JPH03229770A - Recording fluid - Google Patents
Recording fluidInfo
- Publication number
- JPH03229770A JPH03229770A JP2022095A JP2209590A JPH03229770A JP H03229770 A JPH03229770 A JP H03229770A JP 2022095 A JP2022095 A JP 2022095A JP 2209590 A JP2209590 A JP 2209590A JP H03229770 A JPH03229770 A JP H03229770A
- Authority
- JP
- Japan
- Prior art keywords
- group
- water
- recording
- formula
- recording liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012530 fluid Substances 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- -1 alkali metal salt Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 39
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002845 discoloration Methods 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 5
- 238000005562 fading Methods 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 2
- 125000003368 amide group Chemical group 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000004034 viscosity adjusting agent Substances 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 26
- 239000000975 dye Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000001454 recorded image Methods 0.000 description 8
- 239000000306 component Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- UGDAWAQEKLURQI-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;hydrate Chemical compound O.OCCOCCO UGDAWAQEKLURQI-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JUYIUHMASUKIFJ-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol 1-methylpyrrolidin-2-one Chemical compound CN1C(CCC1)=O.C(COCCO)O JUYIUHMASUKIFJ-UHFFFAOYSA-N 0.000 description 2
- JZCZNTBTAPXSPB-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethanol;hydrate Chemical compound O.OCCOCCOCCO JZCZNTBTAPXSPB-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 241001648319 Toronia toru Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012533 medium component Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は記録ヘッドのオリフィスから液滴を飛翔させて
記録を行うインクジェット方式或いは筆記用具に使用す
るのに好適な記録液に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a recording liquid suitable for use in an inkjet system or a writing instrument in which recording is performed by ejecting droplets from an orifice of a recording head.
（従来の技術及びその問題点）
インクジェット記録方法は騒音の発生が少な（、普通紙
に対して特別な定着を要することなく、高速記録が行え
ることから種々のタイプのものが活発に研究されている
。(Prior art and its problems) Various types of inkjet recording methods are being actively researched because they generate less noise (and can perform high-speed recording on plain paper without requiring special fixing). There is.
これらインクジェット記録方法において使用される記録
液としては、粘度、表面張力等の物性値が適正範囲内に
あること、微細な吐出口（オリフィス）を目詰まりさせ
ないこと、鮮明な色調でしかも充分に高い濃度の記録画
像を与えること、保存中に物性変化或いは固形分の析出
等を生じないこと等の緒特性が要求される。The recording liquid used in these inkjet recording methods must have physical properties such as viscosity and surface tension within appropriate ranges, must not clog the fine ejection openings (orifices), and must have a clear color tone and a sufficiently high It is required to have certain characteristics such as providing a recorded image of density and not causing changes in physical properties or precipitation of solid content during storage.
更にこれら特性に加えて、紙に代表される被記録材の種
類を制限せずに記録が行えること、被記録材への定着速
度が大きいこと、耐候性、耐水性、耐摩耗性に優れてい
ること、解像度の優れた画像を与えること等の性質も要
求される。In addition to these properties, it also has the ability to record without limiting the type of recording material such as paper, has a high fixing speed to the recording material, and has excellent weather resistance, water resistance, and abrasion resistance. It is also required to have properties such as high resolution and the ability to provide images with excellent resolution.
インクジェット記録方法に適する記録液は、基本的には
記録剤としての染料とその溶媒とから組成されるもので
あるから、上記の記録液特性は染料固有の性質に左右さ
れるところが大きい、従つて記録液が上記特性を具備す
る様に染料を選択することは斯かる技術分野において極
めて重要な技術である。A recording liquid suitable for an inkjet recording method is basically composed of a dye as a recording agent and its solvent. Selecting a dye so that the recording liquid has the above characteristics is an extremely important technique in this technical field.
特に記録画像の経時安定性は重要であり、これまで光褪
色に関しては多（の研究がなされており、徐々に改良さ
れつつある。殊に含金属アゾ染料は、光には比較的安定
であることが知られている。In particular, the stability of recorded images over time is important, and many studies have been conducted on photofading, and improvements are being made gradually.In particular, metal-containing azo dyes are relatively stable against light. It is known.
