JPH0241436B2 - - Google Patents
Info
- Publication number
- JPH0241436B2 JPH0241436B2 JP57035119A JP3511982A JPH0241436B2 JP H0241436 B2 JPH0241436 B2 JP H0241436B2 JP 57035119 A JP57035119 A JP 57035119A JP 3511982 A JP3511982 A JP 3511982A JP H0241436 B2 JPH0241436 B2 JP H0241436B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- heat
- recording sheet
- color
- sensitive recording
- 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
- -1 hydroxyphthalic acid diester Chemical class 0.000 claims description 15
- MNUOZFHYBCRUOD-UHFFFAOYSA-N hydroxyphthalic acid Natural products OC(=O)C1=CC=CC(O)=C1C(O)=O MNUOZFHYBCRUOD-UHFFFAOYSA-N 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- WVDGHGISNBRCAO-UHFFFAOYSA-N 2-hydroxyisophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1O WVDGHGISNBRCAO-UHFFFAOYSA-N 0.000 claims 1
- 239000000975 dye Substances 0.000 description 11
- 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 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 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 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- CEGHCPGGKKWOKF-UHFFFAOYSA-N 2'-anilino-6'-[cyclohexyl(methyl)amino]-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C=C(C2(C3=CC=CC=C3C(=O)O2)C2=CC(NC=3C=CC=CC=3)=C(C)C=C2O2)C2=CC=1N(C)C1CCCCC1 CEGHCPGGKKWOKF-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UYMBCDOGDVGEFA-UHFFFAOYSA-N 3-(1h-indol-2-yl)-3h-2-benzofuran-1-one Chemical compound C12=CC=CC=C2C(=O)OC1C1=CC2=CC=CC=C2N1 UYMBCDOGDVGEFA-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 class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- VHNFAQLOVBWGGB-UHFFFAOYSA-N benzhydrylbenzene;3h-2-benzofuran-1-one Chemical class C1=CC=C2C(=O)OCC2=C1.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 VHNFAQLOVBWGGB-UHFFFAOYSA-N 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 239000000945 filler Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 239000000314 lubricant 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
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000000203 mixture Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Color Printing (AREA)
Description
本発明は、感熱記録シートに関し、特に感熱記
録シートに用いられる顕色剤に関する。
感熱記録シートは、通常無色ないし淡色の発色
性無色染料と顕色剤とを隔離された状態でバイン
ダーとその添加剤と共に基紙表面に塗布すること
により作成されている。そして、記録装置におい
て、この記録シートにサーマルヘツドや熱ペンな
どの発熱素子が接触した時に染料と顕色剤が反応
して黒色等に発色し、シート上に記録される。
従来、顕色剤としては、フエノール類の顕色剤
が用いられていた。例えば、ビスフエノールＡ
（融点156〜158℃）が品質の安定性、価格、入手
し易さなどの点から現在広く使用されているが、
このビスフエノールＡには熱発色温度が高い欠点
がある。これに対して融点の低いフエノール性物
質、例えば４−ターシヤリブチルフエノール、α
−ナフトール、β−ナフトール等のモノフエノー
ル類を使用した場合には、感熱記録シートの保存
性、安定性が悪く、室温でも次第に地色が発色し
てくるだけでなく、いわゆるフエノール臭が強く
実用的ではない。また、特公昭54−12819号では、
Ｐ，P′−（１−メチル−ノルマルヘキシリデン）
ジフエノールについては、融点が低く、安定性、
発色性の良い感熱記録シートを作成することがで
きるように記録されているが、このものは入手し
にくい欠点がある。
以上の欠点を改善するためにＰ−ヒドロキシ安
息香酸エステル（特開昭56−144193号）が提案さ
れ、特にそのベンジルエステルが実用化されてい
る。しかしながら、これには昇華性が大きく写体
に色むらが生じる等の欠点があつた。
本発明者は、かゝる従来の欠点を改善する方法
について鋭意研究した結果、ヒドロキシフタル酸
のジエステルを顕色剤として用いることによつて
上記欠点を解決しうることを見出し本発明を完成
した。
すなわち、本発明は、通常無色ないし淡色の発
色性無色染料と融点約60〜約120℃であるヒドロ
キシフタル酸ジエステルとを含有することを特徴
とする感熱記録シートに存する。
本発明に用いられるヒドロキシフタル酸ジエス
テルとしては、４−ヒドロキシ−オルソフタル
酸、２−、４−若しくは５−ヒドロキシ−イフタ
ル酸又はヒドロキシ−テレフタル酸のジエステル
があげられる。例えば、第１表に記載されるジア
ルキルエステル及びジフエニルエステル類があげ
られるが、その他ベンジルエステル等も用途に応
じて用いられる。
The present invention relates to a heat-sensitive recording sheet, and particularly to a color developer used in a heat-sensitive recording sheet. A thermosensitive recording sheet is usually prepared by coating a base paper surface with a colorless or light-colored colorless dye and a color developer in a separated state together with a binder and its additives. In the recording apparatus, when a heating element such as a thermal head or a hot pen comes into contact with this recording sheet, the dye and color developer react to develop a color such as black, which is recorded on the sheet. Conventionally, phenolic color developers have been used as color developers. For example, bisphenol A
(melting point 156-158℃) is currently widely used due to its stability of quality, price, and ease of availability.
