JPH01180382A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPH01180382A JPH01180382A JP63004498A JP449888A JPH01180382A JP H01180382 A JPH01180382 A JP H01180382A JP 63004498 A JP63004498 A JP 63004498A JP 449888 A JP449888 A JP 449888A JP H01180382 A JPH01180382 A JP H01180382A
- Authority
- JP
- Japan
- Prior art keywords
- dihydroxydiphenyl ether
- ether
- methyl
- heat
- basic dye
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000981 basic dye Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 abstract description 12
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 abstract description 3
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 abstract 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 12
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution 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
- 239000007864 aqueous solution Substances 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- -1 phenol compound Chemical class 0.000 description 4
- 238000004040 coloring Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 238000002360 preparation method Methods 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
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 description 1
- OAGNKYSIOSDNIG-UHFFFAOYSA-N 1-methyl-3-[2-(3-methylphenoxy)ethoxy]benzene Chemical compound CC1=CC=CC(OCCOC=2C=C(C)C=CC=2)=C1 OAGNKYSIOSDNIG-UHFFFAOYSA-N 0.000 description 1
- GQMJRBJIQKXIPN-UHFFFAOYSA-N 1-phenylethyl 4-hydroxybenzoate Chemical compound C=1C=CC=CC=1C(C)OC(=O)C1=CC=C(O)C=C1 GQMJRBJIQKXIPN-UHFFFAOYSA-N 0.000 description 1
- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- ZCYZMPBYRCSPPN-UHFFFAOYSA-N 3-(dimethylamino)-3h-2-benzofuran-1-one Chemical compound C1=CC=C2C(N(C)C)OC(=O)C2=C1 ZCYZMPBYRCSPPN-UHFFFAOYSA-N 0.000 description 1
- MQJTWPAGXWPEKU-UHFFFAOYSA-N 3-[4-(dimethylamino)phenyl]-3-(1,2-dimethylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C3=CC=CC=C3N(C)C=2C)C2=CC=CC=C2C(=O)O1 MQJTWPAGXWPEKU-UHFFFAOYSA-N 0.000 description 1
- ZKUWHPNJONEJEE-UHFFFAOYSA-N 3-[4-(dimethylamino)phenyl]-3-(2-methyl-1h-indol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C3=CC=CC=C3NC=2C)C2=CC=CC=C2C(=O)O1 ZKUWHPNJONEJEE-UHFFFAOYSA-N 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 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
- 150000004650 carbonic acid diesters Chemical class 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
- 239000004927 clay Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 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
- RQAQWBFHPMSXKR-UHFFFAOYSA-N n-(4-chlorophenyl)-3-(phosphonooxy)naphthalene-2-carboxamide Chemical compound OP(O)(=O)OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=C(Cl)C=C1 RQAQWBFHPMSXKR-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical class C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N salicylic acid benzyl ester Natural products OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］ ′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、かつ白色度の高い感熱記録材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] '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 a high degree of whiteness.
［従来の技術］
少なくとも１種の無色ないし淡色の塩基性染料とフェノ
ール類、有機酸などとの加熱発色反応を利用した感熱記
録材料はこれまでに各種のものが発表され（特公昭４５
−１４０８９号公報など）広く実用化されている。これ
らの感熱記録材料は計測用記録計、コンビニ−ターおよ
び情報通信の端末機、ファクシミリ、乗車券□自動券売
機など広い分野に応用されている。これらの記□録装置
はサーマルヘッドや熱ペンなどの熱素子を備えており、
こめ素子を加熱することにより発色して記録を得ること
ができる。最近では用途の多様化と装置の高性能化が進
み、これに伴い１、感熱記録紙に対する要求品質もより
高度なものとなってきでいる。例えば、ファクシミリで
はＡ４判の記録に従来数分かかったものが１分以内で可
能になっている。このような現状において、感熱記録紙
の感度を自主する方法としては、増感剤を添加使用する
ことが提案されているが、発色感度、発色画像の安定性
、白−度、記録適性、地肌カブリなど、感゛熱記録材料
に要求される性能をバランスよく満足するものはまだ得
られていない。[Prior Art] Various types of heat-sensitive recording materials have been announced so far that utilize a heat-coloring reaction between at least one colorless or light-colored basic dye and phenols, organic acids, etc.