しかしながら、この様な含金属系の染料を用いた記録画
像は室内等に掲示しておくと、強い光が殆ど当たらない
にも係らず褪色してしまう現象がある。この現象は複写
機の近（でより顕著であり、鮮明な色調が変化したり或
いは印字濃度も低下してしまう。その結果著しく画像の
品位が低下してしまう為、是非とも解決しなければなら
ない問題である。However, when images recorded using such metal-containing dyes are displayed indoors or the like, there is a phenomenon in which the images fade even though they are hardly exposed to strong light. This phenomenon is more noticeable in the vicinity of a copying machine, where the sharp color tone changes or the print density decreases.As a result, the quality of the image deteriorates significantly, so it must be resolved. That's a problem.
従って、本発明の目的は、上記従来技術の問題点を解決
し、室内や複写機の近くでも変色や褪色を発生すること
な（、長期間の保存に耐える記録画像が得られる言己録
液を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a self-recording liquid that does not cause discoloration or fading even indoors or near a copying machine, and that provides recorded images that can withstand long-term storage. Our goal is to provide the following.
本発明の別な目的は、記録画像の耐水性を向上させる記
録液を提供することである。水溶性記録液による記録画
像は水溶性である為耐水性に乏しく、印字物が水に濡れ
た場合に画像が消失したり、滲む等して画像品位が低下
することがある。Another object of the present invention is to provide a recording liquid that improves the water resistance of recorded images. Images recorded using a water-soluble recording liquid are water-soluble and therefore have poor water resistance, and when a printed matter gets wet with water, the image may disappear or smudge, resulting in a decrease in image quality.
一般に直接染料を記録剤として用いた場合、直接染料は
紙のセルロース繊維への染着性が強い為に水に濡れても
落ちにくく、又、滲みに（いという利点がある。この傾
向は染料の直線性が高いほどセルロース繊維に吸着され
易く、従って鎖長の長い染料は耐水性が良好であること
が多い。In general, when direct dyes are used as recording agents, they have the advantage of being difficult to remove even when wet with water because they have a strong dyeing property on the cellulose fibers of paper, and are less likely to bleed. The higher the linearity of the dye, the easier it is to be adsorbed on cellulose fibers, and therefore dyes with longer chains often have better water resistance.
（問題点を解決する為の手段） 上記目的は以下の本発明によって達成される。(Means for solving problems) The above objects are achieved by the present invention as described below.
即ち、本発明は、記録剤と水と水溶性有機溶剤とを必須
成分とする記録液において、前記記録剤として下記一般
式（Ａ）で表される構造の化合物を含むことを特徴とす
る記録液である。That is, the present invention provides a recording liquid containing a recording agent, water, and a water-soluble organic solvent as essential components, characterized in that the recording agent contains a compound having a structure represented by the following general formula (A). It is a liquid.
（但し、
式中Ｘは下記構造を、
−ＮＨ−Ｃ”＼−Ｒ３
］１
２
Ｍは２価の金属を、Ｓはスルホン酸基又はそのアルカリ
金属塩〜アンモニウム塩を、ρはｌ又は２を、Ｒ３は水
素原子、アルキル基、スルホン酸基又はアルキルアミド
基を、Ｒ２はスルホン酸基又はアルコキシ基で置換され
てもよいフェノキシ基、アニリノ基又は−ＮＨ（ＣＨａ
）−ＮＨ−Ｒ７（ｍは２〜６の整数）を、Ｒ３は一０Ｈ
１−ＮＲ４Ｒ％又はアルコキシ基を、Ｒ４及びＲ５は夫
々独立して−（ＣＨａＣ）１．０）。−Ｒ６又は−（Ｃ
Ｈ２ＣＨＯＨ） 、、−Ｒ６（ｎは０〜４の整数）を、
Ｒ６は水素原子、メチル基又はメチロール基を。(However, in the formula, X represents the following structure, -NH-C"\-R3 ]12M represents a divalent metal, S represents a sulfonic acid group or its alkali metal salt to ammonium salt, and ρ represents l or 2 , R3 is a hydrogen atom, an alkyl group, a sulfonic acid group, or an alkylamido group, and R2 is a phenoxy group, anilino group, or -NH(CHa
)-NH-R7 (m is an integer of 2 to 6), R3 is -0H
1-NR4R% or an alkoxy group, R4 and R5 are each independently -(CHaC)1.0). -R6 or -(C
H2CHOH) , -R6 (n is an integer from 0 to 4),
R6 is a hydrogen atom, methyl group or methylol group.