This bisphenol A has the disadvantage of a high thermal coloring temperature. In contrast, phenolic substances with low melting points, such as 4-tertiarybutylphenol, α
- When monophenols such as naphthol and β-naphthol are used, the shelf life and stability of the heat-sensitive recording sheet are poor, and not only does the background color gradually develop even at room temperature, but it also has a strong so-called phenol odor, which is difficult to use in practical use. Not the point. Also, in Special Publication No. 54-12819,
P, P'-(1-methyl-n-hexylidene)
Diphenol has a low melting point, stability,
It has been recorded that it is possible to create a heat-sensitive recording sheet with good color development, but it has the disadvantage that it is difficult to obtain. In order to improve the above-mentioned drawbacks, P-hydroxybenzoic acid ester (Japanese Patent Application Laid-Open No. 144193/1983) has been proposed, and its benzyl ester has been put into practical use. However, this method had drawbacks such as high sublimation and color unevenness in the photographic subject. As a result of intensive research into methods for improving the conventional drawbacks, the present inventors discovered that the above drawbacks could be solved by using diester of hydroxyphthalic acid as a color developer, and completed the present invention. . That is, the present invention resides in a heat-sensitive recording sheet characterized by containing a normally colorless to light-colored color-forming colorless dye and a hydroxyphthalic acid diester having a melting point of about 60 to about 120°C. Hydroxyphthalic acid diesters used in the present invention include diesters of 4-hydroxy-orthophthalic acid, 2-, 4- or 5-hydroxy-ifthalic acid or hydroxy-terephthalic acid. Examples include dialkyl esters and diphenyl esters listed in Table 1, but other benzyl esters and the like may also be used depending on the purpose.
【表】
本発明に用いられる上記ヒドロキシフタル酸ジ
エステルは、その融点が約60〜約120℃であるこ
とが必要であり、融点が低いと保存安定性が悪
く、記録画像のコントラストが悪くなり、融点が
高すぎれば高い発色記録温度が要求され微少な熱
量によつて熱応答性が充分得られず最近のような
高速化されたフアクシミリ等に使用できなくな
る。
ヒドロキシフタル酸ジエステルの製造法は、一
般にはオルソー、メタ−又はテレ−フタル酸を常
法によりスルホン化又はハロゲン化したのち、前
者はアルカリ溶融により、後者は苛性ソーダー水
中で加水分解することにより得られるヒドロキシ
フタル酸を酸触媒下にエステル化する一般的方法
によつて容易に合成することができる。
なお、本発明のヒドロキシフタル酸ジエステル
は感熱記録シートの顕色剤として単独に使用する
ことができることは勿論であるが、その用途及び
所要性能に応じて従来使用されているビスフエノ
ールＡ、Ｐ，P′（１−メチル−ノルマルヘキシリ
デン）ジフエノール、Ｐ−ターシヤリ−ブチルフ
エノール、Ｐ−フエニルフエノール、ノボラツク
型フエノール樹脂などのフエノール類或は有機酸
類と併用することも可能である。
また、本発明に使用される通常無色ないし淡色
の発色性無色染料としては、各種の染料が周知で
あり、特に限定されるものではないが、例えば下
記のものがあげられる。
(1) ラクトン環を有する化合物
フルオラン系
○イ ３−ジエチルアミノ−６−メチル−７−
アニリノフルオラン（黒色）
○ロ 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（黒
色）、
○ハ ３−ジエチルアミノ−６−メチル−７−
（オルト、パラージメチルアニリノ）フル
オラン（黒色）、
○ニ ３−ピロリジノー６−メチル−７−アニ
リノフルオラン（黒色）、
○ホ ３−ピペリジノ−６−メチル−７−アニ
リノフルオラン（黒色）、
○ヘ ３−（Ｎ−シクロヘキシル−Ｎ−メチル
アミノ）−６−メチル−７−アニリノフル
オラン（黒色）、
○ト ３−ジエチルアミノ−７−（オルトクロ
ロアニリノ）フルオラン（黒色）、
○チ ３−ジエチルアミノ−７−（メタートリ
フルオロメチルアニリノ）フルオラン（黒
色）、
○リ ３−ジエチルアミノ−６−メチル−クロ
ロフルオラン（赤色）
○ヌ ３−ジエチルアミノ−６−メチル−フル
オラン（赤色）、
○ル ３−シクロヘキシルアミノ−６−クロロ
フルオラン（橙色）、
トリフエニルメタン−フタリド系
○イ CVL（クリスタルバイオレツトラクト
ン）（青色）、
○ロ MGL（緑）、
○ハ グレープ
インドリルフタリド系
○イ インドリルレツド（赤色）
○ロ インドリルブルー（青色）
その他
アザフタリド系、ラクタム系、スピロピラ
ン系、クロメノインドール系もある。
これら染料の中でも、特に好ましいのはフルオ
