JPH0365798B2 - - Google Patents
Info
- Publication number
- JPH0365798B2 JPH0365798B2 JP59099375A JP9937584A JPH0365798B2 JP H0365798 B2 JPH0365798 B2 JP H0365798B2 JP 59099375 A JP59099375 A JP 59099375A JP 9937584 A JP9937584 A JP 9937584A JP H0365798 B2 JPH0365798 B2 JP H0365798B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- general formula
- dye
- recording paper
- 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
- 239000000975 dye Substances 0.000 claims description 47
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 claims description 14
- -1 4-hydroxybenzoyloxybenzoic acid ester Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 7
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- VHNFAQLOVBWGGB-UHFFFAOYSA-N benzhydrylbenzene;3h-2-benzofuran-1-one Chemical compound C1=CC=C2C(=O)OCC2=C1.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 VHNFAQLOVBWGGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000004040 coloring Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000005041 acyloxyalkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 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 6
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 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 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011056 performance test Methods 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ABJAMKKUHBSXDS-UHFFFAOYSA-N 3,3-bis(6-amino-1,4-dimethylcyclohexa-2,4-dien-1-yl)-2-benzofuran-1-one Chemical compound C1=CC(C)=CC(N)C1(C)C1(C2(C)C(C=C(C)C=C2)N)C2=CC=CC=C2C(=O)O1 ABJAMKKUHBSXDS-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
- LYCCNHVQBSOODL-UHFFFAOYSA-N 6-(diethylamino)-3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C=1C(N(CC)CC)=CC=C2C=1C(=O)OC2(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 LYCCNHVQBSOODL-UHFFFAOYSA-N 0.000 description 1
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 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
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 1
- LNYGGKYWZSLKCZ-UHFFFAOYSA-N OC1=C(C=CC(=C1)N(C)C)C1(OC(=O)C2=CC=CC=C12)C1=C(C=CC(=C1)[N+](=O)[O-])OC.OC1=C(C=CC(=C1)N(C)C)C1(OC(=O)C2=CC=CC=C12)C1=C(C=CC(=C1)Cl)OC Chemical compound OC1=C(C=CC(=C1)N(C)C)C1(OC(=O)C2=CC=CC=C12)C1=C(C=CC(=C1)[N+](=O)[O-])OC.OC1=C(C=CC(=C1)N(C)C)C1(OC(=O)C2=CC=CC=C12)C1=C(C=CC(=C1)Cl)OC LNYGGKYWZSLKCZ-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 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
- 239000010419 fine particle Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- 239000006082 mold release agent Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