Ｒ１はスルホン酸基又はアルコキシ基で置換されてもよ
いフェニルスルホニル基又はフェニルアセチル基を、Ｑ
は
Ｒ８〜Ｒ１４は夫々独立してＲ１で示した原子団のうち
のいずれかを表す。）
（作 用）
本発明者等は鋭意研究の結果、前記の様な褪色現象を引
き起こす原因は、空気中に存在するオゾン、Ｎ低、Ｓ帆
等の酸化性ガスによるものであることを見出した。R1 is a phenylsulfonyl group or a phenylacetyl group which may be substituted with a sulfonic acid group or an alkoxy group, and Q
R8 to R14 each independently represent any of the atomic groups represented by R1. ) (Function) As a result of intensive research, the inventors of the present invention discovered that the cause of the above-mentioned fading phenomenon is due to oxidizing gases such as ozone, nitrogen gas, and sulfur gas present in the air. Ta.
そこでこの様な欠点を改善すべく含金属系染料に関する
詳細な研究を行ったところ、前記一般式（Ａ）で示され
る分子構造を含むジスアゾ型染料を含有した記録液が、
耐光性は勿論のこと、オゾン等の酸化性ガス雰囲気下に
おいても変色及び褪色することのない良好な記録画像を
与え、しかも与えられた記録画像の耐水性が良好である
ことを見い出し本発明に至った。Therefore, in order to improve such drawbacks, detailed research on metal-containing dyes was conducted, and it was found that a recording liquid containing a disazo type dye having the molecular structure represented by the general formula (A),
It was discovered that not only light fastness but also good recorded images that do not discolor or fade even in an oxidizing gas atmosphere such as ozone can be obtained, and the recorded images have good water resistance. It's arrived.
（好ましい実施態様）
本発明を主として特徴づける前記一般式（Ａ）で表わさ
れる染料としては、該一般式に包含される限りいずれの
染料でもよいが、好ましい具体例としては、例えば、下
記のＮｏ、１乃至Ｎｏ、 ９の染料が挙げられる。尚、
前記一般式（Ａ）におけるＭは下記例示の銅の他にニッ
ケルやコバルト等の他の２価の金属であり得る。(Preferred Embodiment) The dye represented by the general formula (A), which mainly characterizes the present invention, may be any dye as long as it is included in the general formula, but preferred specific examples include the following No. , No. 1 to No. 9. still,
M in the general formula (A) may be other divalent metals such as nickel and cobalt in addition to copper as exemplified below.
Ｎｏ、 １ Ｎ。No, 1 N.
Ｎｏ。No.
Ｎｏ。No.
Ｎ。N.
Ｎｏ。No.
Ｎｏ。No.
Ｎ。N.
９
本発明の記録液における上述の染料の含有量は、液媒体
成分の種類、記録液に要求される特性等に依存して決定
されるが、一般には記録液全重量に対して、重量パーセ
ントで０．５乃至２０％、好ましくは０．５乃至１５％
、より好ましくは１乃至１０％の範囲とされる。勿論、
これらの特定の染料は単独でも混合物としても使用出来
、更に他の直接染料、酸性染料等の各種染料を併用して
使用することが出来る。9 The content of the above-mentioned dye in the recording liquid of the present invention is determined depending on the type of liquid medium components, the properties required of the recording liquid, etc., but is generally determined as a percentage by weight based on the total weight of the recording liquid. 0.5 to 20%, preferably 0.5 to 15%
, more preferably in the range of 1 to 10%. Of course,
These specific dyes can be used alone or as a mixture, and can also be used in combination with various dyes such as other direct dyes and acid dyes.
本発明の記録液に使用するのに好適な溶媒は、水又は水
と水溶性有機溶剤との混合溶媒であり、特に好適なもの
は水と水溶性有機溶剤と混合溶媒であって、水溶性有機
溶剤として記録液の乾燥防止効果を有する多価アルコー
ルを含有するものである。又、水としては、種々のイオ
ンを含有する一般の水でな（、脱イオン水を使用するの
が好ましい。A suitable solvent for use in the recording liquid of the present invention is water or a mixed solvent of water and a water-soluble organic solvent, and particularly preferred is a mixed solvent of water and a water-soluble organic solvent, which is a water-soluble solvent. It contains polyhydric alcohol, which has the effect of preventing the recording liquid from drying, as an organic solvent. Further, the water is not ordinary water containing various ions (it is preferable to use deionized water).