-14089, etc.) have been widely put into practical use. These heat-sensitive recording materials are applied to a wide range of fields such as measuring recorders, convenience stores, information and communication terminals, facsimile machines, and automatic ticket vending machines. These recording devices are equipped with thermal elements such as thermal heads and thermal pens.
By heating the ink element, it is possible to develop color and obtain a record. Recently, applications have become more diversified and equipment has become more sophisticated, and as a result, the quality required for thermal recording paper has also become more sophisticated. For example, with a facsimile, it is now possible to record an A4 size document in less than a minute, whereas previously it took several minutes. Under these circumstances, the addition of a sensitizer has been proposed as a method to independently adjust the sensitivity of thermal recording paper, but this method has been proposed to improve color sensitivity, stability of colored images, whiteness, recording suitability, and background texture. A material that satisfies the performance requirements for thermal recording materials, such as fog, in a well-balanced manner has not yet been obtained.
感臓□記録紙では、感熱記録層中に発色性物質″とフェ
ノール化合物とをそれぞれ微粒子状に分散して存在させ
ており、加熱によってその一方又は両者が溶解して互い
に密に接触して発色すると考えられている。In sensory recording paper, a color-forming substance and a phenol compound are dispersed in the form of fine particles in the heat-sensitive recording layer, and when heated, one or both of them dissolve and come into close contact with each other, producing color. It is believed that.
このような目的に使用する適当なフェノール化合物とし
ては、価格、品質の安定性などの面から２．２−ビス（
４′−ヒドロキシフェニル）プロパン（ビスフェノール
Ａ、融点１５８℃）が広く使用されている（例えば米国
特許１５０９：３７５号）。しかしながらこのビスフェ
ノールＡは、熱応答性が悪く、感熱記録装置の高速化あ
るいは小型化に伴なう感熱記録紙の高感度化への市場の
要求に必らずしも満足できるものではなかった。この欠
点を補うために多くの増感剤の提案がなされており、例
えばワックス類（特開昭４８−１９２３１号）をはじめ
としてフタル酸エステル類（特開昭５７−１１６６９０
号、特開昭５８−９８２８５号）、ベンジルフェニルエ
ーテル誘導体（特開昭５９−１５５０９６号）、ベンジ
ルビフェニル（特開昭６０−８２３８２号）、ナフトー
ル誘導体（特開昭５８−８７０９４号）、炭酸ジエステ
ル類（特開昭５８−１３６４８９号）などが提案されて
いるが、上記のビスフェノールＡと組み合わせた場合、
白色度、発色感度、カブリなどの面において充分な品質
が得られるに到っていない。発色感度向上のために融点
の低いモノフェノール類、例えばα−ナフトール（融点
９５〜９６℃）、４−ターシャリブチルフェノール（融
点９４〜９９℃）を使用するとフェノール臭が強く実用
性にかける。また特開昭５６−１４４１９８号にはｐ−
ヒドロオキシ安息香酸ベンジル又はｐ−ヒドロオキシ安
息香酸メチルベンジルが感熱記録シートの高感度化のた
めの顕色剤として提案されているが、記録保管時に発色
部が白化（粉ふき）するという現象が発生するためその
保存性に問題がある。以上のように発色特性、白色度ほ
か、高度な市場の品質要求に充分、対応できないのが現
状である。As a suitable phenol compound to be used for this purpose, 2,2-bis(
4'-Hydroxyphenyl)propane (bisphenol A, melting point 158°C) is widely used (eg US Pat. No. 1509:375). However, this bisphenol A has poor thermal responsiveness and cannot necessarily satisfy the market demand for higher sensitivity of thermal recording paper as thermal recording devices become faster and more compact. Many sensitizers have been proposed to compensate for this drawback, including waxes (Japanese Patent Laid-Open No. 19231-1982) and phthalate esters (Japanese Patent Laid-Open No. 116690-1989).