産業上の利用分野
本発明は感熱記録紙に関し、耐光性に優れ、更
に高湿、高温の環境下においても安定な感熱記録
紙に関するものである。
従来の技術
一般に感熱記録紙は通常無色ないし淡色の塩基
性無色染料とフエノール性物質等の有機顕色剤と
を、それぞれ微細な粒子に磨砕分散した後両者を
混合し、バインダー、充填剤、感度向上剤、滑剤
その他の助剤を添加して得た塗液を紙やフイルム
等の支持体に塗工したもので、加熱による瞬時の
化学反応により発色記録を得るものである。この
場合、無色染料の品種を選択することで各種の色
相の発色が得られる。
クリスタルバイオレツトラクトン(CVL)の
ようなロイコ染料とフエノール化合物とが反応し
て呈色することは古くから知られており、前記呈
色反応の感熱紙への応用は、例えば特公昭45−
14039号に記載されている。
しかし、一般にトリフエニルメタン・フタリド
系ロイコ染料とビスフエノールA等のフエノール
化合物との熱反応により得られる発色画像は非常
に鮮明であるが、光・熱・湿度に対して不安定で
ある。特に光に対する安定性に乏しく、長時間さ
らされると退色して画像濃度が薄くなつたり、時
には完全に消色してしまうことがある。
この耐光性の欠点を改良するために、種々の方
法が提案されている。例えばジ−β−ナフチル−
P−フエニレンジアミンの添加(特公昭53−
34904)、ベンゾフエノン系紫外線吸収剤の添加
(特開昭54−18752)、水溶性紫外線吸収剤の添加
(特開昭55−93492)、フエノチアジン類の添加
(特開昭57−167294)などがあげられる。しかし、
これらの耐光性向上剤を添加してもその効果は充
分でない。
又、特開昭57−27782号は感圧感熱記録紙用の
新規なトリフエニルメタン系染料を提案し、感圧
記録紙を想定したCVLの欠点、即ち酸性白土系、
フエノールレジン系やフエノール誘導体金属錯塩
系の顕色剤に対して耐光性が不足するという欠点
を補う上でこの新規染料の併用が有効である旨記
載している。
本発明者らは、感熱記録紙の場合において、上
述の新規染料のみならず、本明細書に一般式
()として示した一定のアミノトリアリールメ
タン系染料は、これをCVLと併用することによ
り耐光性の優れた画像が得られることを確認し
た。
しかしながら、一方、上記の如く耐光性に優れ
ている感熱記録紙も、ビスフエノールAを顕色剤
とする限り、高湿や高温の環境下における安定性
が不十分であつて、記録画像濃度の著しい低下や
白地部分の地発色がみられた。
発明の目的
本発明の目的は、耐光性に加えて、耐湿性や耐
熱性にも優れている感熱記録紙を提供することに
ある。
発明の構成
本発明は通常無色ないし淡色の塩基性無色染料
と有機顕色剤とを含有する感熱発色層を有する感
熱記録紙において、該発色層が有機顕色剤として
下記一般式()で表わされる4−ヒドロキシベ
ンゾイルオキシ安息香酸エステルを使用し、塩基
性無色染料として下記一般式()で示されるア
ミノトリアリールメタン系ロイコ染料及びトリフ
エニルメタン・フタリド系ロイコ染料の2種類の
ロイコ染料を含有するものである。
〔但し、一般式()中、RはC1〜C12のアルキ
ル基、シクロヘキシル基、ベンジル基、α−ナフ
チル基、フエニル基、β−ナフチル基またはβ−
フエネチル基を表わす。]
[但し、一般式()中、Rは
INDUSTRIAL APPLICATION FIELD The present invention relates to a heat-sensitive recording paper, which has excellent light resistance and is stable even in high-humidity and high-temperature environments. Conventional technology Generally, heat-sensitive recording paper is produced by grinding and dispersing a colorless or light-colored basic colorless dye and an organic color developer such as a phenolic substance into fine particles, and then mixing the two. A coating liquid obtained by adding a sensitivity improver, a lubricant, and other auxiliary agents is applied to a support such as paper or film, and color recording is obtained by an instantaneous chemical reaction caused by heating. In this case, various hues can be obtained by selecting the type of colorless dye. It has been known for a long time that a leuco dye such as crystal violet lactone (CVL) reacts with a phenol compound to form a color, and the application of the color reaction to thermal paper has been reported, for example, in Japanese Patent Publication No. 45-1973.