水と混合して使用される水温性有機溶剤としては、例え
ば、メチルアルコール、エチルアルコール、ｎ−プロピ
ルアルコール、イソプロピルアルコール、ｎ−ブチルア
ルコール、５ｅｅ−ブチルアルコール、ｔｅｒｔ−ブチ
ルアルコール、イソブチルアルコール等の炭素数１乃至
４アルキルアルコール類；ジメチルホルムアミド、ジメ
チルアセトアミド等のアミド類：アセトン、ジアセトン
アルコール等のケトン又はケトアルコール類；テトラヒ
ドロフラン、ジオキサン等のエーテル類；ポリエチレン
グリコール、ポリプロピレングリコール等のポリアルキ
レングリコール類；エチレングリコール、プロピレング
リコール、ブチレングリコール、トリエチレングリコー
ル、ｌ、２．６−ヘキサンドリオール、チオジグリコー
ル、ヘキシレングリコール、ジエチレングリコール等の
アルキレン基が２乃至６個の炭素原子を含むアルキレン
グリコール類、グリセリン；エチレングリコールメチル
（又はエチル）エーテル、ジエチレングリコールメチル
（又はエチル）エーテル、トリエチレングリコールモノ
メチル（又はエチル）エーテル等の多価アルコールの低
級アルキルエーテル類；Ｎ−メチル−２−ピロリドン、
１．３−ジメチル−２−イミダゾリジノン等が挙げられ
る。Examples of water-temperature organic solvents used in combination with water include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 5ee-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol. Alkyl alcohols with 1 to 4 carbon atoms; amides such as dimethylformamide and dimethylacetamide; ketone or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol Class: alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexandriol, thiodiglycol, hexylene glycol, diethylene glycol, etc. Glycerin; lower alkyl ethers of polyhydric alcohols such as ethylene glycol methyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether; N-methyl-2-pyrrolidone;
Examples include 1,3-dimethyl-2-imidazolidinone.
これらの多（の水溶性有機溶剤の中でも、ジエチレング
リコール等の多価アルコール、トリエチレングリコール
モノメチル（又はエチル）エーテル等の多価アルコール
の低級アルキルエーテル、Ｎ−メチル−２−ピロリドン
等の含窒素複素環式ケトンが好ましいものである。多価
アルコール類は、記録液中の水が蒸発し、染料が析出す
ることに基づ（ノズルの目詰り現象を防止する為の湿潤
剤としての効果が大きい為好ましいものである。Among these poly(water-soluble organic solvents), polyhydric alcohols such as diethylene glycol, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether, nitrogen-containing complexes such as N-methyl-2-pyrrolidone, etc. Cyclic ketones are preferred.Polyhydric alcohols are highly effective as wetting agents to prevent nozzle clogging, as the water in the recording liquid evaporates and the dye precipitates. Therefore, it is preferable.
記録液中の上記水溶性有機溶剤の含有量は、一般には記
録液の全重量に対して重量％で５乃至９５％、好ましく
は１０乃至８０％、より好ましくはＩ５乃至５０％の範
囲である。The content of the water-soluble organic solvent in the recording liquid is generally in the range of 5 to 95% by weight, preferably 10 to 80%, more preferably I5 to 50%, based on the total weight of the recording liquid. .
このときの水の含有量は、上記溶剤成分の種類、その組
成或いは所望される記録液の特性に依存して広い範囲で
決定されるが、記録液全重量中で一般に１０乃至９０％
、好ましくは１０乃至７０％を占める範囲内とされる。The water content at this time is determined within a wide range depending on the type of solvent component, its composition, and the desired characteristics of the recording liquid, but it is generally 10 to 90% of the total weight of the recording liquid.
, preferably within the range of 10 to 70%.