No., JP-A No. 58-98285), benzyl phenyl ether derivatives (JP-A No. 59-155096), benzylbiphenyl (JP-A No. 60-82382), naphthol derivatives (JP-A No. 58-87094), carbonic acid Diesters (Japanese Unexamined Patent Publication No. 58-136489) have been proposed, but when combined with the above bisphenol A,
Sufficient quality has not been achieved in terms of whiteness, color development sensitivity, fog, etc. When monophenols with low melting points, such as α-naphthol (melting point 95-96°C) and 4-tert-butylphenol (melting point 94-99°C) are used to improve color development sensitivity, the phenol odor is strong and impractical. Also, in Japanese Patent Application Laid-open No. 56-144198, p-
Benzyl hydroxybenzoate or methylbenzyl p-hydroxybenzoate has been proposed as a color developer to increase the sensitivity of heat-sensitive recording sheets, but a phenomenon occurs in which the colored areas turn white (flourishing) during record storage. Therefore, there is a problem with its shelf life. As described above, at present, it is not possible to sufficiently meet the high quality demands of the market in terms of color development characteristics, whiteness, and other aspects.
［発明が解決しようとする問題点］
そこでこのような諸要求を満たす感熱記録材料が求めら
れていた。[Problems to be Solved by the Invention] Therefore, there has been a need for a heat-sensitive recording material that satisfies these various requirements.
本発明は、感熱記録材料に要求される専用的で広い用途
に使用できる発色感度を有し、かつ白色度の高い感熱記
録材料を提供することを、目的とするものである。An object of the present invention is to provide a heat-sensitive recording material that has a coloring sensitivity that can be used for a wide range of purposes and is dedicated to the needs of heat-sensitive recording materials, and has a high degree of whiteness.
［問題点を解決するためΦ手段］
本発明の感熱記録材料は、感熱層中に、少なくとも１種
の無色乃至淡色の塩基性染料とともに、一般式
で表わされるジヒドロキシジフェニルエーテルを含有す
ることを特徴とする。[Φ Means for Solving the Problems] The heat-sensitive recording material of the present invention is characterized in that the heat-sensitive layer contains dihydroxydiphenyl ether represented by the general formula along with at least one colorless to light-colored basic dye. do.
本発明者らはいくつかの難点の改善に鋭意、研究を積み
重ね、数多くのフェノール性顕色性物質を探索した結果
、上記の一般式を有するジヒドロキシジフェニルエーテ
ルが、高感度にして白色度が高く、かつパラオキシ安息
香酸ベンジルにみられるような白化現象が起きない、す
ぐれた顕色剤であることを見出し、本発明を完成するに
いたった。The inventors of the present invention have conducted extensive research to improve several difficulties and have searched for numerous phenolic color-developing substances. As a result, dihydroxydiphenyl ether having the above general formula has high sensitivity and high whiteness. They also discovered that it is an excellent color developer that does not cause the whitening phenomenon seen with benzyl paraoxybenzoate, leading to the completion of the present invention.
本発明の前記の一般式を有するジヒドロキシジフェニル
エーテルとしては、例えば２．２′−ジヒドロキシジフ
ェニルエーテル（融点１２１’Ｃ）、３．３′−ジヒド
ロキシジフェニルエーテル（融点９８℃）、４．４’−
ジヒドロキシジフェニルエーテル（融点１６６℃）が例
示できる。Examples of the dihydroxy diphenyl ether of the present invention having the above general formula include 2.2'-dihydroxydiphenyl ether (melting point 121'C), 3.3'-dihydroxydiphenyl ether (melting point 98°C), 4.4'-dihydroxydiphenyl ether (melting point 98°C),
An example is dihydroxydiphenyl ether (melting point: 166°C).
