JPH0523196B2 - - Google Patents
Info
- Publication number
- JPH0523196B2 JPH0523196B2 JP61275573A JP27557386A JPH0523196B2 JP H0523196 B2 JPH0523196 B2 JP H0523196B2 JP 61275573 A JP61275573 A JP 61275573A JP 27557386 A JP27557386 A JP 27557386A JP H0523196 B2 JPH0523196 B2 JP H0523196B2
- Authority
- JP
- Japan
- Prior art keywords
- color
- carbon atoms
- group
- alkyl group
- substituted
- 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
- 239000003094 microcapsule Substances 0.000 claims description 21
- -1 p-substituted aminophenylindolyl Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- FXSFKECPPGDGBN-UHFFFAOYSA-N 3,3-bis(1h-indol-2-yl)-2-benzofuran-1-one Chemical class C12=CC=CC=C2C(=O)OC1(C=1NC2=CC=CC=C2C=1)C1=CC2=CC=CC=C2N1 FXSFKECPPGDGBN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical class C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000005011 phenolic resin Chemical class 0.000 description 1
- 229920001568 phenolic resin Chemical class 0.000 description 1
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000004654 triazenes Chemical class 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
- B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
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
（発明の分野）
本発明は記録シートに関し、さらに詳しくはほ
ぼ無色の電子供与性染料と電子受容性化合物の発
色反応を利用した記録シートに関する。
（従来技術）
ほぼ無色の電子供与性染料（以下発色剤と称す
る）と電子受容性化合物（以下顕色剤と称する）
を使用した記録シートは、感圧紙、感熱紙、感光
感圧紙、通電感熱記録紙等として既によく知られ
ている。
たとえば英国特許2140449、米国特許4480052、
同4436920、特公昭60−22922、特開昭57−
179836、同60−123556、同60−123557などに詳し
い。
記録シートの具備すべき性能は、(1)発色濃度お
よび発色感度が十分であること、(2)カブリを生じ
ないこと、(3)発色体の堅牢性が十分であること、
(4)発色剤を含有するマイクロカプセル層の耐光性
が十分であること、などである。
これらの記録シートにおいて発色体の堅牢性に
著しく優れた発色体を与える発色剤としてｐ−置
換アミノフエニルインドリルアザフタリド誘導体
を使用することが既に提案されている（特公昭51
−16807、特公昭51−38243、特公昭58−20798、
特公昭61−4856など）。
しかしこのｐ−置換アミノフエニルインドリル
アザフタリド誘導体をマイクロカプセル中に含有
する記録シートは、マイクロカプセル層の耐光性
が十分でない（マイクロカプセル層の光照射によ
り、発色性が低下する）という欠点を有する。
（発明の目的）
本発明の目的は、発色剤としてｐ−置換アミノ
フエニルインドリルアザフタリドをマイクロカプ
セル中に含有する記録シートのマイクロカプセル
層の耐光性を改良した記録シートを提供すること
である。
（発明の構成）
本発明の目的はほぼ無色の電子供与性染料を含
有するマイクロカプセルを含有する記録シートに
おいて、電子供与性染料として(a)ｐ−置換アミノ
フエニルインドリルアザフタリド誘導体と、(b)一
般式〔〕で表わされるビスインドリルフタリド
誘導体を含有することを特徴とする記録シートに
より達成された。
（式中、R1、R1′は炭素原子数６〜18のアルキル
基、または炭素原子数６〜12
のアリール基
R2、R2′は水素原子、炭素原子数１〜８
のアルキル基、または炭素原
子数６〜９のアリール基を表
わす。）
本発明の発色剤として用いるｐ−置換アミノフ
エニルインドリルアザフタリド化合物としては、
下記の一般式で表わされるのが好ましい。
上記の式において、Ｘ及びＹの一方が−Ｎ＝
を、他方が−CH＝を表わし、Ｚは水素原子、ハ
ロゲン原子、C1〜C8のアルキル基、C1〜C12のア
ルコキシ基、C6〜C18のアリールオキシ基、又は
C7〜C13のアラルキルオキシ基、Ｗは水素原子又
はハロゲン原子を表わし、R1は水素原子または
12個以下の炭素原子を有する非置換あるいはハロ
ゲン原子、ヒドロキシル基、シアノ基、または低
級アルコキシ基によつて置換されたアルキル基を
表わし、R2は水素原子、C1〜C8のアルキル基ま
たはC6〜C12のアルール基、R3及びR4は互いに独
立に水素原子または12個以下の炭素原子を有する
非置換あるいはハロゲン原子、ヒドロキシル基、
シアノ基、または低級アルコキシ基によつて置換
されたアルキル基、C5〜C7のシクロアルキル基、
