JPH0533153B2 - - Google Patents
Info
- Publication number
- JPH0533153B2 JPH0533153B2 JP60015042A JP1504285A JPH0533153B2 JP H0533153 B2 JPH0533153 B2 JP H0533153B2 JP 60015042 A JP60015042 A JP 60015042A JP 1504285 A JP1504285 A JP 1504285A JP H0533153 B2 JPH0533153 B2 JP H0533153B2
- Authority
- JP
- Japan
- Prior art keywords
- color
- heat
- sensitive recording
- recording material
- bis
- 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 - Fee Related
Links
- 239000000463 material Substances 0.000 claims description 19
- -1 fluorene compound Chemical class 0.000 claims description 8
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical group C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000005995 Aluminium silicate Substances 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
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000010438 heat treatment 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
- 239000010410 layer Substances 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
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003232 water-soluble binding agent 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
- 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
- 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
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 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
- 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent 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
- 239000011230 binding agent Substances 0.000 description 1
- 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 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
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000005562 fading 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
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000011888 foil 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
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 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
- 230000007257 malfunction 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
- 239000004745 nonwoven fabric 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
- 238000001454 recorded image Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 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
- 238000010186 staining Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 239000001993 wax 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
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
-
- 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
(A) 産業上の利用分野
本発明は２成分発色型の感熱記録材料に関する
ものであり、特に近赤外部に吸収をもつ発色画像
が得られる感熱記録材料に関するものである。
(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、乗車券等自動券売機など広範囲の分