本発明において、ジヒドロキシジフェニルエーテルが、
従来使用されているビスフェノールＡと較べ、白色度が
高（かつ発色感度がすぐれている理由は必らずしも明確
ではないが、塩基性染料あるいは併用する増感剤との相
溶性に起因するものと推定される。In the present invention, dihydroxy diphenyl ether is
Compared to the conventionally used bisphenol A, it has higher whiteness (and better color development sensitivity), although the reason for its superior color development sensitivity is not necessarily clear, but it is due to its compatibility with basic dyes or sensitizers used together. It is estimated that
本発明において、ジヒドロキシジフェニルモーチルの含
有量は、通常発色性塩基性染料１重量部に対してジヒド
ロキシジフェニルエーテルは０．５〜３重量部、好まし
くは１〜２重量部添加するのが普通である。In the present invention, the content of dihydroxydiphenyl motyl is usually 0.5 to 3 parts by weight, preferably 1 to 2 parts by weight of dihydroxydiphenyl ether per 1 part by weight of the color-forming basic dye. .
本発明において、前記のジヒドロキシジフェニルエーテ
ル顕色剤とともに使用する無色乃至淡色の塩基性染料と
しては通常この目的に使用されるものであれば、いかな
る本のであってもよい。例えば下記の物を挙げるｑとが
できる。In the present invention, the colorless to light-colored basic dye used together with the dihydroxydiphenyl ether color developer may be any colorless or light-colored basic dye as long as it is commonly used for this purpose. For example, you can do the following.
３．８−ビス（ｐ−ジメチルアミノフェニル）−６−ジ
メチルアミノフタリド、３．３−ビス（ｐ−ジメチルア
ミノフェニル）フタリド、３−（ｐ−ジメチルアミノフ
ェニル）−３−（１，２−ジメチルインドール−３−イ
ル）フタリド、３− （ｐ−ジメチルアミノフェニル）
−３−（２−メチルインドール−３−イル）フタリド、
３．３−ビス（１，２−ジメチルインドール−３−イル
）−５−ジメチルアミノフタリド、３．３−ビス（ｌ、
２−ジメチルインドール−３−イル）−６−ジメチルア
ミノフタリド、３．３−ビス（９−エチルカルバゾール
−３−イル）−６−ジメチルアミノフタリド、３．８−
ビス（ｌ、２−ジメチルインドール−３−イル）−５−
ジメチルアミノフタリド、３−ｐ−ジメチルアミノフェ
ニル−３−（１−メチルピロール−３−イル）−６−ジ
メチルアミノフタリド等のトリアリルメタン系染料、４
．４ ’−ビスージメチルアミノベンズヒドリルベンジ
ルエーテル、Ｎ−ハロフェニル−ロイコオーラミン、Ｎ
−２，４，５−）リクロロフェニルロイコオーラミン
等のジフェニルメタン系染料、ベンゾイルロイコメチレ
ンブルー、ｐ−ニトロベンゾイルロイコメチレンブルー
等のチアジン系染料、３−メチル−スピロ−ジナフトピ
ラン、３−エチルースピロージナフトピラン、３−フェ
ニル−スピロ゛−ジナフトピラン、３−ベンジル−スピ
ロ−ジナフトピラン、３−メチル−チット（６′−メト
キシベンゾ）スピロピラン、３−プロピル−スピロ−ジ
ベンゾピラン等のスピロ系染料、ローダミン−Ｂ−アニ
リノラクタム、ローダミン（ｐ−ニトロアニリノ）ラク
タム、ローダミン（０−クロロアニリノ）ラクタム等の
ラクタム系染料、３−ジメチルアミノ−７−メトキシフ
ルオラン、３−ジエチルアミノ−６−メトキシフルオラ
ン、３−ジエチルアミノ−７−メトキシフルオラン、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−６−メチル−７−クロロフルオラン、３−ジ
エチルアミノ−６，７−シメチルフルオラン、３−（Ｎ
−エチル−ｐ−）ルイジノ）−７−メチルフルオラン、
゛３−ジエチルアミノー？−Ｎ−アセチル−Ｎ−メチル
アミノフルオラン、３−ジエチルアミノ−７−Ｎ−メチ
ルアミノフルオラン、３−ジエチルアミノ−７−ジベン
ジルアミノフルオラン、３−ジエチルアミノー７−Ｎ−
メチル−Ｎ−ベンジルアミノフルオラン、３−ジエチル
アミノ−７−Ｎ−クロロエチル−Ｎ−メチルアミノフル
オラン、３−ジエチルアミノ−７−Ｎ−ジエチルアミノ
フルオラン、３−（Ｎ−エチル−ｐ−）ルイジノ）−６
−メチル−７−フェニルアミノフルオラン、３−（Ｎ−
エチル−ｐ−）ルイジノ）−６−メチル−７−（ｐ−）
ルイジノ）フルオラン、３−ジエチルアミノ−６−メチ
ル−７−フェニルアミノフルオラン、３−ジブチルアミ
ノ−６−メ ゛チル−７−フェニルアミノフルオラン、
３−ジエチルアミノ−７−（２−カルボメトキシ−フェ
ニルアミノ）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−フェニルアミノ
フルオラン、３−ピロリジノ−６−メチル−７−フェニ
ルアミノフルオラン、３−ピペリジノ−６−メチル−７
−フェニルアミノフルオラン、３−ジエチルアミノ−６
−メチル−７−キシリジノフルオラン、３−ジエチルア
ミノ−７−（Ｏ−クロロフェニルアミノ）フルオラン、
３−ジブチルアミノー７− （ｏ−クロロフェニルアミ
ノ）フルオラン、３−ピロリジノ−６−メチル−７−ｐ
−ブチルフェニルアミノフルオラン、３−（Ｎ−メチル