Described in No. 14039. However, although the colored images obtained by the thermal reaction between triphenylmethane/phthalide leuco dyes and phenol compounds such as bisphenol A are generally very clear, they are unstable against light, heat, and humidity. In particular, it has poor stability against light, and if exposed for a long time, the color may fade, resulting in a decrease in image density, or in some cases, the color may disappear completely. Various methods have been proposed to improve this defect in light resistance. For example, di-β-naphthyl-
Addition of P-phenylenediamine (Special Publication 1973-
34904), addition of benzophenone ultraviolet absorbers (Japanese Patent Application Laid-Open No. 18752, 1983), addition of water-soluble ultraviolet absorbers (Japanese Patent Application Laid-open No. 55-93492), and addition of phenothiazines (Japanese Patent Laid-Open No. 167294, 1983). It will be done. but,
Even if these light resistance improvers are added, the effect is not sufficient. In addition, JP-A No. 57-27782 proposed a new triphenylmethane dye for pressure-sensitive and heat-sensitive recording paper, and addressed the drawbacks of CVL intended for pressure-sensitive recording paper, namely acid clay-based dyes,
It is stated that the combined use of this new dye is effective in compensating for the drawback of insufficient light resistance compared to phenol resin-based and phenol derivative metal complex-based color developers. In the case of thermal recording paper, the present inventors have discovered that not only the above-mentioned new dye but also a certain aminotriarylmethane dye shown in the general formula () in this specification can be used in combination with CVL. It was confirmed that images with excellent light resistance could be obtained. However, as mentioned above, thermal recording paper that has excellent light resistance has insufficient stability in high humidity and high temperature environments as long as bisphenol A is used as a color developer, and the density of recorded images decreases. Significant deterioration and discoloration of white areas were observed. OBJECT OF THE INVENTION An object of the present invention is to provide a heat-sensitive recording paper that has excellent moisture resistance and heat resistance in addition to light resistance. Structure of the Invention The present invention provides a thermosensitive recording paper having a thermosensitive coloring layer containing a basic colorless dye, which is usually colorless or light-colored, and an organic color developer, wherein the coloring layer is represented by the following general formula () as an organic color developer. Contains two types of leuco dyes: aminotriarylmethane-based leuco dyes and triphenylmethane/phthalide-based leuco dyes represented by the following general formula () as basic colorless dyes. It is something to do. [However, in the general formula (), R is a C1 to C12 alkyl group, cyclohexyl group, benzyl group, α-naphthyl group, phenyl group, β-naphthyl group, or β-
