., or a composite sheet made of a combination of these may be used as desired. (E) Examples The present invention will be explained in more detail with examples. Example 1 10 g of 3-diethylamino-6-methyl-7-anilinofluorane was dispersed in a ball mill for 24 hours with 30 g of a 2% polyvinyl alcohol aqueous solution. Meanwhile, 25 g of 4-hydroxy-4'-methyldiphenyl sulfone was added to a 2% polyvinyl alcohol aqueous solution.
75 g was dispersed in a ball mill for 24 hours, and separately, 25 g of 2-benzylthionaphthalene was dispersed in a ball mill with 75 g of a 2% polyvinyl alcohol aqueous solution for 24 hours.
Spread out time. After mixing these three dispersions, 80 g of a 50% dispersion of calcium carbonate was added, and further 25 g of a 20% dispersion of zinc stearate, 10%
200 g of polyvinyl alcohol aqueous solution was added and thoroughly stirred to prepare a coating liquid. Apply the coating liquid to a base paper with a basis weight of 50 g/m 2 at a solid content of 4.0.
A heat-sensitive recording material was obtained which was coated and dried so as to have a weight of 1.5 g/m 2 and treated with a supercalender. Example 2 In place of 4-hydroxy-4'-methyldiphenylsulfone in Example 1, 4-hydroxy-4'-
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that isopropyloxydiphenyl sulfone was used. Comparative Example 1 2,2-bis(4-hydroxyphenyl)propane was used instead of 4-hydroxy-4'-methyldiphenylsulfone in Example 1, and stearamide was used instead of 2-benzylthionaphthalene. A heat-sensitive recording material was obtained in the same manner as in Example 1 except that . Comparative Example 2 A heat-sensitive recording material was obtained in the same manner as in Example 1 except that stearamide was used instead of 2-benzylthionaphthalene. Comparative Example 3 A heat-sensitive recording material was obtained in the same manner as in Example 1 except that 2-benzylthionaphthalene in Example 1 was removed. A heat-sensitive recording material was obtained in the same manner as in Example 1 except that 4,4'-diphenolsulfone was used in place of 4-hydroxy-4'-methyldiphenylsulfone. The heat-sensitive recording material obtained as described above was recorded using a thermal paper long distance abrasion tester manufactured by Matsushita Electronic Components Co., Ltd., and the color density was measured using a Macbeth densitometer. The recording portion was also tested for plasticizer resistance. The results are shown in Table-1.
【表】
耐可塑剤性テスト／記録したサンプルの表面を
食品用ラツプフイルムで被覆し、室温で放置し、
一週間後の発色部濃度をマクベス濃度計で測定し
た。
(F) 効果
表−１に示した結果から明らかな様に実施例
１、２に示した本発明による感熱記録材料は、比
較例１、２、３及び４と比して、熱応答性および
画像安定性の優れたものである。[Table] Plasticizer resistance test/The surface of the recorded sample was covered with food wrap film, left at room temperature,
After one week, the density of the colored area was measured using a Macbeth densitometer. (F) Effect As is clear from the results shown in Table 1, the heat-sensitive recording materials according to the present invention shown in Examples 1 and 2 have better thermal responsiveness and It has excellent image stability.
Claims (1)
時反応して該染料前駆体を発色せしめる顕色剤と
を含有する感熱記録材料において、該顕色剤とし
て、一般式(1)で示される化合物を含有し、さらに
２−ベンジルチオナフタレンを含有する事を特徴
とする感熱記録材料。 一般式(1) （式中Ｒはアルキル基、アルコキシ基、アラルキ
ルオキシ基又はハロゲン原子を表わす）[Scope of Claims] 1. In a heat-sensitive recording material containing a normally colorless or light-colored dye precursor and a color developer that reacts with the dye precursor upon heating to develop color from the dye precursor, as the color developer, the general formula A heat-sensitive recording material characterized by containing the compound represented by (1) and further containing 2-benzylthionaphthalene. General formula (1) (In the formula, R represents an alkyl group, an alkoxy group, an aralkyloxy group, or a halogen atom)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60280493A JPS62138288A (en) | 1985-12-12 | 1985-12-12 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60280493A JPS62138288A (en) | 1985-12-12 | 1985-12-12 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62138288A JPS62138288A (en) | 1987-06-22 |
| JPH0559837B2 true JPH0559837B2 (en) | 1993-09-01 |
Family
ID=17625848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60280493A Granted JPS62138288A (en) | 1985-12-12 | 1985-12-12 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62138288A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019081305A (en) * | 2017-10-31 | 2019-05-30 | 小西化学工業株式会社 | Developer composition and use thereof |
-
1985
- 1985-12-12 JP JP60280493A patent/JPS62138288A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62138288A (en) | 1987-06-22 |
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