−Ｎ−ｎ−アミル）アミノ−６−メチル−７−フェニル
アミノフルオラン、３−（Ｎ−エチル−Ｎ−ｎ−アミル
）アミノ−゛６−メチル−７−フェニルアミノフルオラ
ン、３−（Ｎ−エチル−Ｎ −１ｓｏ−アミル）アミノ
−６−メチル−７−フェニルアミノフルオラン、３−（
Ｎ−メチル−Ｎ−ｎ−ヘキシル）アミノ−６−メチル−
７−フェニルアミノフルオラン、３−（Ｎ−エチル−Ｎ
−ｎ−ヘキシル）アミノ−６−メチル−７−フェニルア
ミノフルオラン、３−（Ｎ−エチル−Ｎ−β−エチルヘ
キシル）アミノ−６−メチル−７−フェニルアミノフル
オラン等が挙げられる。3.8-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3.3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2 -dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)
-3-(2-methylindol-3-yl)phthalide,
3.3-bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3.3-bis(l,
2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3.3-bis(9-ethylcarbazol-3-yl)-6-dimethylaminophthalide, 3.8-
Bis(l,2-dimethylindol-3-yl)-5-
Triallylmethane dyes such as dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methylpyrrol-3-yl)-6-dimethylaminophthalide, 4
．． 4'-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl-leucoolamine, N
-2,4,5-) Diphenylmethane dyes such as dichlorophenyl leuco auramine, thiazine dyes such as benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spirodinaphtho Spiro dyes such as pyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-tit(6'-methoxybenzo)spiropyran, 3-propyl-spiro-dibenzopyran, Rhodamine-B -Lactam dyes such as anilinolactam, rhodamine(p-nitroanilino)lactam, rhodamine(0-chloroanilino)lactam, 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino -7-methoxyfluorane, 3
-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3-(N
-ethyl-p-)luidino)-7-methylfluorane,
゛3-diethylamino? -N-acetyl-N-methylaminofluorane, 3-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-N-
Methyl-N-benzylaminofluorane, 3-diethylamino-7-N-chloroethyl-N-methylaminofluorane, 3-diethylamino-7-N-diethylaminofluorane, 3-(N-ethyl-p-)luidino) -6
-Methyl-7-phenylaminofluorane, 3-(N-
Ethyl-p-)luidino)-6-methyl-7-(p-)
luidino) fluoran, 3-diethylamino-6-methyl-7-phenylaminofluoran, 3-dibutylamino-6-methyl-7-phenylaminofluoran,
3-diethylamino-7-(2-carbomethoxy-phenylamino)fluorane, 3-(N-cyclohexyl-
N-methylamino)-6-methyl-7-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-phenylaminofluorane, 3-piperidino-6-methyl-7
-phenylaminofluorane, 3-diethylamino-6
-methyl-7-xylidinofluorane, 3-diethylamino-7-(O-chlorophenylamino)fluoran,
3-dibutylamino-7-(o-chlorophenylamino)fluoran, 3-pyrrolidino-6-methyl-7-p
-Butylphenylaminofluorane, 3-(N-methyl-N-n-amyl)amino-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-n-amyl)amino-6 -Methyl-7-phenylaminofluorane, 3-(N-ethyl-N-1so-amyl)amino-6-methyl-7-phenylaminofluorane, 3-(
N-methyl-N-n-hexyl)amino-6-methyl-
7-phenylaminofluorane, 3-(N-ethyl-N
-n-hexyl)amino-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-β-ethylhexyl)amino-6-methyl-7-phenylaminofluorane, and the like.