この様な成分から調合される本発明の記録液は、筆記具
用の記録液或は所謂インクジェット記録用の記録液とし
てそれ自体で記録特性（信号応答性、液滴形成の安定性
、吐出安定性、長時間の連続記録性、長時間の記録休止
後の吐出安定性）、保存安定性、被記録材への定着性、
或いは記録画像の色調鮮明性、耐光性、耐候性等いずれ
もバランスのとれた優れたものである。そしてこの様な
特性を更に改良する為に、従来から知られている各種添
加剤を更に添加含有せしめてもよい。The recording liquid of the present invention prepared from such components has excellent recording properties (signal response, stability of droplet formation, ejection stability) as a recording liquid for writing instruments or a recording liquid for so-called inkjet recording. , long-term continuous recording performance, ejection stability after long-term recording pauses), storage stability, fixability to recording materials,
Alternatively, the recorded image has excellent, well-balanced color clarity, light resistance, weather resistance, etc. In order to further improve such properties, various conventionally known additives may be added.
例えば、ポリビニルアルコール、セルロース類、水溶性
樹脂等の粘度調整剤：カチオン、アニオン或いはノニオ
ン系の各種界面活性剤、ジエタノールアミン、トリエタ
ノールアミン等の表面張力調整剤：緩衝液によるｐＨ調
整剤、防カビ剤等を挙げることが出来る。For example, viscosity regulators such as polyvinyl alcohol, cellulose, and water-soluble resins; various cationic, anionic, or nonionic surfactants; surface tension regulators such as diethanolamine and triethanolamine; pH regulators using buffer solutions; and mold prevention agents. Agents, etc. can be mentioned.
又、記録液を帯電するタイプのインクジェット方式に使
用される記録液を調合する為には、塩化リチウム、塩化
アンモニウム、塩化ナトリウム等の無機塩類等の比抵抗
調整剤が添加される。Further, in order to prepare a recording liquid used in an inkjet method of charging the recording liquid, a resistivity adjusting agent such as inorganic salts such as lithium chloride, ammonium chloride, and sodium chloride is added.
尚、熱エネルギーの作用によって記録液を吐出させるタ
イプのインクジェット方式に適用する場合には、熱的な
物性値（例えば、比熱、熱膨張係数、熱伝導率等）が調
整されることもある。Note that when applied to an inkjet system in which recording liquid is ejected by the action of thermal energy, thermal physical property values (eg, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted.
以上の如き本発明の記録液は、種々の筆記具、記録器具
等による記録用記録液として有用なものであり、特にイ
ンクジェット用の記録液として有用である。これのイン
クジェット方式は、記録液をノズルより効果的に離脱さ
せて、射程体である被記録材に記録液を付与し得る方式
であれば、いかなる方式でもよい。The recording liquid of the present invention as described above is useful as a recording liquid for recording with various writing implements, recording instruments, etc., and is particularly useful as a recording liquid for inkjet use. The inkjet method may be any method as long as it can effectively remove the recording liquid from the nozzle and apply the recording liquid to the recording material that is the projectile.
（実施例）
次に実施例及び比較例を挙げて本発明を更に詳細に説明
するが、本発明はこれら実施例に限定されるものではな
い。尚、文中％とあるのは特に断りのない限り重量基準
である。(Examples) Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Note that % in the text is based on weight unless otherwise specified.