野に利用されている。
特に感熱記録用ラベルはPOS（販売時点情報管
理）システム用のバーコードラベル、価格表示ラ
ベル、配送・出荷ラベルなど印字後貼付を必要と
する用途に用いられている。特にスーパーマーケ
ツトやデパート等の大型量販店をはじめ、チエー
ン展開をしている専門店、レストラン等において
POSシステムの普及が著しい。消費者のニーズ
を明確に把握し、合理的な経営戦略を立てるため
に、商品の売上情報を集計、分析することが目的
であり、その一つとして店頭で販売される商品に
表示されたバーコードやOCR文字をスキヤナー
で光学的に読み取る方法が現在急速に伸びてきて
いる。
そこで現在、様々の印刷方式が試みられている
が、その中でも特に感熱記録方式が最も優れてい
るといえる。
なぜなら、印字方式が加熱による物質の化学的
または物理的変化を利用して画像を記録する方法
であり、現像定着を必要とせず、印刷インキの補
充も必要としない。
即ち、機会の小型化、簡素化、記録のスピード
化が可能であり、インキによる手や商品への汚
れ、インキのかすれの心配も全くないなどの多く
の特徴を有するからである。
また発色画像であるバーコード等の読み取りに
は従来より、波長633nｍの赤色光をもつHe・Ne
レーザー光を用いているが、最近、半導体レーザ
が使われるようになつてきた。これは電流で直接
変調でき小型化が可能であり、使い易く、低価格
であること、また発信波長が700〜1500nｍの近
赤外部にあるため汚れによる誤動作が少ないこと
などの利点があり広く普及してきている。従つ
て、感熱記録用ラベルにおいても半導体レーザー
で読み取ることができる発色画像を得ることが望
まれている。しかしながら、従来より用いられて
いるロイコ染料と顕色剤とから成る２成分型感熱
記録材料では黒発色系においても発色画像の吸収
波長は長波長側で550〜620nｍのためHe・Neレ
ーザー光では読み取り可能であるが、近赤外部の
波長をもつ半導体レーザでの読み取りはできなか
つた。
(C) 発明の目的
本発明の目的は、近赤外部に吸収をもつ発色画
像が得られる感熱記録材料を提供することであ
り、他の目的は発色性、保存性に優れた感熱記録
材料を提供することである。
(D) 発明の構成
通常無色又は淡色の染料前駆体と顕色剤とを発
色成分として含有する感熱記録材料において、該
染料前駆体が下記一般式で表わされるフルオレン
化合物を用い、該顕色剤にビス（４―ヒドロキシ
フエニル）スルホンを用いることにより目的とす
る感熱記録材料が提供できる。
一般式中、R1、R2、R3、R4、R5及びR6はそれ
ぞれ低級アルキル基を示す。
前記一般式で示されるフルオレン化合物は、そ
れ自体は無色から淡色の結晶で近赤外部に吸収を
有しないが顕色剤との反応により青色から緑色に
発色し、その発色画像は、近赤外部に吸収をも
つ。
本発明によるフルオレン化合物の具体例を示す
と、例えば、３，６―ビス（ジメチルアミノ）フ
ルオレン―９―スピロ―3′―（6′―ジメチルアミ
ノフタリド）、３―ジエチルアミノ―６―ジメチ
ルアミノフルオレン―９―スピロ―3′―（6′―ジ
メチルアミノフタリド）、３，６―ビス（ジエチ
ルアミノ）フルオレン―９―スピロ―3′―（6′―
ジメチルアミノフタリド）、３―ジブチルアミノ
―６―ジメチルアミノフルオレン―９―スピロ―
3′―（6′―ジメチルアミノフタリド）、３―ジブ
チルアミノ―６―ジエチルアミノフルオレン―９
―スピロ―3′―（6′―ジメチルアミノフタリド）、
３，６―ビス（ジメチルアミノ）フルオレン―９
―スピロ―3′―（6′―ジエチルアミノフタリド）、
３―ジエチルアミノ―６―ジメチルアミノフルオ
レン―９―スピロ―3′―（6′―ジエチルアミノフ
タリド）、３―ジブチルアミノ―６―ジメチルア
ミノフルオレン―９―スピロ―3′―（6′―ジエチ
ルアミノフタリド）、３，６―ビス（ジエチルア
ミノ）フルオレン―９―スピロ―3′―（6′―ジエ
チルアミノフタリド）、３，６―ビス（ジメチル
アミノ）フルオレン―９―スピロ―3′―（6′―ジ
ブチルアミノフタリド）、３―ジブチルアミノ―
６―ジエチルアミノフルオレン―９―スピロ―
3′―（6′―ジエチルアミノフタリド）、３―ジエ
チルアミノ―６―ジメチルアミノフルオレン―９
―スピロ―3′―（6′―ジブチルアミノフタリド）
等が挙げられる。
本発明によるフルオレン化合物を加熱時発色さ
せる顕色剤としては電子受容性化合物が用いられ
るが、発色性、画像保存性の両面を満足させる化
合物は少なく、中でもビス（４―ヒドロキシフエ
ニル）スルホンが発色性、画像保存性に優れてい
ることがわかつた。従来２成分発色型の感熱記録
材料に顕色剤としてビス（４―ヒドロキシフエニ
ル）スルホンを用いた場合、融点が248℃と高く、
他の低融点顕色剤に比べ発色性に劣つていた。し
かし本発明によるフルオレン化合物との組合せで
は他の融点の低い顕色剤に比べても発色性に優れ
ているという効果が見出された。
本発明の感熱記録材料において、発色成分の他
の必要に応じさらに添加される主な成分について
具体的に述べる。
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アンダ
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、カスターワツクス等の
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。
本発明の感熱記録材料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。
本発明の感熱記録材料は一般的に通常フアクシ
ミリ、プリンター等に用いられる他、近赤外光を
検知する特殊用にも用いられる。用途により発色
画像の高保存性が望まれる場合、例えばラベル用
として用いる場合、未発色部及び発色画像部を外
部環境から保護するために感熱記録層の上に保護
層を積層させてもよい。この場合、保護層の主成
分としては、各種の水溶性樹脂、ラテツクス、高
硬化型樹脂が用いられる。また必要に応じて顔
料、耐水化剤、撥水剤、消泡剤、紫外線吸収剤等
を添加することができる。さらにラベル用として