Represents a phenethyl group. ] [However, in the general formula (), R is
【式】【formula】
【式】【formula】
【式】【formula】
【式】または[expression] or
【式】であり、R1、R2、R3、R4、
R5及びR6はそれぞれ、水素原子、低級アルキル
基、ハロアルキル基、アシロキシアルキル基、フ
エニル基、シクロアルキル基、低級アルコキシ
基、ハロゲン原子、ニトロ基で置換されたベンジ
ル基、ベンジル基、ニトロ基で置換されたフエニ
ル基、アラルキル基又はアシル基を表わし、互い
に同一の基であつてもよい。A、B及びCはそれ
ぞれ、水素原子、低級アルキル基、低級アルコキ
シ基、ハロゲン原子又はニトロ基を表わし、互い
に同一の基であつてもよい。置換基数1、m及び
nはそれぞれ1〜3の整数であり、互いに同一で
あつてもよい。]
本発明において、有機顕色剤として使用する一
般式()の化合物の具体例を以下に示す。
上記の有機顕色剤を使用することにより、併用
された無色染料の利点が発揮され、ビスフエノー
ルAを顕色剤とした場合のような耐熱性、耐湿性
の問題が解決した。
本発明に使用するアミノトリアリールメタン系
ロイコ染料は上述した一般式()によつて示さ
れるが、この一般式()の説明中、アルキル基
及びアルコキシ基を限定する“低級”という用語
は通常1〜5の炭素原子を含む基を示す。低級ア
ルキル基としては、メチル基、エチル基、n−プ
ロピル基、イソプロピル基、n−ブチル基、sec
−ブチル基、tert−ブチル基が例示され、低級ア
ルコキシ基としては、メトキシ基、エトキシ基、
n−プロポキシ基、イソプロポキシ基、n−ブト
キシ基又はtert−ブトキシ基が例示される。
また、一般式()において、アルキル基は直
鎖状または分枝鎖状であつてもよく、メチル基、
エチル基、n−プロピル基、イソプロピル基、n
−ブチル基、イソブチル基、sec−ブチル基、ヘ
キシル基、オクチル基、イソオクチル基、イニル
基またはドデシル基が例示され、シクロアルキル
基としては、シクロペンチル基、シクロヘキシル
基、p−tert−ブチルシクロヘキシル基、2−エ
チルシクロヘキシル基が例示される。
上記の一般式()で示されるアミノトリアリ
ールメタン系ロイコ染料としては、下記のものを
例示することができるが、これらに限定されるも
のではない。
一方、トリフエニルメタン・フタリド系ロイコ
染料としては、下記のものを例示することができ
るが、これらに限定されるものではない。
3,3−ビス(P−ジメチルアミノフエニル)
−6−ジメチルアミノフタリド(別名:クリスタ
リバイオレツトラクトン)
3,3−ビス(P−ジメチルアミノフエニル)
−フタリド
3,3−ビス(P−ジメチルアミノフエニル)
−6−ジエチルアミノフタリド
3,3−ビス(P−ジメチルアミノフエニル)
−6−クロルフタリド
3,3−ビス(P−ジブチルアミノフエニル)
−フタリド
4−ヒドロキシ−4′−ジメチルアミノトリフエ
ニルメタンラクトン
4,4′−ビスジヒドロキシ−3,3−ビスジア
ミノトリフエニルメタンラクトン
3−(2′−ヒドロキシ−4′−ジメチルアミノフ
エニル)−3−(2′−メトキシ−5′−クロルフエニ
ル)フタリド
3−(2′−ヒドロキシ−4′−ジメチルアミノフ
エニル)−3−(2′−メトキシ−5′−ニトロフエニ
ル)フタリド
3−(2′−ヒドロキシ−4′−ジエチルアミノフ
エニル)−3−(2′−メトキシ−5′−メチルフエニ
ル)フタリド
3−(2′−メトキシ−4′−ジメチルアミノフエ
ニル)−3−(2′−ヒドロキシ−4′−クロル−5′−
メチルフエニル)フタリド
本発明においては、叙上のアミノトリアリール
メタン系ロイコ染料とトリフエニルメタンフタリ
ド系ロイコ染料の併用により、前者の光に対する
安定な性質と立上り発色が速いという後者の利点
とを調和させることができた。
又、前記一般式()で示されるアミノトリア
リールメタン系ロイコ染料としてロイコクリスタ
ルバイオレツトを選択し、一方トリフエニルメタ
ン・フタリド系ロイコ染料としてCVLを選択し
た場合に、この組み合せから得られる感熱記録紙
は発色画像の安定性が格段に向上する。
アミノトリアリールメタン系ロイコ染料とトリ
フエニルメタン・フタリド系ロイコ染料との混合
比率に関してはトリフエニルメタン・フタリド系
ロイコ染料及びアミノトリアリールメタン系ロイ
コ染料の合計に対してアミノトリアリールメタン
系ロイコ染料を1〜50重量%で添加するのが望ま
しい。1重量%以下では本発明の効果が殆んど期
待できず、50重量%以上では高湿或いは高温の環
境下に長時間おくと白紙部の地色の著しい悪化が
見られるので好ましくない。
前述の有機顕色剤、塩基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乳化装置によつて数ミクロン
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、変性ポリビニ
ルアルコール、ヒドロキシエチルセルローズ、メ
チルセルローズ、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、酸化チタン、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ま
たは有機充填剤を添加するが、このほかに脂肪酸
金属塩基などの離型剤、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紙が得られる。
本発明に使用する各種成分の種類及び量は要求
される性能およ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、通常塩基性無色染
料1部に対して、有機顕色剤は3〜10部、充填材
は1〜20部を使用し、結合剤は全固形分中10〜25
重量%が適当である。
発明の効果
本発明の特長としては、次の諸点があげられ
る。
(1) 高温・高湿度条件下においても画像及び地色
が安定している。(耐候性が良好である)
(2) 光に長時間さらされても画像濃度が低下した
り退色したりすることが殆んどない。(耐光性
が良好である)
(3) 発色速度が速いので印字直後に飽和発色濃度
に達する。
更に、下記のような特長を有するので感熱記
録紙の用途の拡大によつて想定される様々な使
用環境に対しても適応性がある。
(4) 整髪料や油脂類の付着に対して画像が安定し
ている。(耐油性が良好である)
(5) 水滴がかかり易い使用環境下で使用しても画
像が安定している。(耐水性が良好である)
実施例
次に、代表的な実施例によつて本発明を説明す
る。
実施例
A液(顕色剤分散液)
有機顕色剤(表1参照) 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
B液(染料分散液1)
アミノトリアリールメタン系ロイコ染料(表1
参照) 1部
10%ポリビニルアルコール水溶液 2.3部
C液(染料分散液2)