又、感熱記録材料におシ１て、添加することができる補
助物質を組み合わせて使用することができる。例えば、
増感剤としてパラベンジルビフェニル、ジベンジルテレ
フタレート、１−ヒドロキシ−２−ナフトエ酸フェニル
、シュウ酸ジベンジル、アジピン酸ジーＯ−クロルベン
ジル、１．２−ジ（３−メチルフェノキシ）エタン、シ
ュウ酸ジーｐ−クロルベンジルなどを使用できる。また
、サーマルヘッドへのスティッキングや粕付着を改善す
るために炭酸カルシウム、タルク、酸化チタン、ケイ酸
アルミニウム、微粒子状無水シリカ、クレーなどを配合
したり、サーマルヘッドとの摩擦抵抗を下げ、またステ
ィッキング防止のためにステアリン酸亜鉛、ステアリン
酸カルシウム、パラフィンワックス、各種エステルワッ
クス、ポリエチレンなどを配合することもできる。この
外、必要により消泡剤、蛍光染料、着色染料、有機顔料
を添加して何ら差支えない。Further, auxiliary substances that can be added to the heat-sensitive recording material can be used in combination. for example,
Sensitizers include parabenzylbiphenyl, dibenzyl terephthalate, phenyl 1-hydroxy-2-naphthoate, dibenzyl oxalate, di-O-chlorobenzyl adipate, 1,2-di(3-methylphenoxy)ethane, di-oxalate. p-chlorobenzyl and the like can be used. In addition, in order to improve the sticking and lees adhesion to the thermal head, we have added calcium carbonate, talc, titanium oxide, aluminum silicate, fine particulate anhydrous silica, clay, etc., to reduce the frictional resistance with the thermal head, and to prevent sticking. For prevention, zinc stearate, calcium stearate, paraffin wax, various ester waxes, polyethylene, etc. can also be blended. In addition, an antifoaming agent, fluorescent dye, coloring dye, or organic pigment may be added as necessary.
バインダーとしては、デンプン類、ポリビニルアルコー
ル、各種変性ポリビニルアルコール、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、アラビヤゴム、スチレン
、無水マレイン酸共重合体、アクリルアミドなどが使用
できる。As the binder, starches, polyvinyl alcohol, various modified polyvinyl alcohols, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, styrene, maleic anhydride copolymer, acrylamide, etc. can be used.
支持体は特に限定されない。紙、顔料塗工紙、合成紙、
合成フィルムなどが使用される。The support is not particularly limited. paper, pigment coated paper, synthetic paper,
Synthetic films are used.
本発明において、記録層を形成する方法は、特に限定さ
れない。例えば従来からよく知られている方法、例えば
エアーナイフコーター、ブレードコーター、バーコータ
ーなどが使用できる。塗工量は特に規定されるものでは
ないが、通常乾燥重量で１乃至１５ｇ／ゴ、好ましくは
２乃至９ｔｘ／ｒｄの範囲で塗布される。In the present invention, the method of forming the recording layer is not particularly limited. For example, conventionally well-known methods such as an air knife coater, blade coater, bar coater, etc. can be used. Although the coating amount is not particularly limited, it is usually applied in a dry weight range of 1 to 15 g/rd, preferably 2 to 9 tx/rd.