は、印字後別の固体表面に容易に貼付できるよう
に裏面に粘着層を設けてもよい。この場合、粘着
層には離型紙が設けられる。
(E) 実施例
次に本発明を実施例によりさらに詳細に説明す
る。
実施例 １
３，６―ビス（ジメチルアミノ）フルオレン―
９―スピロ―3′―（6′―ジメチルアミノフタリ
ド）20ｇを１％ポリビニルアルコール水溶液80ｇ
と共にボールミルで分散した。一方ビス（４―ヒ
ドロキシフエニル）スルホン50ｇを１％ポリビニ
ルアルコール水溶液200ｇと共にボーミルで分散
した。これらの分散液を混合した後炭酸カルシウ
ムの40％分散液250ｇを加え、さらにステアリン
酸亜鉛の25％分散液40ｇ、ステアリン酸アミドの
25％分散液200ｇ、８％ポリビニルアルコール水
溶液625ｇを加え十分撹拌して塗液とした。この
塗液を坪量55ｇ／m2の原紙上に固型分塗布量とし
て６ｇ／m2となるように塗布乾燥し感熱記録材料
を得た。
比較例 １〜３
実施例１のビス（４―ヒドロキシフエニル）ス
ルホンのかわりに次の化合物を用いた以外は実施
例１と同様にして感熱記録材料を得た。
４，4′―イソプロピリデンジフエノール（比較
例１）、
４，4′―シクロヘキシリデンジフエノール（比
較例２）、
４―ヒドロキシ安息香酸ベンジルエステル（比
較例３）
評 価
実施例１、比較例１〜３で得られた感熱記録材
料については次の評価を行い結果を表１に示し
た。
(1) 発色濃度；16.00V、3.0ミリ秒の条件で印字
し、発色画像の高学濃度をマクベスRD918を
用いて測定した。
(2) 画像保存性；発色画像を60℃の環境下に24時
間保存した。保存前後の光学濃度を測定し、画
像保存率を下式より求めた。
画像保存率＝保存後の光学濃度／保存前の光学濃度
×100
(3) 画像耐水性；発色画像を20℃水道水２中に
水浸けし、20時間保存した。保存前後の光学濃
度を測定し、画像保存率を同様にして求めた。
(4) 近赤外光読み取り；GaAs半導体レーザー
（780nｍ）を用いてバーコード印字後の読み取
りの可否を調べた。
(A) Industrial Application Field The present invention relates to a two-component color-forming heat-sensitive recording material, and particularly to a heat-sensitive recording material capable of producing a colored image that absorbs in the near-infrared region. (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, thermal 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, including automatic ticket vending machines, labels, and train tickets. In particular, thermal recording labels are used for applications that require pasting after printing, such as barcode labels for POS (point of sale) systems, price display labels, and shipping/shipping labels. Especially at large mass retailers such as supermarkets and department stores, as well as chain specialty stores and restaurants.
The popularity of POS systems is remarkable. Its purpose is to aggregate and analyze product sales information in order to clearly understand consumer needs and formulate rational management strategies. The method of optically reading codes and OCR characters using scanners is currently rapidly growing. Therefore, various printing methods are currently being tried, and among them, the thermal recording method can be said to be the most excellent. This is because the printing method uses chemical or physical changes in substances due to heating to record images, and does not require development and fixing, nor does it require replenishment of printing ink. That is, this is because it has many features such as being able to reduce the size of the machine, simplify it, and speed up recording, and there is no fear of ink staining hands or products or ink fading. In addition, for reading barcodes, etc., which are colored images, it has been conventionally necessary to use He/Ne, which has red light with a wavelength of 633 nm.
