JP2585692B2 - New leuco dye - Google Patents
New leuco dyeInfo
- Publication number
- JP2585692B2 JP2585692B2 JP63064893A JP6489388A JP2585692B2 JP 2585692 B2 JP2585692 B2 JP 2585692B2 JP 63064893 A JP63064893 A JP 63064893A JP 6489388 A JP6489388 A JP 6489388A JP 2585692 B2 JP2585692 B2 JP 2585692B2
- Authority
- JP
- Japan
- Prior art keywords
- tetrakis
- ethenyl
- bis
- leuco dye
- dimethylaminophenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 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
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- -1 fluoran compound Chemical class 0.000 description 60
- 239000000975 dye Substances 0.000 description 54
- 239000000463 material Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- 238000004040 coloring Methods 0.000 description 17
- 239000013078 crystal Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003086 colorant Substances 0.000 description 7
- 239000003094 microcapsule Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 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 2
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000012015 optical character recognition Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229940037312 stearamide Drugs 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
- ZUTFYXKSZOFQMZ-UHFFFAOYSA-N 1,1,5,5-tetrakis[4-(dimethylamino)phenyl]penta-2,4-dienyl perchlorate Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=CC=CC(OCl(=O)(=O)=O)(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZUTFYXKSZOFQMZ-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
- VDNCBORANQOHNZ-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]penta-2,4-dienyl perchlorate Chemical compound Cl(=O)(=O)(=O)OC(C=CC=C)C1=CC=C(C=C1)N(C)C VDNCBORANQOHNZ-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 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
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- NFKGQHYUYGYHIS-UHFFFAOYSA-N dibutyl propanedioate Chemical compound CCCCOC(=O)CC(=O)OCCCC NFKGQHYUYGYHIS-UHFFFAOYSA-N 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
- 238000005406 washing 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
- B41M5/323—Organic colour formers, e.g. leuco dyes
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
【発明の詳細な説明】 〔技術分野〕 本発明は、新規な画像形成用ロイコ染料に関し、特に
感熱記録や感圧記録における近赤外吸収ロイコ染料に関
する。Description: TECHNICAL FIELD The present invention relates to a novel leuco dye for image formation, and particularly to a near-infrared absorbing leuco dye in heat-sensitive recording and pressure-sensitive recording.
ロイコ染料を用いる記録材料は古くから知られてお
り、感圧記録紙や、感熱記録紙等として利用され、年々
その使用量も増えてきている。ロイコ系感圧記録材料
は、一般に、ほゞ無色のロイコ染料とそのロイコ染料を
接触時発色せしめ着色像を形成しうる呈色剤との間の化
学反応を利用したものである。具体的には、ロイコ染料
の有機溶剤溶液をマイクロカプセル化したものを塗布し
た発色剤シートと、呈色剤を結着剤と共に塗布した呈色
剤シートとを、互いの表面を重ね合せ、背面より筆圧等
で加圧し、カプセルを破壊して呈色反応をおこなわしめ
るものである。Recording materials using leuco dyes have been known for a long time, and are used as pressure-sensitive recording paper, heat-sensitive recording paper, and the like, and the amount of use thereof is increasing year by year. A leuco-based pressure-sensitive recording material generally utilizes a chemical reaction between a nearly colorless leuco dye and a color former capable of forming a colored image by contacting the leuco dye upon contact. Specifically, a color former sheet coated with a microcapsule of an organic solvent solution of a leuco dye and a color former sheet coated with a color former together with a binder are superimposed on each other, Pressing with a pen pressure or the like further breaks the capsule to cause a color reaction.
一方、ロイコ系感熱記録材料は、支持体上に、ロイコ
染料と呈色剤を支持させたものであり、微少発熱抵抗体
素子により熱的に画像信号を与えると、発色画像を与え
る。On the other hand, the leuco-based heat-sensitive recording material has a leuco dye and a coloring agent supported on a support, and gives a color-developed image when an image signal is given thermally by a minute heating resistor element.
このような感圧及び感熱記録紙は、他の記録材料、例
えば、電子写真や、静電記録材料に比べ、現像、定着な
どの煩雑な処理を施すことなく、比較的簡単な装置で短
時間に記録が得られること等から多方面に利用されてい
る。このような記録材料のロイコ染料として主に使用さ
れるのは、クリスタルバイオレットラクトンや、ロイコ
クリスタルバイオレットに代表される青発色染料や、７
位アニリノ置換のフルオラン化合物に代表される黒発色
染料等である。近年、光学文字読取装置や、ラベルバー
コード読取装置が開発され、その使用割合が増加してき
ているが、これらの装置においては、その光源として、
発光ダイオードや、半導体レーザーを用いた光波長が70
0nm以上の光源が一般的に使用されている。ところが、
上記の青発色染料や黒発色染料では700nm以上の近赤外
域の光吸収がほとんどないため、前記の読取装置ではそ
の発色読取りが不可能である。従って、発色体の光吸収
波長が700nm以上であるロイコ染料の新規開発が強く要
望されているのが現状である。Such pressure-sensitive and heat-sensitive recording paper can be used in a relatively simple apparatus for a short time without performing complicated processing such as development and fixing compared to other recording materials, for example, electrophotography and electrostatic recording material. It is used in various fields because it is possible to obtain records. The main leuco dyes used for such recording materials are crystal violet lactone, blue dyes represented by leuco crystal violet, and 7
And a black coloring dye represented by an anilino-substituted fluoran compound. In recent years, optical character readers and label barcode readers have been developed, and their use ratio has been increasing.
Light wavelength of 70 using light emitting diode or semiconductor laser
Light sources of 0 nm or more are commonly used. However,
Since the blue coloring dye and the black coloring dye hardly absorb light in the near-infrared region of 700 nm or more, the color reading cannot be performed by the above-described reading apparatus. Therefore, at present, there is a strong demand for new development of leuco dyes in which the light absorption wavelength of the color former is 700 nm or more.
従来、長波長吸収のロイコ染料についていくつかの提
案がなされており、例えば、特開昭51-121035、特開昭5
1-121037号、特開昭51-121038号、特開昭57-167979号公
報に示されているが、これらの染料は合成が困難で、コ
ストが非常に高いという欠点がある。Heretofore, several proposals have been made for leuco dyes having long wavelength absorption, for example, JP-A-51-121035,
These are described in JP-A-1-121037, JP-A-51-121038 and JP-A-57-167979, but these dyes have a drawback that synthesis is difficult and cost is extremely high.
本発明は、慣用の感熱及び感圧記録材料に使用されて
きたロイコ染料に見られなかった、近赤外領域に強い吸
収帯を有する新規なロイコ染料を提供することを目的と
する。An object of the present invention is to provide a novel leuco dye having a strong absorption band in the near infrared region, which has not been found in leuco dyes used in conventional heat-sensitive and pressure-sensitive recording materials.