［実 施 例］
以下に本発明の実施例を示すが、これによって本発明が
特に限定されるものではない。実施例および比較例中の
部および％は重量部および重量％を示す。[Example] Examples of the present invention are shown below, but the present invention is not particularly limited by these. Parts and % in Examples and Comparative Examples indicate parts by weight and % by weight.
実施例 １
■Ａ液調製
３− （Ｎ−シクロヘキ、シルーＮ−メチルアミノ）−
６−メチル−７−フェニル
アミノフルオラン ４０部ｌＯ％ポリ
ビニルアルコール水溶液 ２０部水
２０部この組成物をサンド
グラインダーで平均粒径１μｓまで粉砕した。Example 1 ■Preparation of liquid A 3- (N-cyclohex, sil-N-methylamino)-
6-Methyl-7-phenylaminofluorane 40 parts lO% polyvinyl alcohol aqueous solution 20 parts water
20 parts of this composition was ground with a sand grinder to an average particle size of 1 μs.
■ Ｂ液調製
２．２′−ジヒドロキシジフェニルエーテル ４０部１
０％ポリビニルアルコール水溶液 ２０部水
２０部この組成物を
サンドグラインダーで平均粒径１．５μｓまで粉砕した
。■ Preparation of B solution 2.2'-dihydroxydiphenyl ether 40 parts 1
0% polyvinyl alcohol aqueous solution 20 parts water
20 parts of this composition was ground with a sand grinder to an average particle size of 1.5 μs.
■ Ｃ波調製
バラベンジルビフェニル ４０部ｌＯ％
ポリビニルアルコール水溶液 ２０部水
２０部この組成物をサ
ンドグラインダーで平均粒径１．５−まで粉砕した。■ C-wave prepared rosebenzyl biphenyl 40 parts lO%
Polyvinyl alcohol aqueous solution 20 parts water
20 parts of this composition were ground in a sand grinder to an average particle size of 1.5-.
Ａ液ｌＯ部、Ｂ液２０部、Ｃ液２０部、５０％炭酸カル
シウム分散液３０部、３０％ステアリン酸亜鉛の分散液
８部に１０％ポリビニルアルコール水溶液７５部を加え
て、撹拌し、塗液とした。この塗液を５０ｇ／ｒｒｒの
原紙に乾燥後の塗布重量が７ｇ／ｒｒｒとなるように塗
布乾燥して感熱記録紙を得た。75 parts of a 10% polyvinyl alcohol aqueous solution was added to 10 parts of solution A, 20 parts of solution B, 20 parts of solution C, 30 parts of a 50% calcium carbonate dispersion, and 8 parts of a 30% zinc stearate dispersion, stirred, and coated. It was made into a liquid. This coating liquid was applied to a base paper of 50 g/rrr so that the coated weight after drying was 7 g/rrr and dried to obtain a heat-sensitive recording paper.
実施例 ２
Ｂ液調製にあたって、２．２’−ジヒドロキシジフェニ
ルエーテルの代わりに同量の４．４′−ジヒドロキシジ
フェニルエーテルを用いた以外は、実施例１と同様にし
て感熱記録紙を得た。Example 2 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that the same amount of 4,4'-dihydroxydiphenyl ether was used in place of 2,2'-dihydroxydiphenyl ether in preparing Liquid B.
実施例 ３
Ｂ液調製にあたって、２．２′−ジヒドロキシジフェニ
ルエーテルの代わりに同量の３．３′−ジヒドロキシジ
フェニルエーテルを用いた以外は、実施例１と同様にし
て感熱記録紙を得た。Example 3 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that the same amount of 3.3'-dihydroxydiphenyl ether was used in place of 2.2'-dihydroxydiphenyl ether in preparing Liquid B.