ベンジル基、またはフエニル基を表わし、さらに
−NR3R4としてピロリジニル基を形成していて
もよい。
上記一般式で表わされるｐ−置換アミノフエニ
ルインドリルアザフタリド化合物として好ましい
(Field of the Invention) The present invention relates to a recording sheet, and more particularly to a recording sheet that utilizes a color-forming reaction between a nearly colorless electron-donating dye and an electron-accepting compound. (Prior art) Almost colorless electron-donating dye (hereinafter referred to as color former) and electron-accepting compound (hereinafter referred to as color developer)
Recording sheets using the above are already well known as pressure-sensitive paper, thermal paper, light-sensitive pressure-sensitive paper, electrically conductive heat-sensitive recording paper, etc. For example, UK patent 2140449, US patent 4480052,
4436920, JP 60-22922, JP 57-
I am familiar with 179836, 60-123556, 60-123557, etc. The performance that a recording sheet should have is (1) sufficient color density and color development sensitivity, (2) no fogging, (3) sufficient fastness of the color material,
(4) The microcapsule layer containing the color former has sufficient light resistance. It has already been proposed to use a p-substituted aminophenylindolyl azaphthalide derivative as a coloring agent that provides a coloring material with extremely excellent fastness in these recording sheets (Japanese Patent Publication No.
−16807, Special Publication Showa 51-38243, Special Publication No. 58-20798,
Tokuko Sho 61-4856, etc.) However, in recording sheets containing this p-substituted aminophenyl indolyl azaphthalide derivative in microcapsules, it is said that the light resistance of the microcapsule layer is insufficient (the color development property decreases when the microcapsule layer is irradiated with light). It has its drawbacks. (Object of the Invention) An object of the present invention is to provide a recording sheet containing p-substituted aminophenylindolyl azaphthalide as a coloring agent in the microcapsules, in which the light resistance of the microcapsule layer is improved. It is. (Structure of the Invention) An object of the present invention is to provide a recording sheet containing microcapsules containing an almost colorless electron-donating dye, in which (a) a p-substituted aminophenylindolyl azaphthalide derivative is used as the electron-donating dye. , (b) A recording sheet characterized by containing a bisindolyl phthalide derivative represented by the general formula []. (In the formula, R 1 and R 1 ' are an alkyl group having 6 to 18 carbon atoms, or an alkyl group having 6 to 12 carbon atoms.
The aryl groups R 2 and R 2 ′ are hydrogen atoms and have 1 to 8 carbon atoms.