本発明によれば、一般式（Ｉ） 〔式中、R1，R2，R3，R4，R5，R6，R7及びR8は低級アル
キル基を、R9及びR10は水素原子（但し双方が水素原子
である場合を除く、）、−CN又は−COR11を、並びにR11
はフェニル基、ハロゲンで置換されたフェニル基、ナフ
チル基、低級アルキル基又は低級アルコキシ基を、夫々
表わす、〕で表わされるロイコ染料が提供される。According to the present invention, general formula (I) [Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are lower alkyl groups, and R 9 and R 10 are hydrogen atoms (provided that both are hydrogen atoms) ), -CN or -COR 11 and R 11
Represents a phenyl group, a phenyl group substituted with a halogen, a naphthyl group, a lower alkyl group or a lower alkoxy group, respectively.
本発明の一般式（Ｉ）で表わされるロイコ染料は、新
規物質であって、大気中で安定な、無色又はわずかに着
色している固体であり、活性白土、酸性白土等の無機酸
や、有機酸、フェノール性合成物およびそれらの誘導
体、酸化剤等の電子受容性化合物と分子レベルで接触す
ると、発色反応がすばやく起り、深い青色の色素を形成
し、この発色した色素は優れた保存性を有しているため
色素前駆体として有用である。この色素の光吸収スペク
トルのλmaxは、溶液中では約800〜820nmであり、記録
紙上での発色部は約500〜900nmである。The leuco dye represented by the general formula (I) of the present invention is a novel substance, a colorless or slightly colored solid that is stable in the air, and is an inorganic acid such as activated clay and acid clay. When it comes into contact with electron-accepting compounds such as organic acids, phenolic compounds and their derivatives, and oxidizing agents at the molecular level, a color-forming reaction occurs quickly, forming a deep blue dye, and this dye has excellent storage stability. Is useful as a dye precursor. The λmax of the light absorption spectrum of this dye is about 800 to 820 nm in a solution, and the color-developed part on a recording paper is about 500 to 900 nm.
本発明の前記一般式（Ｉ）で表わされるロイコ染料は
次の方法で製造される。The leuco dye of the present invention represented by the general formula (I) is produced by the following method.
一般式（II） 〔式中、R1，R2，R3，R4，R5，R6，R7及びR8は低級アル
キル基を表わす、） で表わされる1,1,5,5−テトラキス−（ｐ−ジアルキル
アミノフェニル）−2,4−ペンタジエン−１−オールパ
ークロレートと、一般式（III） 〔式中、R9及びR10は水素原子（但し、双方が水素原子
である場合を除く、）、−CN又は−COR11を、並びにR11
はフェニル基、ハロゲンで置換されたフェニル基、ナフ
チル基、低級アルキル基又は低級アルコキシ基を、夫々
表わす、〕 で表わされる化合物とを、有機溶媒中０〜80℃の温度で
反応させ、得られた生成物を精製することにより、一般
式（Ｉ）で表わされる化合物が白色若しくは淡く着色し
た結晶として得られる。General formula (II) [Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 represent a lower alkyl group.] 1,1,5,5-tetrakis- (p -Dialkylaminophenyl) -2,4-pentadiene-1-ol perchlorate and a compound of the general formula (III) [Wherein, R 9 and R 10 represent a hydrogen atom (except when both are hydrogen atoms), —CN or —COR 11 , and R 11
Represents a phenyl group, a phenyl group substituted with a halogen, a naphthyl group, a lower alkyl group or a lower alkoxy group, respectively) with a compound represented by the formula (1) in an organic solvent at a temperature of 0 to 80 ° C. By purifying the resulting product, the compound represented by the general formula (I) is obtained as white or pale colored crystals.
なお、一般式（II）で表わされる1,1,5,5−テトラキ
ス−（ｐ−ジアルキルアミノフェニル）−2,4−ペンタ
ジエン−１−オールパークロレートの製造は、ジャーナ
ル・オブ・ザ・アメリカン・ケミカル・ソサイエティ80
巻3772頁（1958年）に記載されている合成例が参照され
る。The production of 1,1,5,5-tetrakis- (p-dialkylaminophenyl) -2,4-pentadiene-1-ol perchlorate represented by the general formula (II) is described in Journal of the American・ Chemical Society 80
Reference is made to the synthesis examples described in Volume 3772 (1958).
本発明の前記一般式（Ｉ）で表わされる化合物の具体
例を示すと、次のようなものが挙げられるが、もちろん
これらに限定されるものではない。Specific examples of the compound represented by the general formula (I) of the present invention include the following, but are not limited thereto.
1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジメチルアミノフェニル）−エテニル〕−2,2−ジニ
トリルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジエチルアミノフェニル）−エテニル〕−2,2−ジニ
トリルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジピロピルアミノフェニル）−エテニル〕−2,2−ジ
ニトリルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジ−ｎ−ブチルアミノフェニル）−エテニル〕−2,2
−ジニトリルエタン、 3,3−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジメチルアミノフェニル）−エテニル〕−２−ニトリ
ル−プロピオン酸エチルエステル、 3,3−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジエチルアミノフェニル）−エテニル〕−２−ニトリ
ル−プロピオン酸エチルエステル、 3,3−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジプロイルアミノフェニル）−エテニル〕−２−ニト
リル−プロピオン酸エチルエステル、 3,3−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジ−ｎ−ブチルアミノフェニル）−エテニル〕−２−
ニトリル−プロピオン酸エチルエステル、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジメチルアミノフェニル）−エテニル〕−２−ベンゾ
イルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジエチルアミノフェニル）−エテニル〕−２−ベンゾ
イルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジプロピルアミノフェニル）−エテニル〕−２−ベン
ゾイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジ−ｎ−ブチルアミノフェニル）−エテニル〕−２−
ベンゾイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジメチルアミノフェニル）−エテニル〕−２−ｐ−ク
ロロベンゾイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジエチルアミノフェニル）−エテニル〕−２−ｐ−ク
ロロベンゾイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジプロピルアミノフェニル）−エテニル〕−２−ｐ−
クロロベンゾイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジ−ｎ−ブチルアミノフェニル）−エテニル〕−２−
ｐ−クロロベンゾイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジメチルアミノフェニル）−エテニル〕−２−β−ナ
フトイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジエチルアミノフェニル）−エテニル〕−２−β−ナ
フトイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジプロピルアミノフェニル）−エテニル〕−２−β−
ナフトイルエタン 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジ−ｎ−ブチルアミノフェニル）−エテニル〕−２−
β−ナフトイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジメチルアミノフェニル）−エテニル〕−２−２−ジ
アセチルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジエチルアミノフェニル）−エテニル〕−２−２−ジ
アセチルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジプロピルアミノフェニル）−エテニル〕−２−２−
ジアセチルエタン 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジ−ｎ−ブチルアミノフェニル）−エテニル〕−２−
２−ジアセチルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジメチルアミノフェニル）−エテニル〕−２−２−ジ
ベンゾイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジエチルアミノフェニル）−エテニル〕−２−２−ジ
ベンゾイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジプロピルアミノフェニル）−エテニル〕−２−２−
ジベンゾイルエタン、 1,1−ビス−〔２′,2′,2″,2″−テトラキス−（ｐ
−ジ−ｎ−ブチルアミノフェニル）−エテニル〕−２−
２−ジベンゾイルエタン、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジメチル
アミノフェニル）−エテニル〕−メチルマロン酸ジメチ
ルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジエチル
アミノフェニル）−エテニル〕−メチルマロン酸ジメチ
ルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジプロピ
ルアミノフェニル）−エテニル〕−メチルマロン酸ジメ
チルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジ−ｎ−
ブチルアミノフェニル）−エテニル〕−メチルマロン酸
ジメチルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジメチル
アミノフェニル）−エテニル〕−メチルマロン酸ジエチ
ルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジエチル
アミノフェニル）−エテニル〕−メチルマロン酸ジエチ
ルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジプロピ
ルアミノフェニル）−エテニル〕−メチルマロン酸ジエ
チルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジ−ｎ−
ブチルアミノフェニル）−エテニル〕−メチルマロン酸
ジエチルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジメチル
アミノフェニル）−エテニル〕−メチルマロン酸ジ−イ
ソプロピルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジエチル
アミノフェニル）−エテニル〕−メチルマロン酸ジ−イ
ソプロピルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジプロピ
ルアミノフェニル）−エテニル〕−メチルマロン酸ジ−
イソプロピルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジ−ｎ−
ブチルアミノフェニル）−エテニル〕−メチルマロン酸
ジ−イソプロピルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジメチル
アミノフェニル）−エテニル〕−メチルマロン酸ジ−ｎ
−ブチルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジエチル
アミノフェニル）−エテニル〕−メチルマロン酸ジ−ｎ
−ブチルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジプロピ
ルアミノフェニル）−エテニル〕−メチルマロン酸ジ−
ｎ−ブチルエステル、 ビス−〔2,2,2′,2′−テトラキス−（ｐ−ジ−ｎ−
ブチルアミノフェニル）−エテニル〕−メチルマロン酸
ジ−ｎ−ブチルエステル、 本発明のロイコ染料は、従来のロイコ染料と同様に、
感圧記録材料や、感熱記録材料、熱転写型記録材料等の
記録材料における発色剤として使用することができる。1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dimethylaminophenyl) -ethenyl] -2,2-dinitrileethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Diethylaminophenyl) -ethenyl] -2,2-dinitrileethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dipropylaminophenyl) -ethenyl] -2,2-dinitrileethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Di-n-butylaminophenyl) -ethenyl] -2,2
-Dinitrileethane, 3,3-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dimethylaminophenyl) -ethenyl] -2-nitrile-propionic acid ethyl ester, 3,3-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Diethylaminophenyl) -ethenyl] -2-nitrile-propionic acid ethyl ester, 3,3-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Diproylaminophenyl) -ethenyl] -2-nitrile-propionic acid ethyl ester, 3,3-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Di-n-butylaminophenyl) -ethenyl] -2-
Nitrile-propionic acid ethyl ester, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dimethylaminophenyl) -ethenyl] -2-benzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Diethylaminophenyl) -ethenyl] -2-benzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dipropylaminophenyl) -ethenyl] -2-benzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Di-n-butylaminophenyl) -ethenyl] -2-
Benzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dimethylaminophenyl) -ethenyl] -2-p-chlorobenzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Diethylaminophenyl) -ethenyl] -2-p-chlorobenzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dipropylaminophenyl) -ethenyl] -2-p-
Chlorobenzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Di-n-butylaminophenyl) -ethenyl] -2-
p-chlorobenzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dimethylaminophenyl) -ethenyl] -2-β-naphthoylethane, 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p
-Diethylaminophenyl) -ethenyl] -2-β-naphthoylethane, 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p
-Dipropylaminophenyl) -ethenyl] -2-β-
Naphthoylethane 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Di-n-butylaminophenyl) -ethenyl] -2-
β-naphthoylethane, 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p
-Dimethylaminophenyl) -ethenyl] -2-diacetylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Diethylaminophenyl) -ethenyl] -2-diacetylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dipropylaminophenyl) -ethenyl] -2-2-
Diacetylethane 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Di-n-butylaminophenyl) -ethenyl] -2-
2-diacetylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dimethylaminophenyl) -ethenyl] -2-dibenzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Diethylaminophenyl) -ethenyl] -2-dibenzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Dipropylaminophenyl) -ethenyl] -2-2-
Dibenzoylethane, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p
-Di-n-butylaminophenyl) -ethenyl] -2-
2-dibenzoylethane, bis- [2,2,2 ', 2'-tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester, bis- [2,2,2', 2 ' -Tetrakis- (p-diethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester, bis- [2,2,2 ', 2'-tetrakis- (p-dipropylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester Ester, bis- [2,2,2 ', 2'-tetrakis- (p-di-n-
Butylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester, bis- [2,2,2 ', 2'-tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid diethyl ester, bis- [2 , 2,2 ', 2'-Tetrakis- (p-diethylaminophenyl) -ethenyl] -methylmalonic acid diethyl ester, bis- [2,2,2', 2'-tetrakis- (p-dipropylaminophenyl) -Ethenyl] -methylmalonic acid diethyl ester, bis- [2,2,2 ', 2'-tetrakis- (p-di-n-
Butylaminophenyl) -ethenyl] -methylmalonic acid diethyl ester, bis- [2,2,2 ', 2'-tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid di-isopropyl ester, bis- [2,2,2 ', 2'-tetrakis- (p-diethylaminophenyl) -ethenyl] -methylmalonic acid di-isopropyl ester, bis- [2,2,2', 2'-tetrakis- (p-di Propylaminophenyl) -ethenyl] -methylmalonic acid di-
Isopropyl ester, bis- [2,2,2 ', 2'-tetrakis- (p-di-n-
Butylaminophenyl) -ethenyl] -methylmalonic acid di-isopropyl ester, bis- [2,2,2 ', 2'-tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid di-n
-Butyl ester, bis- [2,2,2 ', 2'-tetrakis- (p-diethylaminophenyl) -ethenyl] -methylmalonic acid di-n
-Butyl ester, bis- [2,2,2 ', 2'-tetrakis- (p-dipropylaminophenyl) -ethenyl] -methylmalonic acid di-
n-butyl ester, bis- [2,2,2 ', 2'-tetrakis- (p-di-n-
Butylaminophenyl) -ethenyl] -methylmalonic acid di-n-butyl ester, the leuco dye of the present invention, like the conventional leuco dye,
It can be used as a color former in recording materials such as pressure-sensitive recording materials, heat-sensitive recording materials, and thermal transfer recording materials.