トリフエニルメタン・フタリド系ロイコ染料
(表1参照) 1部
10%ポリビニルアルコール水溶液 2.3部
上記の組成物の各液をボールミルで粒子径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(顕色剤分散液) 36.5部
B液(染料分散液1) 3.3部
C液(染料分散液2) 3.3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200〜600秒になるように
処理した。得られた青発色の感熱記録紙について
品質性能試験を行つた結果を表1に示す。
比較例
D液(顕色剤分散液)
有機顕色剤(表2参照) 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
E液(染料分散液1)
アミノトリアリールメタン系ロイコ染料(表2
参照) 1部
10%ポリビニルアルコール水溶液 2.3部
F液(染料分散液2)
トリフエニルメタン・フタリド系ロイコ染料
(表2参照) 1部
10%ポリビニルアルコール水溶液 2.3部
上記の組成物の各液をボールミルで粒子径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。
D液(顕色剤分散液) 36.5部
E液(染料分散液1) 3.3部
F液(染料分散液2) 3.3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200〜600秒になるように
処理した。得られた青発色の感熱記録紙について
品質性能試験を行つた結果を表2に示す。[Formula], and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each a hydrogen atom, a lower alkyl group, a haloalkyl group, an acyloxyalkyl group, a phenyl group, a cycloalkyl group, a lower alkoxy group, a halogen atom, a benzyl group substituted with a nitro group, a benzyl group, a phenyl group substituted with a nitro group, an aralkyl group, or an acyl group, and may be the same groups. A, B and C each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom or a nitro group, and may be the same group. The number of substituents 1, m and n are each an integer of 1 to 3, and may be the same. ] Specific examples of the compound of general formula () used as an organic color developer in the present invention are shown below. By using the above-mentioned organic color developer, the advantages of the colorless dye used in combination are exhibited, and the problems of heat resistance and moisture resistance that occur when bisphenol A is used as a color developer are solved. The aminotriarylmethane leuco dye used in the present invention is represented by the above-mentioned general formula (). In the explanation of this general formula (), the term "lower" which limits the alkyl group and alkoxy group is usually used. Indicates a group containing 1 to 5 carbon atoms. Examples of lower alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec
Examples include -butyl group and tert-butyl group, and examples of lower alkoxy groups include methoxy group, ethoxy group,
Examples include n-propoxy group, isopropoxy group, n-butoxy group, and tert-butoxy group. Further, in the general formula (), the alkyl group may be linear or branched, and the alkyl group may be a methyl group,
Ethyl group, n-propyl group, isopropyl group, n
-butyl group, isobutyl group, sec-butyl group, hexyl group, octyl group, isooctyl group, inyl group or dodecyl group, and examples of the cycloalkyl group include cyclopentyl group, cyclohexyl group, p-tert-butylcyclohexyl group, An example is 2-ethylcyclohexyl group. Examples of the aminotriarylmethane leuco dye represented by the above general formula () include, but are not limited to, the following. On the other hand, examples of triphenylmethane phthalide leuco dyes include, but are not limited to, the following. 3,3-bis(P-dimethylaminophenyl)
-6-dimethylaminophthalide (also known as crystalliviolet lactone) 3,3-bis(P-dimethylaminophenyl)