represents an alkyl group or an aryl group having 6 to 9 carbon atoms. ) The p-substituted aminophenyl indolyl azaphthalide compound used as the color former of the present invention includes:
It is preferably represented by the following general formula. In the above formula, one of X and Y is −N=
, the other one represents -CH=, and Z is a hydrogen atom, a halogen atom, a C1 - C8 alkyl group, a C1 - C12 alkoxy group, a C6 - C18 aryloxy group, or
C7 to C13 aralkyloxy group, W represents a hydrogen atom or a halogen atom, R1 is a hydrogen atom or
represents an alkyl group having up to 12 carbon atoms, unsubstituted or substituted by a halogen atom, a hydroxyl group, a cyano group, or a lower alkoxy group, and R 2 is a hydrogen atom, a C 1 -C 8 alkyl group, or C 6 to C 12 aral group, R 3 and R 4 are each independently a hydrogen atom or an unsubstituted or halogen atom having up to 12 carbon atoms, a hydroxyl group,
an alkyl group substituted with a cyano group or a lower alkoxy group, a C5 - C7 cycloalkyl group,
It represents a benzyl group or a phenyl group, and -NR 3 R 4 may further form a pyrrolidinyl group. Preferred as p-substituted aminophenylindolyl azaphthalide compound represented by the above general formula
【表】【table】
【表】
本発明の発色剤として用いるビスインドリルフ
タリド化合物は、一般式〔〕においてR2、
R2′は水素原子、メチル基またはフエニル基が好
ましい。
一般式〔〕で表わされるビスインドリルフタ
リド化合物の好ましい具体例を第２表に表示す
る。[Table] The bisindolyl phthalide compound used as the coloring agent of the present invention has R 2 ,
R 2 ' is preferably a hydrogen atom, a methyl group or a phenyl group. Preferred specific examples of the bisindolyl phthalide compound represented by the general formula [] are shown in Table 2.
【表】【table】
【表】
発色剤としては、ｐ−置換アミノフエニルイン
ドリルアザフタリド誘導体及びビスインドリルフ
タリド誘導体の他にトリフエニルメタンフタリド
系化合物、フルオラン系化合物、フエノチアジン
系化合物、インドリルフタリド系化合物、ロイコ
オーラミン系化合物、ローダミンラクタム系化合
物、トリフエニルメタン系化合物、トリアゼン系
化合物、スピロピラン系化合物等を併用してもよ
い。併用する発色剤としては、クリスタルバイオ
レツトラクトンが色相及び発色濃度の点で好まし
い。
この場合、本発明の(a)ｐ−置換アミノフエニル
インドリルアザフタリド誘導体と、(b)ビスインド
リルフタリド誘導体の合計が発色剤全体の量の30
重量％以上になるように用いることが、発色体の
堅牢性の点から望ましい。また(a)と(b)の併用比率
は重量比で(a)／(b)＝50／50〜90／10が好ましい。
本発明に使用する発色剤は溶媒に溶解してカプ
セル化して支持体に塗布される。
溶媒としては天然又は合成油を単独又は併用し
て用いることができる。溶媒の例として、綿実
油、灯油、パラフイン、ナフテン油、アルキル化
ビフエニル、アルキル化ターフエル、塩素化パラ
フイン、アルキル化ナフタレン、ジフエニルアル
カンなどを挙げることができる。
発色剤含有マイクロカプセルの製造方法として
は、界面重合法、内部重合法、相分離法、外部重
合法、コアセルベーシヨン法などが用いられる。
発色剤含有マイクロカプセルを含む塗液を調整
するにあたり一般に水溶性バインダー、ラテツク
ス系バインダーが使用される。さらにカプセル保
護剤例えば、セルロース粉末、デンプン粒子、タ
ルクなどを添加して発色剤含有マイクロカプセル
塗布液を得る。