ラン系化合物であり、その他の染料は退色性があ
つたり、使用前に光によつて変質する等の欠点が
あり、用途は限定される。
前述の顕色剤および発色性無色染料は、ボール
ミル、アトライター、サンドグラインダーなどの
磨砕機あるいは適当な浮化装置によつて該ミクロ
ン以下の粒子径になるまで微粒化し、目的に応じ
て各種の添加材料を加えて塗液とする。この塗液
には通常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、デンプン類、
スチレン−無水マレイン酸共重合体、酢酸ビニル
−無水マレイン酸共重合体、スチレン−ブタジエ
ン共重合体などの結合剤、並びにカオリン、焼成
カオリン、ケイソウ土、タルク、チタン、炭酸カ
ルシウム、炭酸マグネシウム、水酸化アルミニウ
ムなどの無機又は有機充填剤を添加するが、この
他に脂肪酸金属塩などの離型剤、ワツクス類など
の滑剤、ベンゾフエノン系やトリアゾール系の紫
外線吸収剤、グリオキザールなどの耐水化剤、分
散剤、消泡剤などを使用することができる。この
塗液を紙および各種フイルム類に塗布することに
よつて目的とする感熱記録シートが得られる。
本発明に使用するヒドロキシフタル酸ジエステ
ルの種類及び量、その他の各種成分の量は、要求
される性能及び記録適性に従つて決定され、特に
限定されるものではないが、通常発色性染料１部
に対してヒドロキシフタル酸ジエステル２〜10
部、充填剤は１〜20部を使用し、結合剤は全固形
分中10〜20％の量が適当である。
次に、本発明を実施例をあげて具体的に説明す
る。
実施例 １
Ａ液（染料分散液）
３−ジエチルアミノ−６−メチル−７−アニリノ
フルオラン 2.0部
10％ポリビニルアルコール水溶液 4.6部
水 2.5部
Ｂ液（顕色剤分散液）
顕色剤*（第２表参照） 6.0部
ステアリン酸亜鉛 0.5部
10％ポリビニルアルコール水溶液 30部
＊顕色剤としては第２表に示すごとくヒドロキ
シフタル酸ジエステル類およびビスフエノー
ルＡを使用。
上記の組成物の各液をボールミル粒子径３ミク
ロンまで磨砕する。
次いで下記の割合で分散液を混合して塗液とす
る。
Ａ液（染料分散液） 9.1部
Ｂ液（顕色剤分散液） 36.5部
カオリンクレー（50％分散液） 12部
この塗液を50ｇ／m2の基紙の片面に塗布量6.0
ｇ／m2になるよう塗布乾燥し、そのシートをスー
パーカレンダーで平滑度が200〜300秒になるよう
に処理した。得られた黒発色の感熱記録シートに
ついて品質性能試験を行つた結果を第２表に示
す。[Table] The above-mentioned hydroxyphthalic acid diester used in the present invention must have a melting point of about 60 to about 120°C. If the melting point is low, storage stability will be poor, and the contrast of recorded images will be poor. If the melting point is too high, a high color development recording temperature is required, and sufficient thermal responsiveness cannot be obtained due to the small amount of heat, making it impossible to use it in recent high-speed facsimiles. Hydroxyphthalic acid diesters are generally produced by sulfonating or halogenating ortho-, meta-, or tere-phthalic acid by a conventional method, and then the former is obtained by alkali melting, and the latter is obtained by hydrolyzing in caustic soda water. It can be easily synthesized by a general method of esterifying hydroxyphthalic acid under an acid catalyst. It goes without saying that the hydroxyphthalic acid diester of the present invention can be used alone as a color developer for heat-sensitive recording sheets, but depending on the application and required performance, conventionally used bisphenols A, P, It is also possible to use it in combination with phenols or organic acids such as P'(1-methyl-n-hexylidene) diphenol, P-tertiary-butylphenol, P-phenylphenol, and novolak type phenolic resin. Various dyes are well known as the normally colorless to light-colored colorless dyes used in the present invention, and are not particularly limited, but include, for example, the following. (1) Compounds with a lactone ring Fluorane type ○I 3-diethylamino-6-methyl-7-
Anilinofluorane (black) ○Ro 3-(N-ethyl-P-toluidino)-6
-Methyl-7-anilinofluorane (black), ○C 3-diethylamino-6-methyl-7-