本発明のロイコ染料を用いて感圧記録材料を得るに
は、先ず、ロイコ染料溶解油のマイクロカプセルを調製
する。この場合、マイクロカプセルの調製は、例えば、
米国特許大2800457号明細書に記載されているような方
法で、ゼラチン等の樹脂を硬化させた外殻壁中に１〜４
％のロイコ染料を溶解したジイソプロピルナフタレン系
やターフェニル系の油を包蔵させることによって行うこ
とができる。マイクロカプセルの粒径は通常５μｍ前後
である。このマイクロカプセルをバインダーを用いて紙
やプラスチックフィルム等の支持体上に支持させて、発
色剤シートを得る。この発色剤シートを、呈色剤として
の電子受容性化合物層を有する呈色剤シートと重ね、等
圧等で加圧してカプセルを破壊し、ロイコ染料と呈色剤
とを接触させることによって、呈色剤シート上に発色画
像を得ることができる。In order to obtain a pressure-sensitive recording material using the leuco dye of the present invention, first, microcapsules of leuco dye-dissolved oil are prepared. In this case, the preparation of the microcapsules is, for example,
In a method as described in U.S. Pat.
% Leuco dye is dissolved in diisopropylnaphthalene-based or terphenyl-based oil. The particle size of the microcapsules is usually around 5 μm. The color capsule sheet is obtained by supporting the microcapsules on a support such as paper or a plastic film using a binder. By overlaying this color former sheet with a color former sheet having an electron-accepting compound layer as a color former, breaking the capsule by applying pressure at an equal pressure or the like, by contacting the leuco dye with the color former, A color image can be obtained on the colorant sheet.
本発明のロイコ染料を用いて感熱記録材料を得るに
は、ロイコ染料、呈色剤（電子受容性化合物）及び炭酸
カルシウムなどの填料やステアリン酸アミドなどの熱可
融性物質等の補助成分をそれぞれ水媒体に分散させ、そ
れらの混合液をバインダーと共に支持体上に塗布、乾燥
する。この場合、ロイコ染料の粒子径は体積平均粒子径
で0.1〜５μｍ程度にするのが好ましい。粒子径は小さ
い方が呈色剤と多く接触するため感度の向上をもたらす
が、極端に微粒子化すると地肌カブリの原因となる。従
って地肌カブリや熱感度低下を防止するためには、特に
体積平均粒子径で１〜４μｍ程度とするのが好ましい。
この感熱記録材料は、これをサーマルヘッド等で加熱
し、ロイコ染料と呈色剤を溶融接触させることにより、
発色画像を得ることができる。In order to obtain a thermosensitive recording material using the leuco dye of the present invention, an auxiliary component such as a leuco dye, a color former (an electron-accepting compound), a filler such as calcium carbonate, and a heat-fusible substance such as stearamide is used. Each of them is dispersed in an aqueous medium, and a mixture thereof is applied on a support together with a binder and dried. In this case, the particle diameter of the leuco dye is preferably about 0.1 to 5 μm in terms of volume average particle diameter. The smaller the particle size, the more contact with the coloring agent improves the sensitivity. However, if the particle size is extremely small, fogging of the background is caused. Therefore, in order to prevent background fog and a decrease in thermal sensitivity, the volume average particle diameter is particularly preferably about 1 to 4 μm.
This thermosensitive recording material is heated by a thermal head or the like, and the leuco dye and the colorant are brought into melting contact with each other,
A color image can be obtained.
また、本発明のロイコ染料を用いて熱転写型記録材料
を得るには、ロイコ染料を支持体に支持させて感熱転写
シートを作成し、呈色剤を支持体に支持させて受容シー
トを作成する。転写シートと受容シートを重ね、転写シ
ートの表面から加熱すると、受容シート上に発色画像が
得られる。To obtain a thermal transfer recording material using the leuco dye of the present invention, a heat-sensitive transfer sheet is prepared by supporting the leuco dye on a support, and a receptor sheet is prepared by supporting a colorant on the support. . When the transfer sheet and the receiving sheet are overlapped and heated from the surface of the transfer sheet, a color image is obtained on the receiving sheet.
本発明のロイコ染料は、従来のものと同様に種々の分
野において利用されるが、殊に、その優れた近赤外光吸
収特性を利用して、光学文字読取り装置用や、ラベルバ
ーコーダー、バーコードリーダーの記録読取り用の記録
材料における発色剤として利用することができる。The leuco dye of the present invention is used in various fields as well as conventional ones. In particular, the leuco dye is used for an optical character reader, a label bar coder, It can be used as a color former in a recording material for reading a record by a bar code reader.
なお、本発明のロイコ染料を感熱記録型ラベルシート
に使用する場合、支持体の一方の面に本発明のロイコ染
料と呈色剤を含む感熱発色層を設け、支持体の他方の面
に接着剤層を介して剥離台紙を設けた構造のものにすれ
ばよく、また、この場合、必要に応じ、画像安定性を高
めるために、感熱発色層表面に水溶性樹脂層等の保護層
を設けることもできる。When the leuco dye of the present invention is used for a heat-sensitive recording type label sheet, a thermosensitive coloring layer containing the leuco dye of the present invention and a coloring agent is provided on one surface of the support, and is adhered to the other surface of the support. In this case, a protective layer such as a water-soluble resin layer may be provided on the surface of the thermosensitive coloring layer in order to enhance image stability, if necessary. You can also.
本発明による前記一般式（Ｉ）で表される新規なロイ
コ染料を用いた記録材料は、その発色部が近赤外領域の
光を吸収し、汎用の半導体レーザーを用いた画像読取装
置によりその発色を読取ることができるという利点を有
している。さらに該記録材料は、発色濃度が高くしかも
その発色部は耐熱性、耐光性、耐湿性に優れている。ま
た本発明のロイコ染料は、種々の記録分野に応用され
る。しかも、本発明のロイコ染料は比較的簡単に安価な
コストで製造することができる。The recording material using the novel leuco dye represented by the general formula (I) according to the present invention has a coloring portion absorbing light in the near-infrared region, and a recording material using a general-purpose semiconductor laser. There is an advantage that color development can be read. Further, the recording material has a high coloring density and the coloring portion is excellent in heat resistance, light resistance and moisture resistance. Further, the leuco dye of the present invention is applied to various recording fields. In addition, the leuco dye of the present invention can be produced relatively easily at low cost.
次に本発明を実施例によりさらに詳細に説明する。な
お以下において示す％および部はいずれも重量基準であ
る。Next, the present invention will be described in more detail with reference to examples. The percentages and parts shown below are based on weight.