本発明の記録シートに用いられる発色剤と反応
する顕色剤の例としては、酸性白土、活性白土、
アタバルジヤイト、ゼオライト、ベントナイト、
カオリンの如き粘土物質、芳香族カルボン酸の金
属塩およびフエノール樹脂等があげられる。
これらの顕色剤は、スチレンブタジエンラテツ
クスの如きバインダーと共に紙等の支持体に塗布
される。
本発明の記録シートは次に示す顕色剤シートを
用いてその性能を試験した。
（顕色剤シートの調整）
水70部に酸化亜鉛２部と炭酸カルシウム18部及
び３，５−ジ−α−メチルベンジルサリチル酸亜
鉛４物を添加混合し、次にアトライターにより30
分分散した液に、カルボキシ変性SBRラテツク
スを固形分にて2.5部と10wt％PVA（ケン化度99
％、重合度1000）水溶性12部を添加し、均一に撹
拌して塗布液とした。この塗布液を50ｇ/m2の原
紙に４ｇ/m2の固形分が塗布されるようなエアナ
イフ塗布機にて塗布乾燥して顕色剤シートを得
た。
（発明の実施例）
以下実施例により本発明を具体的に説明する。
本発明は実施例に限定されるものではない。
実施例１〜８及び比較例１〜５
PH４に調整されたポリビニルベンゼンスルホン
酸の一部ナトリウム塩（平均分子量500000）の
4.4％水溶液100部に、第３表に示す発色剤をジイ
ソプロピルナフタレン100部に溶解した発色剤油
を乳化分散して平均粒径5.5μの粒子サイズを持つ
乳化液を得た。別に、メラミン６部、37重量％ホ
ルムアルデヒド水溶液11部、水30部を60℃に加熱
撹拌して30分後に透明なメラミンとホルムアルデ
ヒド及びメラミンホルムアルデヒド初期縮合物の
混合水溶液を得た。この混合水溶液のPHは6.0〜
8.0であつた。以下このメラミンとホルムテルデ
ヒド及びメラミン−ホルムアルデヒド初期縮合物
の混合水溶液を初期縮合物溶液と称する。上記の
方法で得た初期縮合物溶液を上記乳化混合物に添
加混合し、撹拌しながら3.6重量％の塩酸溶液に
てPHを6.0に調節し、液温を65℃に上げ360分撹拌
し続けた。このカプセル液を室温まで冷却し20重
量％の水酸化ナトリウムでPH9.0に調節した。
このカプセル分散液に対して10重量％ポリビニ
ルアルコール水溶液100部及びカルボキシ変性
SBRラテツクスを固形分で10部およびデンプン
粒子50部及び炭酸カルシウム10部を添加し水を加
えて固形分濃度20％に調整し発色剤含有マイクロ
カプセル塗布液を調整した。
この塗布液を50ｇ/m2の原紙に５ｇ/m2の固形分
が塗布されるようにエアーナイフコーターにて塗
布、乾燥し感圧複写用マイクロカプセルシートを
得た。
比較試験
(1) マイクロカプセル層の耐光性
実施例及び比較用マイクロカプセルシートのマ
イクロカプセル層を螢光灯退色試験機
（33000lux）で８時間照射した後、顕色剤シート
上に重ね、300Kg/cm2の荷重圧をかけ発色させた。
暗所にて24時間放置した後、波長380〜780nm間
の発色体の分光吸収曲線を測定し、吸収極大にお
ける濃度Ｄを測定した。
別に未照射の実施例及び比較用マイクロカプセ
ルシートを顕色剤シート上に重ね、300Kg/cm2の荷
重圧をかけ発色させた。暗所にて24時間放置した
後、波長380〜780nm間の発色体の分光吸収曲線
を測定し、吸収極大における濃度（フレツシユ濃
度（D0））を測定した。
分光吸収曲線の測定は、日立カラーアナライザ
ー307型を用いて行ない、次の式で求めた耐光値
を第３表に示す。
耐光値＝螢光灯照射後の吸収極大における濃度（Ｄ）
／吸収極大におけるフレツシユ濃度（D0）
耐光値が大きいほど、マイクロカプセル層の耐
光性が優れていることを示す。
第３表に示すように、本発明のマイクロカプセ
ルシートは比較用のマイクロカプセルシートに比
べマイクロカプセル層の耐光性が優れていること
がわかる。[Table] In addition to p-substituted aminophenyl indolyl azaphthalide derivatives and bis-indolylphthalide derivatives, color formers include triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, and indolyl phthalide. type compounds, leuco auramine type compounds, rhodamine lactam type compounds, triphenylmethane type compounds, triazene type compounds, spiropyran type compounds, etc. may be used in combination. As the coloring agent used in combination, crystal violet lactone is preferable in terms of hue and coloring density. In this case, the total amount of (a) the p-substituted aminophenyl indolyl azaphthalide derivative and (b) the bis-indolylphthalide derivative of the present invention is 30% of the total amount of the color former.