Laser light is used, but recently semiconductor lasers have come into use. This is widely used because it can be directly modulated by current, can be miniaturized, is easy to use, is low cost, and has the advantage of being less likely to malfunction due to dirt because the emission wavelength is in the near-infrared range of 700 to 1500 nm. I've been doing it. Therefore, it is desired to obtain colored images that can be read with a semiconductor laser even on heat-sensitive recording labels. However, in the conventional two-component heat-sensitive recording material consisting of a leuco dye and a color developer, the absorption wavelength of a colored image is 550 to 620 nm on the long wavelength side even in a black color system, so He/Ne laser light cannot be used. Although it was possible to read it, it was not possible to read it using a semiconductor laser with a near-infrared wavelength. (C) Purpose of the Invention The purpose of the present invention is to provide a heat-sensitive recording material capable of producing colored images with absorption in the near-infrared region, and another purpose of the present invention is to provide a heat-sensitive recording material with excellent color development and storage stability. It is to provide. (D) Structure of the Invention In a heat-sensitive recording material containing a normally colorless or light-colored dye precursor and a color developer as color forming components, the dye precursor is a fluorene compound represented by the following general formula, and the color developer is By using bis(4-hydroxyphenyl) sulfone, the desired heat-sensitive recording material can be provided. In the general formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each represent a lower alkyl group. The fluorene compound represented by the above general formula is a colorless to light-colored crystal that does not have absorption in the near-infrared region, but it develops a color from blue to green by reaction with a color developer, and the color image shows the color in the near-infrared region. has absorption. Specific examples of the fluorene compounds according to the present invention include 3,6-bis(dimethylamino)fluorene-9-spiro-3'-(6'-dimethylaminophthalide), 3-diethylamino-6-dimethylamino Fluorene-9-spiro-3'-(6'-dimethylaminophthalide), 3,6-bis(diethylamino)fluorene-9-spiro-3'-(6'-
dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-
3'-(6'-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9
-Spiro-3'-(6'-dimethylaminophthalide),
3,6-bis(dimethylamino)fluorene-9
-Spiro-3'-(6'-diethylaminophthalide),
3-diethylamino-6-dimethylaminofluorene-9-spiro-3'-(6'-diethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3'-(6'-diethylaminophthalide) ), 3,6-bis(diethylamino)fluorene-9-spiro-3'-(6'-diethylaminophthalide), 3,6-bis(dimethylamino)fluorene-9-spiro-3'-(6' -dibutylaminophthalide), 3-dibutylamino-
6-diethylaminofluorene-9-spiro-
3'-(6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9
-Spiro-3'-(6'-dibutylaminophthalide)
etc. An electron-accepting compound is used as a color developer that causes the fluorene compound according to the present invention to develop color when heated, but there are few compounds that satisfy both color development properties and image storage stability, and among them, bis(4-hydroxyphenyl) sulfone is used. It was found to have excellent color development and image storage properties. Conventionally, when bis(4-hydroxyphenyl) sulfone was used as a color developer in a two-component color-forming heat-sensitive recording material, the melting point was as high as 248°C.
It was inferior in color development compared to other low melting point color developers. However, in combination with the fluorene compound according to the present invention, it was found that the color developing property is superior to that of other color developers with low melting points. In the heat-sensitive recording material of the present invention, the main components that may be added as necessary in addition to the color-forming components will be specifically described. 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-soluble 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 of the present invention, but various nonwoven fabrics, plastic films, synthetic papers, metal foils, etc., or composite sheets made of a combination of these can also be used as desired. The heat-sensitive recording material of the present invention is generally used for facsimile machines, printers, etc., and is also used for special applications that detect near-infrared light. When a high preservability of a colored image is desired depending on the application, for example when used for a label, a protective layer may be laminated on the heat-sensitive recording layer in order to protect the uncolored area and the colored image area from the external environment. In this case, various water-soluble resins, latexes, and highly curable resins are used as the main components of the protective layer. Further, pigments, water resistant agents, water repellents, antifoaming agents, ultraviolet absorbers, etc. can be added as necessary. Further, for use as a label, an adhesive layer may be provided on the back surface so that it can be easily attached to another solid surface after printing. In this case, a release paper is provided on the adhesive layer. (E) Examples Next, the present invention will be explained in more detail using examples. Example 1 3,6-bis(dimethylamino)fluorene-
20g of 9-spiro-3'-(6'-dimethylaminophthalide) in 80g of 1% polyvinyl alcohol aqueous solution
It was also dispersed in a ball mill. On the other hand, 50 g of bis(4-hydroxyphenyl) sulfone was dispersed with 200 g of a 1% polyvinyl alcohol aqueous solution using a Baumill. After mixing these dispersions, 250 g of a 40% dispersion of calcium carbonate was added, and then 40 g of a 25% dispersion of zinc stearate and 40 g of a 25% dispersion of stearic acid amide were added.