実施例１ 1,1−ビス〔２′,2′,2″,2″−テトラキス（ｐ−ジ
メチルアミノフェニル）−エテニル〕−2,2−ジニトリ
ルエタンの合成 N,N−ジメチルホルムアミド（DMF）200mlに含量60％
の水素化ナトリウム1.5gを入れ、室温で撹拌した後、更
にマロンニトリル3.3gをゆっくり加えた。水素ガスの発
生が止み、しばらく撹拌した後、更に1,1,5,5−テトラ
キス−（ｐ−ジメチルアミノフェニル）−2,4−ペンタ
ジエン−１−オールパークロレート16.1gをゆっくり加
えた。室温で３時間反応させた後、反応溶液に水300ml
を加え、析出した褐色結晶を濾過、水洗、乾燥した。こ
の結晶をアセトン200ml中で１時間撹拌し、濾過したと
ころ、薄い赤色の結晶が9.1g得られた。この化合物の分
解点は191−195℃であった。Example 1 Synthesis of 1,1-bis [2 ', 2', 2 ", 2" -tetrakis (p-dimethylaminophenyl) -ethenyl] -2,2-dinitrileethane 60% content in 200 ml of N, N-dimethylformamide (DMF)
Was stirred at room temperature, and then 3.3 g of malononitrile was slowly added. After the generation of hydrogen gas was stopped and the mixture was stirred for a while, 16.1 g of 1,1,5,5-tetrakis- (p-dimethylaminophenyl) -2,4-pentadien-1-ol perchlorate was further slowly added. After reacting at room temperature for 3 hours, add 300 ml of water to the reaction solution.
Was added, and the precipitated brown crystals were filtered, washed with water and dried. The crystals were stirred in 200 ml of acetone for 1 hour and filtered to obtain 9.1 g of pale red crystals. The decomposition point of this compound was 191-195 ° C.
実施例２ 3,3−ビス〔２′,2′,2″,2″−テトラキス（ｐ−ジ
メチルアミノフェニル）−エテニル〕−2,2−ニトリル
−プロピオン酸エチルエスタルの合成 実施例１のマロンニトリル3.3gの代わりにシアノ酢酸
エチルエステル5.7gを使用した以外は、実施例１と同様
に操作したところ、薄い赤色の結晶が10.2g得られた。
この化合物の分解点は180.5〜183.5℃であった。Example 2 Synthesis of 3,3-bis [2 ', 2', 2 ", 2" -tetrakis (p-dimethylaminophenyl) -ethenyl] -2,2-nitrile-ethyl propionate The same operation as in Example 1 was carried out except that 5.7 g of cyanoacetate ethyl ester was used instead of 3.3 g of malononitrile in Example 1, whereby 10.2 g of pale red crystals were obtained.
The decomposition point of this compound was 180.5-183.5 ° C.
実施例３ 1,1−ビス〔２′,2′,2″,2″−テトラキス（ｐ−ジ
メチルアミノフェニル）−エテニル〕−２−ベンゾイル
エタンの合成 アセトフェノン100mlに含量60％の水素ナトリウム2.0
gを加え、しばらく撹拌した後、1,1,5,5−テトラキス−
（ｐ−ジメチルアミノフェニル）−2,4−ペンタジエン
−１−オールパークロレート16.1gを加え、55℃で３時
間反応させた。反応後、水100mlを加え、減圧濃縮し
た。残渣のタール状物にアセトン200mlを加えてしばら
く撹拌していると、結晶が析出してきて、薄い橙色の結
晶が5.3g得られた。この化合物の融点は132.5〜135℃で
あった。Example 3 Synthesis of 1,1-bis [2 ', 2', 2 ", 2" -tetrakis (p-dimethylaminophenyl) -ethenyl] -2-benzoylethane Sodium hydrogen 2.0 with a content of 60% in acetophenone 100 ml
g, and after stirring for a while, 1,1,5,5-tetrakis-
16.1 g of (p-dimethylaminophenyl) -2,4-pentadiene-1-ol perchlorate was added and reacted at 55 ° C. for 3 hours. After the reaction, 100 ml of water was added, and the mixture was concentrated under reduced pressure. When 200 ml of acetone was added to the residual tar-like substance and the mixture was stirred for a while, crystals began to precipitate, and 5.3 g of pale orange crystals were obtained. The melting point of this compound was 132.5-135 ° C.
実施例４ 1,1−ビス〔２′,2′,2″,2″−テトラキス（ｐ−ジ
メチルアミノフェニル）−エテニル〕−２−ｐ−クロロ
ベンゾイルエタンの合成 DMF200mlに含量60％の水素化ナトリウム1.5gを入れ、
室温で撹拌した後、更にｐ−クロロアセトフェノン7.73
gをゆっくり加えた。しばらく撹拌した後、1,1,5,5−テ
トラキス（ｐ−ジメチルアミノフェニル）−エテニル）
−2,4−ペンタジエン−１−オールパークロレート16.1g
をゆっくり加えた。50℃で３時間反応させた後、反応溶
液に水300mlを加え、析出したハルツを水洗し乾燥後、
アセトン200ml中でしばらく撹拌していると結晶化し、
橙色結晶が3.2g得られた。この化合物の融点は118〜12
0.5℃であった。Example 4 Synthesis of 1,1-bis [2 ', 2', 2 ", 2" -tetrakis (p-dimethylaminophenyl) -ethenyl] -2-p-chlorobenzoylethane 1.5 g of sodium hydride with a content of 60% was placed in 200 ml of DMF,
After stirring at room temperature, p-chloroacetophenone 7.73 was further added.
g was added slowly. After stirring for a while, 1,1,5,5-tetrakis (p-dimethylaminophenyl) -ethenyl)
-2,4-pentadiene-1-all perchlorate 16.1 g
Was slowly added. After reacting at 50 ° C for 3 hours, 300 ml of water was added to the reaction solution, and the precipitated Harz was washed with water and dried.
Crystallizes when stirred for a while in 200 ml of acetone,
3.2 g of orange crystals were obtained. The melting point of this compound is 118-12
0.5 ° C.
実施例５ 1,1−ビス〔２′,2′,2″,2″−テトラキス（ｐ−ジ
メチルアミノフェニル）−エテニル〕−２−β−ナフト
イルエタンの合成 実施例４のｐ−クロロアセトフェノン7.73gの代わり
に２−アセチルナフタレン8.5gを使用した以外は、実施
例４と同様に操作したところ、薄い黄色結晶が4.8g得ら
れた。この化合物の融点は199〜203℃であった。Example 5 Synthesis of 1,1-bis [2 ', 2', 2 ", 2" -tetrakis (p-dimethylaminophenyl) -ethenyl] -2-β-naphthoylethane By operating in the same manner as in Example 4 except that 8.5 g of 2-acetylnaphthalene was used instead of 7.73 g of p-chloroacetophenone in Example 4, 4.8 g of pale yellow crystals were obtained. The melting point of this compound was 199-203 ° C.
実施例６ 1,1−ビス〔２′,2′,2″,2″−テトラキス（ｐ−ジ
メチルアミノフェニル）−エテニル〕−２−β−ジアセ
チルエタンの合成 実施例４のｐ−クロロアセトフェノン7.73gの代わり
にアセチルアセトン5.0gを使用した以外は、実施例４と
同様に操作したところ、薄い黄色結晶が14.6g得られ
た。この化合物の融点は108〜110.5℃であった。Example 6 Synthesis of 1,1-bis [2 ', 2', 2 ", 2" -tetrakis (p-dimethylaminophenyl) -ethenyl] -2-β-diacetylethane The same operation as in Example 4 was carried out except that 5.0 g of acetylacetone was used instead of 7.73 g of p-chloroacetophenone in Example 4, whereby 14.6 g of pale yellow crystals were obtained. The melting point of this compound was 108-110.5 ° C.