It is desirable to use it in an amount of at least % by weight from the viewpoint of the fastness of the color former. The combined ratio of (a) and (b) is preferably (a)/(b) = 50/50 to 90/10 by weight. The coloring agent used in the present invention is dissolved in a solvent, encapsulated, and applied to a support. As a solvent, natural or synthetic oils can be used alone or in combination. Examples of solvents include cottonseed oil, kerosene, paraffin, naphthenic oil, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene, diphenylalkane, and the like. As a method for manufacturing the color former-containing microcapsules, an interfacial polymerization method, an internal polymerization method, a phase separation method, an external polymerization method, a coacervation method, etc. are used. In preparing a coating solution containing microcapsules containing a color former, a water-soluble binder or a latex-based binder is generally used. Further, a capsule protectant such as cellulose powder, starch particles, talc, etc. is added to obtain a color former-containing microcapsule coating solution. Examples of the color developer that reacts with the color forming agent used in the recording sheet of the present invention include acid clay, activated clay,
attabulgite, zeolite, bentonite,
Examples include clay materials such as kaolin, metal salts of aromatic carboxylic acids, and phenolic resins. These color developers are applied to a support such as paper along with a binder such as styrene butadiene latex. The performance of the recording sheet of the present invention was tested using the following color developer sheet. (Adjustment of color developer sheet) Add and mix 2 parts of zinc oxide, 18 parts of calcium carbonate, and 4 zinc 3,5-di-α-methylbenzylsalicylates to 70 parts of water, and then use an attritor to
Add 2.5 parts of carboxy-modified SBR latex and 10 wt% PVA (saponification degree 99) to the dispersed liquid.
%, degree of polymerization 1000) was added and stirred uniformly to prepare a coating solution. This coating solution was coated on a 50 g/m 2 base paper using an air knife coater capable of coating a solid content of 4 g/m 2 and dried to obtain a color developer sheet. (Examples of the Invention) The present invention will be specifically described below with reference to Examples.
The invention is not limited to the examples. Examples 1 to 8 and Comparative Examples 1 to 5 Partial sodium salt of polyvinylbenzenesulfonic acid (average molecular weight 500,000) adjusted to pH 4
A color former oil prepared by dissolving the color former shown in Table 3 in 100 parts of diisopropylnaphthalene was emulsified and dispersed in 100 parts of a 4.4% aqueous solution to obtain an emulsion having a particle size of 5.5 μm on average. Separately, 6 parts of melamine, 11 parts of a 37% by weight formaldehyde aqueous solution, and 30 parts of water were heated and stirred at 60°C, and after 30 minutes, a transparent mixed aqueous solution of melamine, formaldehyde, and melamine-formaldehyde initial condensate was obtained. The pH of this mixed aqueous solution is 6.0~
It was 8.0. Hereinafter, this mixed aqueous solution of melamine, formterdehyde, and melamine-formaldehyde initial condensate will be referred to as an initial condensate solution. The initial condensate solution obtained by the above method was added to and mixed with the above emulsified mixture, and while stirring, the pH was adjusted to 6.0 with a 3.6% by weight hydrochloric acid solution, and the liquid temperature was raised to 65°C and stirring was continued for 360 minutes. . This capsule liquid was cooled to room temperature and adjusted to pH 9.0 with 20% by weight sodium hydroxide. For this capsule dispersion, 100 parts of a 10% by weight polyvinyl alcohol aqueous solution and carboxy-modified
A coloring agent-containing microcapsule coating solution was prepared by adding 10 parts of solid content of SBR latex, 50 parts of starch particles, and 10 parts of calcium carbonate, and adjusting the solid content concentration to 20% by adding water. This coating solution was applied to a 50 g/m 2 base paper using an air knife coater so that the solid content was 5 g/m 2 and dried to obtain a microcapsule sheet for pressure-sensitive copying. Comparative test (1) Light resistance of microcapsule layer The microcapsule layers of the example and comparative microcapsule sheets were irradiated with a fluorescent lamp fading tester (33000 lux) for 8 hours, and then stacked on a developer sheet and tested at 300 kg/ A load pressure of cm 2 was applied to develop color.