実施例１
Ｎｏ、 １の染料 ３％ジエ
チレングリコール ３０％イオン交換水（
以後水と略す） ６７％実施例２
Ｎｏ、 ２の染料
ポリエチレングリコール（平均分子量
５％
３００）
１０％
２０％
６５％
ジエチレングリコール
水
実施例３
Ｎｏ、３の染料
Ｎ−メチル−２−ピロリドン
ジエチレングリコール
水
実施例４
胤４の染料
３％
１５％
１５％
６７％
２％
トリエチレングリコール
水
実施例５
Ｎα５の染料
エチレングリコール
水
実施例６
Ｎα６の染料
ジエチレングリコール
エチルアルコール
水
実施例７
徹７の染料
グリセリン
ポリエチレングリコール
２８％
６７％
７％
４０％
５３％
４％
２０％
５％
７１％
ジエチレングリコール
水
実施例８
１１ｋｔ８の染料
６％
５％
（平均分子量３００）
ｌ ０％
２０％
５９％
３％
ジエチレングリコール ３０％イオン交換
水（以後水と略す） ６７％実施例９
歯、９の染料 ５％ポリエチ
レングリコール（平均分子量３００）１０％
ジエチレングリコール ２０％水
６５％上記の配合
各成分は容器の中で充分混合溶解し、孔径０．４５ＬＬ
ｍのテフロンフィルターで加圧濾過して本発明の記録液
とした。Example 1 No. 1 dye 3% diethylene glycol 30% ion exchange water (
67% Example 2 No. 2 dye polyethylene glycol (average molecular weight 5% 300) 10% 20% 65% diethylene glycol water Example 3 No. 3 dye N-methyl-2-pyrrolidone diethylene glycol water Implementation Example 4 Seed 4 Dye 3% 15% 15% 67% 2% Triethylene Glycol Water Example 5 Nα5 Dye Ethylene Glycol Water Example 6 Nα6 Dye Diethylene Glycol Ethyl Alcohol Water Example 7 Toru 7 Dye Glycerin Polyethylene Glycol 28 % 67% 7% 40% 53% 4% 20% 5% 71% Diethylene glycol water Example 8 11kt8 dye 6% 5% (average molecular weight 300) l 0% 20% 59% 3% Diethylene glycol 30% ion exchange water ( (hereinafter abbreviated as water) 67% Example 9 Tooth, Dye 9 5% Polyethylene glycol (average molecular weight 300) 10% Diethylene glycol 20% Water
65% The above ingredients are thoroughly mixed and dissolved in a container with a pore size of 0.45LL.
The recording liquid of the present invention was obtained by pressure filtration using a Teflon filter.
これらの記録液を発熱素子をインクの吐出エネルギー源
として利用したインクジェットプリンターＢＪ−１３０
Ａ （キャノン製、ノズル数４８本）に搭載して下記の
被記録材Ａ及びＢに１５ｍｍＸ３０ｍｇ＋のベタ印字を
した後、変褪色の促進法としてオゾン濃度が宮にｌＯ±
５ｐｐｍの範囲に保たれる遮光された槽内に印字物を１
２０分間放置して試験前後の印字物の色差ΔＥ″ａｂを
測定（ＪＩＳ Ｚ ８７３０に準拠）したところ、いず
れの場合もΔＥ”ａｂ値はｌＯ以下で変褪色の程度は少
な（、良好な結果が得られた。Inkjet printer BJ-130 uses these recording liquids as a heat generating element as an ink ejection energy source.
A (manufactured by Canon, number of nozzles: 48) and after printing a solid print of 15 mm x 30 mg+ on the following recording materials A and B, the ozone concentration was increased to 10± as a method to accelerate discoloration and fading.
One print is placed in a light-shielded tank maintained within the 5 ppm range.
When the color difference ΔE"ab of the printed matter before and after the test was measured after being left for 20 minutes (according to JIS Z 8730), the ΔE"ab value was less than 1O in each case, and the degree of discoloration was small (good results). was gotten.
被記録材Ａ、三菱製紙製インクジェット用コート紙ＮＭ
被記録材Ｂ キャノン製ビクセルプロ用専用指定紙
被記録材Ｃ：キヤノン製ＮＰ−６１５０用推奨紙
被記録材Ｄ＝ゼロックス製４０２４紙
次に同様に実施例に示した成分の記録液で作成した印字
片を、キセノンフェードメーターで９６時間照射前後の
ΔＥ″１゜で耐光性を評価したところ、いずれの場合も
５以下で変褪色の程度は少な（良好な結果が得られた。Recording material A: coated paper for inkjet manufactured by Mitsubishi Paper Industries NM Recording material B: specified paper exclusively for Canon's Bixel Pro Recording material C: recommended paper for Canon's NP-6150 Recording material D: 4024 paper manufactured by Xerox Next, do the same When the light resistance of a printed piece made with a recording liquid having the components shown in the example was evaluated using a xenon fade meter at ΔE''1° before and after 96 hours of irradiation, it was 5 or less in all cases, indicating that the degree of discoloration was small. (Good results were obtained.