実施例７ 1,1−ビス〔２′,2′,2″,2″−テトラキス（ｐ−ジ
メチルアミノフェニル）−エテニル〕−２−２−ジベン
ゾイルエタンの合成 実施例４のｐ−クロロアセトフェノン7.73gの代わり
にジベンゾイルメタン11.2gを使用した以外は、実施例
４と同様に操作したところ、黄緑色を帯びた白色結晶が
15.8g得られた。この化合物の融点は107.5〜108℃であ
った。Example 7 Synthesis of 1,1-bis [2 ', 2', 2 ", 2" -tetrakis (p-dimethylaminophenyl) -ethenyl] -2--2-dibenzoylethane The same operation as in Example 4 was carried out except that 11.2 g of dibenzoylmethane was used instead of 7.73 g of p-chloroacetophenone in Example 4, and a yellow-greenish white crystal was obtained.
15.8 g was obtained. The melting point of this compound was 107.5-108 ° C.
実施例８ ビス〔2,2,2′,2′−テトラキス（ｐ−ジメチルアミ
ノフェニル）−エテニル〕−メチルマロン酸ジメチルエ
ステルの合成 実施例１のマロンニトリル3.3gの代わりにマロン酸ジ
メチルエステル6.61gを用いた以外は、実施例１と同様
に操作したところ、淡く黄緑色の帯びた白色結晶が11.5
g得られた。この化合物の融点は159〜161℃であった。Example 8 Synthesis of bis [2,2,2 ', 2'-tetrakis (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester The same operation as in Example 1 was carried out except that malonic acid dimethyl ester 6.61 g was used instead of malononitrile 3.3 g in Example 1, to obtain pale yellow-greenish white crystals of 11.5 g.
g was obtained. The melting point of this compound was 159-161 ° C.
実施例９ ビス〔2,2,2′,2′−テトラキス（ｐ−ジメチルアミ
ノフェニル）−エテニル〕−メチルマロン酸ジエチルエ
ステルの合成 実施例１のマロンニトリル3.3gの代わりにマロン酸ジ
エチルエステル8.0gを用いた以外は、実施例１と同様に
操作したところ、淡く黄緑色の帯びた白色結晶が15.8g
得られた。この化合物の融点は151〜152℃であった。Example 9 Synthesis of bis [2,2,2 ', 2'-tetrakis (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid diethyl ester The same operation as in Example 1 was performed except that 8.0 g of malonic acid diethyl ester was used instead of 3.3 g of malononitrile in Example 1, whereby 15.8 g of pale yellowish greenish white crystals were obtained.
Obtained. The melting point of this compound was 151-152 ° C.
実施例10 ビス〔2,2,2′,2′−テトラキス（ｐ−ジメチルアミ
ノフェニル）−エテニル〕−メチルマロン酸ジ−イソプ
ロピルエステルの合成 実施例１のマロンニトリル3.3gの代わりにマロン酸ジ
−イソプロピルエステル9.41gを用いた以外は、実施例
１と同様にして反応を行なった。反応後、水を加えると
ハルツ状の塊が得られた。このハルツを水洗し乾燥後、
アセトン150ml中で１時間撹拌し、濾過したところ、淡
く黄緑色の帯びた白色結晶が13.8g得られた。この化合
物の融点は141〜143℃であった。Example 10 Synthesis of bis [2,2,2 ', 2'-tetrakis (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid di-isopropyl ester The reaction was carried out in the same manner as in Example 1 except that instead of 3.3 g of malononitrile, 9.41 g of malonic acid di-isopropyl ester was used. After the reaction, when water was added, a Harz-like mass was obtained. After washing and drying this Harz,
After stirring in 150 ml of acetone for 1 hour and filtration, 13.8 g of pale yellowish greenish white crystals were obtained. The melting point of this compound was 141-143 ° C.
実施例11 ビス〔2,2,2′,2′−テトラキス（ｐ−ジメチルアミ
ノフェニル）−エテニル〕−メチルマロン酸ジ−ｎ−ブ
チルエステルの合成 実施例１のマロンニトリル3.3gの代わりにマロン酸ジ
−ｎ−ブチルエステル10.8gを用いた以外は、実施例１
と同様にして反応をおこなった。反応後、水を加えると
タール状物が得られた。このタール状物をｎ−ヘキサン
とアセトンとの混合溶媒（体積比9:1）で加熱抽出し、
抽出液を放置したところ、黄色粒状結晶が10.7g得られ
た。この化合物の融点は112〜114.5℃であった。Example 11 Synthesis of bis [2,2,2 ', 2'-tetrakis (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid di-n-butyl ester Example 1 except that 10.8 g of malonic acid di-n-butyl ester was used in place of 3.3 g of malononitrile of Example 1.
The reaction was carried out in the same manner as described above. After the reaction, tar was obtained by adding water. This tar-like substance was heated and extracted with a mixed solvent of n-hexane and acetone (volume ratio 9: 1),
When the extract was allowed to stand, 10.7 g of yellow granular crystals were obtained. The melting point of this compound was 112 to 114.5 ° C.
実施例12〜20 前記の実施例と同様な方法で得られた新規ロイコ染料
のシリカゲル上での発色色調を調べた。その結果を表−
１に示す。Examples 12 to 20 The color tone on silica gel of the novel leuco dye obtained in the same manner as in the above examples was examined. Table-
It is shown in FIG.
応用例１ 感熱記録紙の製造 下記組成の各混合物を、それぞれボールミルで分散し
て〔Ａ〕〜〔Ｄ〕液を調製した。 Application Example 1 Production of Thermal Recording Paper Each mixture having the following composition was dispersed in a ball mill to prepare [A] to [D] solutions.
実施例１のロイコ染料 10部 ヒドロキシエチルセルロース10％水溶液 10部 水 55部 なお、ロイコ染料の分散粒子は体積平均粒子径で2.58
μｍであった。Leuco dye of Example 1 10 parts Hydroxyethylcellulose 10% aqueous solution 10 parts Water 55 parts The dispersed particles of the leuco dye had a volume average particle diameter of 2.58.
μm.
ステアリン酸アミド 20部 メチルセルロース５％水溶液 20部 分散剤 ２部 水 60部 〔Ｃ液〕 炭酸カルシウム 30部 メチルセルロース５％水溶液 30部 分散剤 ２部 水 60部 〔Ｄ液〕 ビスフェノールＡ 40部 ポリビニルアルコール10％水溶液 20部 水 140部 上記の如くして得られた〔Ａ液〕、〔Ｂ液〕、〔Ｃ
液〕、〔Ｄ液〕を、1:1:1:3の割合で混合して塗料を作
成し、この塗液を坪量50g/m2の上質紙上に乾燥付着量が
染料だけで0.45/m2となるよう塗布し乾燥して、感熱記
録紙を得た。Stearamide 20 parts 5% aqueous solution of methylcellulose 20 parts Dispersant 2 parts Water 60 parts [liquid C] 30 parts Calcium carbonate 30 parts 5% aqueous solution of methylcellulose 30 parts Dispersant 2 parts water 60 parts [liquid D] Bisphenol A 40 parts polyvinyl alcohol 10 % Aqueous solution 20 parts water 140 parts [solution A], [solution B], [C
Liquid) and (Liquid D) were mixed at a ratio of 1: 1: 1: 3 to prepare a coating, and this coating liquid was dried on a high-quality paper having a basis weight of 50 g / m 2 with a dry adhesion of 0.45 / m 2 and dried to obtain a thermosensitive recording paper.