比較例 Ｉ
Ｂ液調製にあたって、２．２′−ジヒドロキシジフェニ
ルエーテルの代わりに同量の２，２−ビス（４′−ヒド
ロキシフェニル）プロパン（ビスフェノールＡ）を用い
た以外は、実施例１と同様にして感熱記録紙を得た。Comparative Example I The same procedure as in Example 1 was carried out, except that the same amount of 2,2-bis(4'-hydroxyphenyl)propane (bisphenol A) was used instead of 2,2'-dihydroxydiphenyl ether in preparing Solution B. A thermosensitive recording paper was obtained.
このようにして得た４種類の感熱記録紙について、スー
パーカレンダー仕上げを行ない、白色度と記録濃度につ
いて測定を行なった。白色度についてはハンター白色度
計を用い、記録濃度については松下電送側製ＵＦ−８０
で印字後、マクベス社製ＲＤ−１００Ｒ型濃度計で記録
濃度を測定した。The four types of heat-sensitive recording paper thus obtained were subjected to supercalender finishing, and the whiteness and recording density were measured. For whiteness, we used a Hunter whiteness meter, and for recording density, we used UF-80 manufactured by Matsushita Electric Transmission.
After printing, the recorded density was measured using a Macbeth RD-100R type densitometer.
表より明らかなように各実施例の感熱記録紙は、比較例
の場合に比し記録濃度、白色度の点で従来の感熱記録紙
よりすぐれている。As is clear from the table, the thermal recording paper of each example is superior to the conventional thermal recording paper in terms of recording density and whiteness compared to the comparative example.
［発明の効果］
本発明では前記の一般式を有するジヒドロキシジフェニ
ルエーテルを顕色剤として使用したことにより、実用的
で広い用途に使用できる発色感度を有し、かつ白色度の
高い、高度な品質要求に対応することができる感熱記録
材料を提供することができた。[Effects of the Invention] In the present invention, by using dihydroxydiphenyl ether having the above general formula as a color developer, it has color development sensitivity that can be used in a wide range of practical applications, and has high whiteness, which meets the high quality requirements. We were able to provide a heat-sensitive recording material that can handle the following.
Claims (1)
料と一般式 ▲数式、化学式、表等があります▼ で表わされるジヒドロキシジフェニルエーテルとを含む
ことを特徴とする感熱記録材料。[Scope of Claims] A heat-sensitive recording material characterized in that the heat-sensitive layer contains at least one colorless or light-colored basic dye and dihydroxydiphenyl ether represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ .
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63004498A JPH01180382A (en) | 1988-01-12 | 1988-01-12 | Thermal recording material |
| CA000587318A CA1312730C (en) | 1988-01-12 | 1988-12-30 | Thermal recording material |
| EP89300177A EP0324576A3 (en) | 1988-01-12 | 1989-01-10 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63004498A JPH01180382A (en) | 1988-01-12 | 1988-01-12 | Thermal recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01180382A true JPH01180382A (en) | 1989-07-18 |
Family
ID=11585728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63004498A Pending JPH01180382A (en) | 1988-01-12 | 1988-01-12 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01180382A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0701905A1 (en) | 1994-09-14 | 1996-03-20 | New Oji Paper Co., Ltd. | Thermosensitive reversible colordeveloping and disappearing agent |
| JP2005206650A (en) * | 2004-01-21 | 2005-08-04 | Pilot Ink Co Ltd | Thermochromic composition and thermochromic microcapsule pigment encapsulating the same |
-
1988
- 1988-01-12 JP JP63004498A patent/JPH01180382A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0701905A1 (en) | 1994-09-14 | 1996-03-20 | New Oji Paper Co., Ltd. | Thermosensitive reversible colordeveloping and disappearing agent |
| JP2005206650A (en) * | 2004-01-21 | 2005-08-04 | Pilot Ink Co Ltd | Thermochromic composition and thermochromic microcapsule pigment encapsulating the same |
| JP4485213B2 (en) * | 2004-01-21 | 2010-06-16 | パイロットインキ株式会社 | Reversible thermochromic composition and reversible thermochromic microcapsule pigment containing the same |
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