-phthalide 3,3-bis(P-dimethylaminophenyl)
-6-diethylaminophthalide 3,3-bis(P-dimethylaminophenyl)
-6-Chlorphthalide 3,3-bis(P-dibutylaminophenyl)
-Phthalide 4-Hydroxy-4'-dimethylaminotriphenylmethanelactone 4,4'-bisdihydroxy-3,3-bisdiaminotriphenylmethanelactone 3-(2'-hydroxy-4'-dimethylaminophenyl)- 3-(2'-Methoxy-5'-chlorophenyl)phthalide 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)phthalide 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenyl)phthalide3-(2'-methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy- 4′−chlor−5′−
Methylphenyl) phthalide In the present invention, by using the aminotriarylmethane leuco dye mentioned above and the triphenylmethane phthalide leuco dye in combination, the former's stable property against light and the latter's advantage of rapid color development are harmonized. I was able to do it. Furthermore, when leuco crystal violet is selected as the aminotriarylmethane-based leuco dye represented by the general formula () and CVL is selected as the triphenylmethane/phthalide-based leuco dye, the thermal record obtained from this combination With paper, the stability of colored images is greatly improved. Regarding the mixing ratio of aminotriarylmethane leuco dyes and triphenylmethane/phthalide leuco dyes, the ratio of aminotriarylmethane leuco dyes to the total of triphenylmethane/phthalide leuco dyes and aminotriarylmethane leuco dyes is It is desirable to add 1 to 50% by weight. If it is less than 1% by weight, hardly any effect of the present invention can be expected, and if it is more than 50% by weight, the background color of white paper areas will deteriorate significantly if left in a high humidity or high temperature environment for a long time, which is not preferable. The organic color developer and basic colorless dye mentioned above are atomized to a particle size of several microns or less using a grinder such as a ball mill, attritor, or sand grinder, or an appropriate emulsifying device, and various additives are added depending on the purpose. Add the ingredients to make the coating liquid. This coating liquid usually contains polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, starches, styrene-maleic anhydride copolymer, vinyl acetate maleic anhydride copolymer, styrene-butadiene copolymer, etc. binders, and inorganic or organic fillers such as kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, as well as mold release agents such as fatty acid metal bases. , lubricants such as waxes,
Benzophenone-based or triazole-based ultraviolet absorbers, water-resistant agents such as glyoxal, dispersants, antifoaming agents, and the like can be used. By applying this coating liquid to paper and various films,
The desired thermal recording paper is obtained. The types and amounts of various components used in the present invention are determined according to the required performance and recording suitability, and are not particularly limited. Use 3 to 10 parts of filler, 1 to 20 parts of filler, and 10 to 25 parts of binder in total solids.