このようにして得た感熱記録紙について、熱傾斜試験
機を用い、130℃、１秒間（印加圧2.0Kg/cm2）で発色さ
せた。このときの発色濃度は、マクベス濃度計の黒用フ
ィルター（フィルターNo.:KodakラッテンNo.25）で測定
したところ1.03であり、地肌濃度は0.10であった。また
発色色調は濃青色を示し、発色部の吸収領域は約500〜9
00nmまであり、かなり強い吸収をもっている。その反射
スペクトルを第１図に示す（曲線１）。The heat-sensitive recording paper thus obtained was colored at 130 ° C. for 1 second (applied pressure: 2.0 kg / cm 2 ) using a thermal gradient tester. The color density at this time was 1.03 as measured with a black filter (filter No .: Kodak Ratten No. 25) of a Macbeth densitometer, and the background density was 0.10. In addition, the color tone is dark blue, and the absorption area of the colored portion is about 500 to 9
It has a very strong absorption up to 00 nm. The reflection spectrum is shown in FIG. 1 (curve 1).
応用例２ 感熱記録紙の製造 応用例１の〔Ａ液〕において、実施例１のロイコ染料
の代わりに実施例６のロイコ染料（分散粒子は体積平均
粒子径で2.54μｍ）を用いた以外は、応用例１と同様に
して感熱記録紙を得た。Application Example 2 Production of thermosensitive recording paper Except for using the leuco dye of Example 6 (the dispersed particles are 2.54 μm in volume average particle diameter) instead of the leuco dye of Example 1 in [Solution A] of Application Example 1, In the same manner as in Application Example 1, a thermosensitive recording paper was obtained.
得られた感熱記録紙について、応用例１と同様に発色
テストを行なったところ、発色濃度は1.01であり、地肌
濃度は0.10であった。また発色色調は濃青色を示し、発
色部の吸収領域は約500〜900nmまであり、かなり強い吸
収をもっている。その反射スペクトルを第２図に示す
（曲線２）。When a coloring test was performed on the obtained thermosensitive recording paper in the same manner as in Application Example 1, the coloring density was 1.01 and the background density was 0.10. The color tone is deep blue, and the color region has an absorption region of about 500 to 900 nm, and has a very strong absorption. The reflection spectrum is shown in FIG. 2 (curve 2).
応用例３ 感熱記録紙の製造 応用例１の〔Ａ液〕において、実施例１のロイコ染料
の代わりに実施例５のロイコ染料を用いた以外は、応用
例１と同様にして感熱記録紙を得、且つそれぞれ発色さ
せた。その発色部の反射スペクトルを第２図に示す（曲
線３）。Application Example 3 Production of Thermosensitive Recording Paper A thermosensitive recording paper was prepared in the same manner as in Application Example 1 except that the leuco dye of Example 5 was used in place of the leuco dye of Example 1 in [Solution A] of Application Example 1. And colored. FIG. 2 shows the reflection spectrum of the coloring portion (curve 3).
応用例４ 感熱記録紙の製造 応用例１の〔Ａ液〕において、実施例１のロイコ染料
の代わりに実施例８のロイコ染料（分散粒子は体積平均
粒子径で2.23μｍ）を用いた以外は、応用例１と同様に
して感熱記録紙を得た。Application Example 4 Production of thermosensitive recording paper Except for using the leuco dye of Example 8 (the dispersed particles are 2.23 μm in volume average particle diameter) in place of the leuco dye of Example 1 in [Solution A] of Application Example 1, In the same manner as in Application Example 1, a thermosensitive recording paper was obtained.
得られた感熱記録紙について、応用例１と同様に発色
テストを行なったところ、発色濃度は1.02であり、地肌
濃度は0.10であった。また発色色調は濃青色を示し、発
色部の吸収領域は約500〜900nmまであり、かなり強い吸
収をもっている。その反射スペクトルを第３図に示す
（曲線４）。A color development test was performed on the obtained heat-sensitive recording paper in the same manner as in Application Example 1. As a result, the color density was 1.02, and the background density was 0.10. The color tone is deep blue, and the color region has an absorption region of about 500 to 900 nm, and has a very strong absorption. The reflection spectrum is shown in FIG. 3 (curve 4).
比較例 感熱記録紙の製造 ロイコ染料としてPSD−150（商品名、新日曹化工社
製）を用いた以外は応用例１と同様な方法で感熱記録紙
を得、且つそれを発色させた。その発色部の反射スペク
トルを第１〜３図に示す（曲線５）。Comparative Example Production of Thermosensitive Recording Paper A thermosensitive recording paper was obtained in the same manner as in Application Example 1 except that PSD-150 (trade name, manufactured by Shin Nisso Kako Co., Ltd.) was used as a leuco dye, and was colored. The reflection spectrum of the colored portion is shown in FIGS. 1 to 3 (curve 5).
第１図等から明らかなように、この発色部は光波長約
700nm以上に対しては殆ど光吸収を示さない。As is apparent from FIG.
There is almost no light absorption for 700 nm or more.
応用例５ 感圧複写紙の製造 ゼラチン10部及びアラビアゴム10部を40℃の水400部
に溶解し、これに乳化剤としてロート油0.2部を添加
し、さらに実施例２のロイコ染料を２％溶解したジイソ
プロピルナフタレン油40部を乳化分散する。油滴の大き
さが平均５μｍになるところで乳化を止めて、40℃の水
を加えて全体を900部にして撹拌を続ける。この時、液
温が40℃以下にならないようにする。次に、10％酢酸を
加えて、液のpHを4.0〜4.2に調整して、コアセルベーシ
ョンを起こさせる。更に撹拌を続けて、20分後に冷却し
て、油滴の周囲に沈着したコアセルベート膜をゲル化す
る。液温を20℃にして、37％ホルムアルデヒド７部を添
加し、10℃になった後、15％苛性ソーダ水溶液を加え、
pHを９にする。この時、苛性ソーダの添加はゆっくり注
意しておこなう。続いて、20分撹拌加温して、50℃にす
ると、ロイコ染料溶解油のマイクロカプセルが作成され
る。得られたマイクロカプセルを、水溶性澱粉をバイン
ダーとして、支持体の下面に6g/m2塗布し、乾燥して上
用紙を得た。Application Example 5 Manufacture of pressure-sensitive copying paper 10 parts of gelatin and 10 parts of gum arabic are dissolved in 400 parts of water at 40 ° C., 0.2 parts of funnel oil is added as an emulsifier, and 2% of the leuco dye of Example 2 is added. 40 parts of the dissolved diisopropyl naphthalene oil are emulsified and dispersed. The emulsification is stopped when the average size of the oil droplets reaches 5 μm, and water is added at 40 ° C. to make the whole 900 parts, and stirring is continued. At this time, make sure that the liquid temperature does not fall below 40 ° C. Next, 10% acetic acid is added to adjust the pH of the solution to 4.0 to 4.2 to cause coacervation. Stirring is further continued and cooling is performed after 20 minutes to gel the coacervate film deposited around the oil droplets. The liquid temperature was adjusted to 20 ° C, 7 parts of 37% formaldehyde was added, and after the temperature reached 10 ° C, a 15% aqueous solution of caustic soda was added.