(ortho, p-dimethylanilino) fluorane (black), ○d 3-pyrrolidino-6-methyl-7-anilinofluorane (black), ○e 3-piperidino-6-methyl-7-anilinofluorane (black) ), ○h 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran (black), ○h 3-diethylamino-7-(orthochloroanilino)fluoran (black), ○3-diethylamino-7-(meth-trifluoromethylanilino)fluoran (black), ○2 3-diethylamino-6-methyl-chlorofluoran (red) ○nu 3-diethylamino-6-methyl-fluoran (red) ), ○3-cyclohexylamino-6-chlorofluorane (orange), triphenylmethane-phthalide series ○A CVL (crystal violet lactone) (blue), ○B MGL (green), ○C Grape indolyl phthalide ○B Indolyl Red (Red) ○B Indolyl Blue (Blue) Others There are also azaphthalides, lactams, spiropyrans, and chromenoindoles. Among these dyes, fluoran compounds are particularly preferred; other dyes have disadvantages such as fading and deterioration by light before use, and their uses are limited. The above-mentioned color developer and color-forming colorless dye are atomized using a grinder such as a ball mill, attritor, or sand grinder, or an appropriate flotation device, to a particle size of less than a micron, and then processed into various types depending on the purpose. Add additive materials to make a coating liquid. This coating liquid usually contains polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, starches,
Binders such as styrene-maleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, styrene-butadiene copolymer, and kaolin, calcined kaolin, diatomaceous earth, talc, titanium, calcium carbonate, magnesium carbonate, and water. Inorganic or organic fillers such as aluminum oxide are added, but in addition, mold release agents such as fatty acid metal salts, lubricants such as waxes, ultraviolet absorbers such as benzophenone and triazole, water resistance agents such as glyoxal, and dispersion are added. agents, antifoaming agents, etc. can be used. By applying this coating liquid to paper and various films, the desired heat-sensitive recording sheet can be obtained. The type and amount of hydroxyphthalic acid diester and the amounts of other various components used in the present invention are determined according to the required performance and recording suitability, and are not particularly limited, but usually one part of color-forming dye is used. Hydroxyphthalic acid diester 2 to 10
The filler is used in an amount of 1 to 20 parts, and the binder is suitably used in an amount of 10 to 20% based on the total solid content. Next, the present invention will be specifically explained with reference to Examples. Example 1 Liquid A (dye dispersion) 3-diethylamino-6-methyl-7-anilinofluorane 2.0 parts 10% polyvinyl alcohol aqueous solution 4.6 parts Water 2.5 parts Liquid B (developer dispersion) Color developer * ( (See Table 2) 6.0 parts Zinc stearate 0.5 parts 10% polyvinyl alcohol aqueous solution 30 parts * Hydroxyphthalic acid diesters and bisphenol A are used as color developers as shown in Table 2. Each of the above compositions is ball milled to a particle size of 3 microns. Next, the dispersion liquid is mixed in the proportions shown below to prepare a coating liquid. Part A (dye dispersion) 9.1 parts Part B (developer dispersion) 36.5 parts Kaolin clay (50% dispersion) 12 parts Apply this coating solution to one side of 50 g/m 2 base paper in an amount of 6.0
g/m 2 and dried, and the sheet was treated with a supercalender to a smoothness of 200 to 300 seconds. Table 2 shows the results of a quality performance test performed on the obtained black-colored heat-sensitive recording sheet.