200 g of a 25% dispersion and 625 g of an 8% aqueous polyvinyl alcohol solution were added and thoroughly stirred to prepare a coating liquid. This coating liquid was applied onto a base paper having a basis weight of 55 g/m 2 to a solid coating weight of 6 g/m 2 and dried to obtain a heat-sensitive recording material. Comparative Examples 1 to 3 Heat-sensitive recording materials were obtained in the same manner as in Example 1, except that the following compounds were used in place of bis(4-hydroxyphenyl)sulfone in Example 1. 4,4'-isopropylidene diphenol (Comparative example 1), 4,4'-cyclohexylidene diphenol (Comparative example 2), 4-hydroxybenzoic acid benzyl ester (Comparative example 3) Evaluation Example 1, Comparative example The heat-sensitive recording materials obtained in Examples 1 to 3 were evaluated as follows, and the results are shown in Table 1. (1) Color density: Printing was performed under the conditions of 16.00 V and 3.0 milliseconds, and the high density of the colored image was measured using Macbeth RD918. (2) Image storage: Colored images were stored at 60°C for 24 hours. The optical density before and after storage was measured, and the image preservation rate was calculated from the formula below. Image storage rate = Optical density after storage / Optical density before storage x 100 (3) Image water resistance: The colored image was immersed in tap water 2 at 20°C and stored for 20 hours. The optical density before and after storage was measured, and the image preservation rate was determined in the same manner. (4) Near-infrared light reading: Using a GaAs semiconductor laser (780 nm), we investigated whether the barcode could be read after it was printed.
【表】
(F) 発明の効果
表１で示されるように本発明の感熱記録材料
は、その発色画像を近赤外光をもつ半導体レーザ
ーにより読み取ることができると共に、画像の発
色性、保存性に優れていることがわかる。[Table] (F) Effects of the Invention As shown in Table 1, the heat-sensitive recording material of the present invention has a color image that can be read by a semiconductor laser that emits near-infrared light, as well as improved color development and storage stability of the image. It can be seen that it is excellent.
Claims (1)
色成分として含有する感熱記録材料において、該
染料前駆体が下記一般式で表わされるフルオレン
化合物であり、該顕色剤がビス（４―ヒドロキシ
フエニル）スルホンであることを特徴とする感熱
記録材料。 （式中、R1、R2、R3、R4、R5及びR6はそれぞれ
低級アルキル基を示す。）[Scope of Claims] 1. In a heat-sensitive recording material containing a normally colorless or light-colored dye precursor and a color developer as color-forming components, the dye precursor is a fluorene compound represented by the following general formula, and the color developer A heat-sensitive recording material characterized in that is bis(4-hydroxyphenyl)sulfone. (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each represent a lower alkyl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60015042A JPS61172791A (en) | 1985-01-28 | 1985-01-28 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60015042A JPS61172791A (en) | 1985-01-28 | 1985-01-28 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61172791A JPS61172791A (en) | 1986-08-04 |
| JPH0533153B2 true JPH0533153B2 (en) | 1993-05-18 |
Family
ID=11877779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60015042A Granted JPS61172791A (en) | 1985-01-28 | 1985-01-28 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61172791A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63126785A (en) * | 1986-11-18 | 1988-05-30 | Mitsubishi Paper Mills Ltd | Recording material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5711088A (en) * | 1980-06-17 | 1982-01-20 | Mitsubishi Paper Mills Ltd | Thermosensitive recording sheet |
| JPS58119893A (en) * | 1982-01-13 | 1983-07-16 | Ricoh Co Ltd | Heat-sensitive recording material |
| JPS59199757A (en) * | 1983-04-28 | 1984-11-12 | Yamamoto Kagaku Gosei Kk | Fluorene compound, its manufacture, and recording material using the same |
-
1985
- 1985-01-28 JP JP60015042A patent/JPS61172791A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5711088A (en) * | 1980-06-17 | 1982-01-20 | Mitsubishi Paper Mills Ltd | Thermosensitive recording sheet |
| JPS58119893A (en) * | 1982-01-13 | 1983-07-16 | Ricoh Co Ltd | Heat-sensitive recording material |
| JPS59199757A (en) * | 1983-04-28 | 1984-11-12 | Yamamoto Kagaku Gosei Kk | Fluorene compound, its manufacture, and recording material using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61172791A (en) | 1986-08-04 |
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