Adjust the pH to 9. At this time, caustic soda is added slowly and carefully. Subsequently, the mixture is heated to 50 ° C. by stirring and heating for 20 minutes, whereby microcapsules of leuco dye-dissolved oil are produced. The obtained microcapsules were coated on the lower surface of the support at 6 g / m 2 using water-soluble starch as a binder, and dried to obtain upper paper.
この上用紙と市販感圧呈色シートとを重ね合せ、筆圧
などで加圧したところ、呈色シートに濃青色の鮮明な複
写像が得られた。When the upper sheet and the commercially available pressure-sensitive coloring sheet were overlapped and pressed with pen pressure or the like, a clear copy image of dark blue was obtained on the coloring sheet.
応用例６ 感圧複写紙の製造 応用例５において、実施例２のロイコ染料の代りに実
施例７のロイコ染料を用いた以外は、応用例５と同様に
して上用紙を得た。Application Example 6 Production of pressure-sensitive copying paper An upper paper was obtained in the same manner as in Application Example 5, except that the leuco dye of Example 7 was used instead of the leuco dye of Example 2.
この上用紙と市販感圧呈色シートとを重ね合せ、筆圧
などで加圧したところ、応用例５と同様、呈色シートに
濃青色の鮮明な複写像が得られた。When the upper sheet and the commercially available pressure-sensitive coloring sheet were overlaid and pressed with pen pressure or the like, a clear copy image of dark blue was obtained on the coloring sheet as in Application Example 5.
応用例７ 感圧複写紙の製造 応用例５において、実施例２のロイコ染料の代りに実
施例９のロイコ染料を用いた以外は、応用例５と同様に
して上用紙を得た。Application Example 7 Production of pressure-sensitive copying paper An upper paper was obtained in the same manner as in Application Example 5, except that the leuco dye of Example 9 was used instead of the leuco dye of Example 2.
この上用紙と市販感圧呈色シートとを重ね合せ、筆圧
などで加圧したところ、応用例５と同様、呈色シートに
濃青色の鮮明な複写像が得られた。When the upper sheet and the commercially available pressure-sensitive coloring sheet were overlaid and pressed with pen pressure or the like, a clear copy image of dark blue was obtained on the coloring sheet as in Application Example 5.
第１〜３図は本発明の電子供与性発色剤を用いて得られ
た感熱記録紙及び市販の電子供与性発色剤を用いて得ら
れた感熱記録紙の発色像の各光波長に対する反射率を示
す。 曲線１（実線）：応用例１で得られた感熱記録紙の発色
像反射スペクトル 曲線２（実線）：応用例２で得られた感熱記録紙の発色
像反射スペクトル 曲線３（一点鎖線）：応用例３で得られた感熱記録紙の
発色像反射スペクトル 曲線４（実線）：応用例４で得られた感熱記録紙の発色
像反射スペクトル 曲線５（点線）：比較例で得られた感熱記録紙の発色像
反射スペクトルFIGS. 1 to 3 show reflectances of color images of a thermosensitive recording paper obtained by using the electron donating color former of the present invention and a thermosensitive recording paper obtained by using a commercially available electron donating colorant with respect to each light wavelength. Is shown. Curve 1 (solid line): Color image reflection spectrum of thermosensitive recording paper obtained in Application Example 1 Curve 2 (solid line): Color image reflection spectrum of thermosensitive recording paper obtained in Application Example 2 Curve 3 (dashed-dotted line): Application Colored image reflection spectrum of thermal recording paper obtained in Example 3 Curve 4 (solid line): Colored image reflection spectrum of thermal recording paper obtained in Application Example 4 Curve 5 (dotted line): Thermal recording paper obtained in Comparative Example Image reflection spectrum of
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−254165（ＪＰ，Ａ) 特開 昭63−254166（ＪＰ，Ａ) 特開 昭63−272581（ＪＰ，Ａ) 特開 昭63−30281（ＪＰ，Ａ) 特開 昭64−26675（ＪＰ，Ａ) 特開 平１−178555（ＪＰ，Ａ) 特開 平１−237192（ＪＰ，Ａ) 特開 昭62−225562（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-63-254165 (JP, A) JP-A-63-254166 (JP, A) JP-A-63-272581 (JP, A) JP-A-63-254581 30281 (JP, A) JP-A-64-26675 (JP, A) JP-A-1-178555 (JP, A) JP-A-1-237192 (JP, A) JP-A-62-225562 (JP, A)
Claims (1)
キル基を、R9及びR10は水素原子（但し双方が水素原子
である場合を除く、）、−CN又は−COR11を、並びにR11
はフェニル基、ハロゲンで置換されたフェニル基、ナフ
チル基、低級アルキル基又は低級アルコキシ基を、夫々
表わす、〕で表わされる新規なロイコ染料。(1) General formula [Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are lower alkyl groups, and R 9 and R 10 are hydrogen atoms (provided that both are hydrogen atoms) ), -CN or -COR 11 and R 11
Represents a phenyl group, a halogen-substituted phenyl group, a naphthyl group, a lower alkyl group or a lower alkoxy group, respectively.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63064893A JP2585692B2 (en) | 1988-03-17 | 1988-03-17 | New leuco dye |
| US07/291,675 US4939117A (en) | 1988-01-08 | 1988-12-29 | Leuco dyes and recording material employing the same |
| US07/512,208 US5057154A (en) | 1988-01-08 | 1990-04-20 | Leuco dyes and recording material employing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63064893A JP2585692B2 (en) | 1988-03-17 | 1988-03-17 | New leuco dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01236279A JPH01236279A (en) | 1989-09-21 |
| JP2585692B2 true JP2585692B2 (en) | 1997-02-26 |
Family
ID=13271217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63064893A Expired - Fee Related JP2585692B2 (en) | 1988-01-08 | 1988-03-17 | New leuco dye |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2585692B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5084593A (en) * | 1988-06-20 | 1992-01-28 | Ricoh Company, Ltd. | Leuco dyes and recording material employing the same |
-
1988
- 1988-03-17 JP JP63064893A patent/JP2585692B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01236279A (en) | 1989-09-21 |
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