【表】
第２表から明らかのように、本発明の実施例１
の１−１〜５−１はビスフエノールＡを使用した
対照例６−１に比べて、地色が良好であり、経時
変化も少ない。また対照例に比べても発色濃度、
特にフアクシミリで記録した場合の動的発色濃度
が高く、白ぬけも殆んど認められない。[Table] As is clear from Table 2, Example 1 of the present invention
Samples 1-1 to 5-1 have better ground colors and less change over time than Control Example 6-1 using bisphenol A. Also, compared to the control example, the color density
In particular, when recorded by facsimile, the dynamic color density is high and almost no white spots are observed.
Claims (1)
が約60〜約120℃であるヒドロキシフタル酸ジエ
ステルとを含有することを特徴とする感熱記録シ
ート。 ２ 染料がフルオラン系の染料である特許請求の
範囲第１項記載の感熱記録シート。 ３ ヒドロキシフタル酸ジエステルがヒドロキシ
オルソフタル酸、ヒドロキシイソフタル酸又はヒ
ドロキシテレフタル酸のそれぞれのジアルキルエ
ステルである特許請求の範囲第１項記載の感熱記
録シート。[Scope of Claims] 1. A heat-sensitive recording sheet characterized by containing a normally colorless to light-colored colorless dye and a hydroxyphthalic acid diester having a melting point of about 60 to about 120°C. 2. The heat-sensitive recording sheet according to claim 1, wherein the dye is a fluoran dye. 3. The heat-sensitive recording sheet according to claim 1, wherein the hydroxyphthalic acid diester is a dialkyl ester of hydroxyorthophthalic acid, hydroxyisophthalic acid, or hydroxyterephthalic acid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57035119A JPS58153692A (en) | 1982-03-08 | 1982-03-08 | Heat-sensitive recording sheet |
| DE19833330540 DE3330540A1 (en) | 1982-03-08 | 1983-08-24 | Heat-sensitive plane recording material |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57035119A JPS58153692A (en) | 1982-03-08 | 1982-03-08 | Heat-sensitive recording sheet |
| DE19833330540 DE3330540A1 (en) | 1982-03-08 | 1983-08-24 | Heat-sensitive plane recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58153692A JPS58153692A (en) | 1983-09-12 |
| JPH0241436B2 true JPH0241436B2 (en) | 1990-09-17 |
Family
ID=25813435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57035119A Granted JPS58153692A (en) | 1982-03-08 | 1982-03-08 | Heat-sensitive recording sheet |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS58153692A (en) |
| DE (1) | DE3330540A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62299382A (en) * | 1986-06-19 | 1987-12-26 | Ricoh Co Ltd | Two color thermal recording material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58173695A (en) * | 1982-04-06 | 1983-10-12 | Jujo Paper Co Ltd | Heat sensitive recording sheet |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5887093A (en) * | 1981-11-17 | 1983-05-24 | Kanzaki Paper Mfg Co Ltd | Heat-sensitive recording material |
-
1982
- 1982-03-08 JP JP57035119A patent/JPS58153692A/en active Granted
-
1983
- 1983-08-24 DE DE19833330540 patent/DE3330540A1/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58173695A (en) * | 1982-04-06 | 1983-10-12 | Jujo Paper Co Ltd | Heat sensitive recording sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3330540C2 (en) | 1991-07-18 |
| DE3330540A1 (en) | 1985-03-14 |
| JPS58153692A (en) | 1983-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0226874B2 (en) | ||
| JPH0241436B2 (en) | ||
| JPH0347790A (en) | Thermal recording material | |
| US4442176A (en) | Heat-sensitive recording sheet | |
| JPH0211439B2 (en) | ||
| US5322831A (en) | Thermal recording sheet | |
| JP2754447B2 (en) | Thermal recording medium | |
| JP2761658B2 (en) | Thermal recording medium | |
| JPS6410358B2 (en) | ||
| JPH0528194B2 (en) | ||
| JPH0257028B2 (en) | ||
| JPS63132087A (en) | Heat-sensitive recording sheet | |
| JP2694656B2 (en) | Thermal recording medium | |
| JP2711360B2 (en) | Thermal recording medium | |
| JPS60127189A (en) | Thermal recording paper | |
| JPS60151094A (en) | Thermal recording sheet | |
| JPS60220787A (en) | Thermal recording sheet | |
| JPS588691A (en) | Heat-sensitive recording sheet | |
| GB2145236A (en) | Heat-sensitive recording sheet | |
| JPH0784098B2 (en) | Thermal recording | |
| JP2003246152A (en) | Developer and thermal recording material containing the same | |
| JPS60147386A (en) | Thermal recording paper | |
| JPS60151093A (en) | Thermal recording material | |
| JPH08197847A (en) | Red and black two colors thermal recording material | |
| JPH0338378A (en) | Thermal recording material |