Weight % is appropriate. Effects of the Invention The features of the present invention include the following points. (1) Image and background color are stable even under high temperature and high humidity conditions. (Good weather resistance) (2) There is almost no decrease in image density or fading even when exposed to light for a long time. (Good light resistance) (3) Color development speed is fast, reaching saturated color density immediately after printing. Furthermore, since it has the following features, it is adaptable to various usage environments expected as the uses of thermal recording paper expand. (4) The image is stable against adhesion of hair products and oils and fats. (Good oil resistance) (5) Stable images even when used in environments where water droplets are likely to be present. (Good water resistance) Examples Next, the present invention will be explained using typical examples. Examples Liquid A (color developer dispersion) Organic color developer (see Table 1) 6.0 parts Zinc stearate 0.5 parts 10% polyvinyl alcohol aqueous solution 30 parts Liquid B (dye dispersion 1) Aminotriarylmethane leuco dye ( Table 1
Reference) 1 part 10% polyvinyl alcohol aqueous solution 2.3 parts Solution C (dye dispersion 2) Triphenylmethane phthalide leuco dye (see Table 1) 1 part 10% polyvinyl alcohol aqueous solution 2.3 parts Each solution of the above composition was ball milled. Grind to a particle size of 3 microns. Next, the dispersion liquid is mixed in the proportions shown below to prepare a coating liquid. Solution A (developer dispersion) 36.5 parts Solution B (dye dispersion 1) 3.3 parts Solution C (dye dispersion 2) 3.3 parts Kaolin clay (50% dispersion) 12 parts Coating amount 6.0 on one side of base paper
The sheet was coated and dried to give a smoothness of 200 to 600 seconds using a supercalender . Table 1 shows the results of a quality performance test performed on the obtained blue-colored thermosensitive recording paper. Comparative example Liquid D (developer dispersion) Organic color developer (see Table 2) 6.0 parts Zinc stearate 0.5 parts 10% polyvinyl alcohol aqueous solution 30 parts Liquid E (dye dispersion 1) Aminotriarylmethane leuco dye ( Table 2
Reference) 1 part 10% polyvinyl alcohol aqueous solution 2.3 parts Solution F (dye dispersion 2) Triphenylmethane phthalide leuco dye (see Table 2) 1 part 10% polyvinyl alcohol aqueous solution 2.3 parts Each solution of the above composition was ball milled. Grind to a particle size of 3 microns. Next, the dispersion liquid is mixed in the proportions shown below to prepare a coating liquid. Solution D (developer dispersion) 36.5 parts Solution E (dye dispersion 1) 3.3 parts Solution F (dye dispersion 2) 3.3 parts Kaolin clay (50% dispersion) 12 parts Coating amount 6.0 on one side of base paper
The sheet was coated and dried to give a smoothness of 200 to 600 seconds using a supercalender . Table 2 shows the results of a quality performance test on the obtained blue-colored thermal recording paper.
【表】【table】
【表】【table】
【表】
○;優れている,△;劣つている,×;極めて劣つ
ている
[Table] ○: Excellent, △: Poor, ×: Extremely poor
【表】【table】
【表】【table】
【表】
未処理の発色濃度
[Table] Untreated color density
【表】
表1及び表2より、本発明の感熱記録紙は耐油
性、耐水性、耐光性、耐候性及び発色速度の点で
著しく優れていると共に、NOxによる黄変も殆
どなく、実用性の高いものであることがわかる。[Table] Tables 1 and 2 show that the thermal recording paper of the present invention is extremely excellent in oil resistance, water resistance, light resistance, weather resistance, and color development speed, and has almost no yellowing due to NOx, making it practical. It can be seen that this is a high value.
Claims (1)
顕色剤とを含有する感熱発色層を有する感熱記録
紙において、該発色層が有機顕色剤として下記一
般式()で表わされる4−ヒドロキシベンゾイ
ルオキシ安息香酸エステルを使用し、塩基性無色
染料として下記一般式()で示されるアミノト
リアリールメタン系ロイコ染料及びトリフエニル
メタン・フタリド系ロイコ染料の2種類のロイコ
染料を含有することを特徴とする感熱記録紙。 [但し、一般式()中、RはC1〜C12のアルキ
ル基、シクロヘキシル基、ベンジル基、α−ナフ
チル基、フエニル基、β−ナフチル基またはβ−
フエネチル基を表わす。] [但し、一般式()中、Rは【式】 【式】 【式】 【式】 または 【式】 であり、R1、R2、R3、R4、R5及びR6はそれぞ