After leaving it in a dark place for 24 hours, the spectral absorption curve of the chromophore between wavelengths of 380 to 780 nm was measured, and the concentration D at the absorption maximum was measured. Separately, unirradiated Example and Comparative microcapsule sheets were stacked on a developer sheet, and a load of 300 Kg/cm 2 was applied to develop color. After being left in a dark place for 24 hours, the spectral absorption curve of the chromophore was measured in the wavelength range of 380 to 780 nm, and the concentration at maximum absorption (fresh density (D 0 )) was measured. The measurement of the spectral absorption curve was carried out using Hitachi Color Analyzer Model 307, and the light fastness values determined by the following formula are shown in Table 3. Lightfastness value = concentration at maximum absorption after fluorescent lamp irradiation (D)
/Fresh density at absorption maximum (D 0 ) The larger the light resistance value, the better the light resistance of the microcapsule layer. As shown in Table 3, it can be seen that the light resistance of the microcapsule layer of the microcapsule sheet of the present invention is superior to that of the comparative microcapsule sheet.
【表】【table】
Claims (1)
ロカプセルを含有する記録シートにおいて、電子
供与性染料として(a)ｐ−置換アミノフエニルイン
ドリルアザフタリド誘導体と(b)一般式〔〕で表
わされるビスインドリルフタリド誘導体を含有す
ることを特徴とする記録シート。 （式中、R1、R1′は炭素原子数６〜18のアルキル
基、または炭素原子数６〜12
のアリール基 R2、R2′は水素原子、炭素原子数１〜８
のアルキル基、または炭素原
子数６〜９のアリール基を表
わす。[Scope of Claims] 1. A recording sheet containing microcapsules containing an almost colorless electron-donating dye, comprising (a) a p-substituted aminophenylindolyl azaphthalide derivative and (b) a p-substituted aminophenylindolyl azaphthalide derivative as the electron-donating dye. A recording sheet characterized by containing a bisindolyl phthalide derivative represented by the general formula []. (In the formula, R 1 and R 1 ' are an alkyl group having 6 to 18 carbon atoms, or an alkyl group having 6 to 12 carbon atoms.
The aryl groups R 2 and R 2 ′ are hydrogen atoms and have 1 to 8 carbon atoms.
represents an alkyl group or an aryl group having 6 to 9 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61275573A JPS63128979A (en) | 1986-11-19 | 1986-11-19 | Recording sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61275573A JPS63128979A (en) | 1986-11-19 | 1986-11-19 | Recording sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63128979A JPS63128979A (en) | 1988-06-01 |
| JPH0523196B2 true JPH0523196B2 (en) | 1993-03-31 |
Family
ID=17557335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61275573A Granted JPS63128979A (en) | 1986-11-19 | 1986-11-19 | Recording sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63128979A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4827369A (en) * | 1971-08-17 | 1973-04-11 | ||
| JPS4992112A (en) * | 1971-11-26 | 1974-09-03 | ||
| JPS5820798A (en) * | 1981-07-27 | 1983-02-07 | Nec Corp | Oxide optical material |
-
1986
- 1986-11-19 JP JP61275573A patent/JPS63128979A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4827369A (en) * | 1971-08-17 | 1973-04-11 | ||
| JPS4992112A (en) * | 1971-11-26 | 1974-09-03 | ||
| JPS5820798A (en) * | 1981-07-27 | 1983-02-07 | Nec Corp | Oxide optical material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63128979A (en) | 1988-06-01 |
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