れ、水素原子、低級アルキル基、ハロアルキル
基、アシロキシアルキル基、フエニル基、シクロ
アルキル基、低級アルコキシ基、ハロゲン原子、
ニトロ基で置換されたベンジル基、ベンジル基、
ニトロ基で置換されたフエニル基、アラルキル
基、又はアシル基を表わし、互いに同一の基であ
つてもよい。A、B及びCはそれぞれ、水素原
子、低級アルキル基、低級アルコキシ基、ハロゲ
ン原子又はニトロ基を表わし、互いに同一の基で
あつてもよい。置換基数1、m及びnはそれぞれ
1〜3の整数であり、互いに同一であつてもよ
い。] 2 前記一般式()で示されるアミノトリアリ
ールメタン系ロイコ染料としてロイコクルスタル
バイオレツトを使用し、かつトリフエニルメタ
ン・フタリド系ロイコ染料としてクリスタルバイ
オレツトラクトンを使用することを特徴とする特
許請求の範囲第1項記載の感熱記録紙。[Scope of Claims] 1. A thermosensitive recording paper having a thermosensitive coloring layer containing a normally colorless or light-colored basic colorless dye and an organic color developer, in which the coloring layer has the following general formula () as an organic color developer. Using 4-hydroxybenzoyloxybenzoic acid ester represented by the formula (2), two types of leuco dyes, an aminotriarylmethane leuco dye and a triphenylmethane/phthalide leuco dye, represented by the following general formula () are used as basic colorless dyes. A thermal recording paper characterized by containing: [However, in the general formula (), R is a C1 to C12 alkyl group, cyclohexyl group, benzyl group, α-naphthyl group, phenyl group, β-naphthyl group, or β-
Represents a phenethyl group. ] [However, in the general formula (), R is [Formula] [Formula] [Formula] [Formula] or [Formula], and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are respectively, Hydrogen atom, lower alkyl group, haloalkyl group, acyloxyalkyl group, phenyl group, cycloalkyl group, lower alkoxy group, halogen atom,
benzyl group substituted with nitro group, benzyl group,
It represents a phenyl group, an aralkyl group, or an acyl group substituted with a nitro group, and may be the same group. A, B and C each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom or a nitro group, and may be the same group. The number of substituents 1, m and n are each an integer of 1 to 3, and may be the same. ] 2 A patent claim characterized in that leucocrustal violet is used as the aminotriarylmethane leuco dye represented by the general formula (), and crystal violet lactone is used as the triphenylmethane phthalide leuco dye. The thermosensitive recording paper according to item 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59099375A JPS60242092A (en) | 1984-05-17 | 1984-05-17 | Thermal recording paper |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59099375A JPS60242092A (en) | 1984-05-17 | 1984-05-17 | Thermal recording paper |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60242092A JPS60242092A (en) | 1985-12-02 |
JPH0365798B2 true JPH0365798B2 (en) | 1991-10-15 |
Family
ID=14245781
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59099375A Granted JPS60242092A (en) | 1984-05-17 | 1984-05-17 | Thermal recording paper |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60242092A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2812040B2 (en) * | 1992-02-29 | 1998-10-15 | 王子製紙株式会社 | Thermal recording medium |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5727782A (en) * | 1980-07-29 | 1982-02-15 | Mitsui Toatsu Chem Inc | Colorant for pressure-sensitive, heat-sensitive recording paper |
JPS58166098A (en) * | 1982-03-27 | 1983-10-01 | Ricoh Co Ltd | Heat-sensitive recording material |
JPS58183289A (en) * | 1982-04-22 | 1983-10-26 | Ricoh Co Ltd | Heat-sensitive recording material |
-
1984
- 1984-05-17 JP JP59099375A patent/JPS60242092A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5727782A (en) * | 1980-07-29 | 1982-02-15 | Mitsui Toatsu Chem Inc | Colorant for pressure-sensitive, heat-sensitive recording paper |
JPS58166098A (en) * | 1982-03-27 | 1983-10-01 | Ricoh Co Ltd | Heat-sensitive recording material |
JPS58183289A (en) * | 1982-04-22 | 1983-10-26 | Ricoh Co Ltd | Heat-sensitive recording material |
Also Published As
Publication number | Publication date |
---|---|
JPS60242092A (en) | 1985-12-02 |
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LAPS | Cancellation because of no payment of annual fees |