又、上記と同様に実施例で示した成分の記録液で被記録
材Ｃ及びＤにベタ印字した印字片及び文字の印字物を静
水中に５分間浸漬した後、ベタ印字片のＯＤ値を浸漬前
のベタ印字物の初期ＯＤ値で割った値をＯＤ残存率（％
）で評価したところ、いずれの場合も７０％以上を示し
、更に文字の印字物には滲みが認められず、良好な耐水
性を示した。In addition, in the same manner as above, the printed pieces and characters printed solidly on the recording materials C and D with the recording liquid having the components shown in the examples were immersed in still water for 5 minutes, and then the OD value of the solid printed pieces was determined. The OD residual rate (%) is calculated by dividing the initial OD value of the solid print before dipping.
), the results were 70% or higher in all cases, and no bleeding was observed in the printed characters, indicating good water resistance.
尚、比較の為に比較例に示した成分の記録液で上記と同
様な方法で被記録材Ｃ及びＤ上に作成したベタ及び文字
による印字物について同様の耐水試験を行ったところ、
いずれの場合も５０％以下のＯＤ残存率で文字は著しく
褪色し判読困難となった。For comparison, a similar water resistance test was conducted on solid and character prints made on recording materials C and D in the same manner as above using a recording liquid with the components shown in the comparative example.
In all cases, when the OD residual rate was 50% or less, the characters were significantly faded and difficult to read.
比較例Ｉ
Ｃ，１，リアクティブブラック３１ ３％ジエ
チレングリコール ３０％水
６７％比較例２
下記構造式の染料 ５％ポリエチレ
ングリコール（平均分子量３００）ジエチレングリコー
ル
水
１０％
２０％
６５％
比較例３
下記構造式の染料
Ｎ−メチル−２−ピロリドン
ジエチレングリコール
水
３％
１５％
１５％
６７％
比較例４
下記構造式の染料
トリエチレングリコール
水
２％
２８％
７０％
比較例５
下記構造式の染料
エチレングリコール
水
比較例６
下記構造式の染料
ジエチレングリコール
エチルアルコール
水
７％
４０％
５３％
４％
２０％
５％
７１％
（発明の効果）
以上の通り、本発明の記録液はインクジェット言己録用
、筆記具用等に適している。Comparative Example I C,1, Reactive Black 31 3% diethylene glycol 30% water
67% Comparative Example 2 Dye with the following structural formula 5% polyethylene glycol (average molecular weight 300) diethylene glycol water 10% 20% 65% Comparative Example 3 Dye with the following structural formula N-methyl-2-pyrrolidone diethylene glycol water 3% 15% 15% 67% Comparative Example 4 Dye with the following structural formula, triethylene glycol water 2% 28% 70% Comparative Example 5 Dye with the following structural formula, ethylene glycol water Comparative Example 6 Dye with the following structural formula, diethylene glycol ethyl alcohol water 7% 40% 53% 4 % 20% 5% 71% (Effects of the Invention) As described above, the recording liquid of the present invention is suitable for inkjet recording, writing instruments, and the like.
特にインクジェット記録に用いた場合、記録特性（吐出
安定性、長時間の連続記録性）、保存安定性は勿論のこ
と、記録画像の耐光性等及びオゾン、Ｎｏ、、 ＳＯ，
等の酸化性ガスに対しても極めて安定でとりわけ普通紙
上の耐水性に優れた印字を得ることが出来、非常に有用
である。In particular, when used for inkjet recording, not only recording characteristics (ejection stability, long-term continuous recording), storage stability, but also light resistance of recorded images, ozone, No. 2, SO, etc.
It is extremely stable against oxidizing gases such as, and is extremely useful, as it can produce prints with excellent water resistance, especially on plain paper.
Claims (1)
記録液において、前記記録剤として下記一般式（Ａ）で
表される構造の化合物を含むことを特徴とする記録液。 ▲数式、化学式、表等があります▼（Ａ） （但し、式中Ｘは下記構造を、 ▲数式、化学式、表等があります▼ Ｍは２価の金属を、Ｓはスルホン酸基又はそのアルカリ
金属塩〜アンモニウム塩を、ｌは１又は２を、Ｒ＿１は
水素原子、アルキル基、スルホン酸基又はアルキルアミ
ド基を、Ｒ＿２はスルホン酸基又はアルコキシ基で置換
されてもよいフェノキシ基、アニリノ基又は−ＮＨ（Ｃ
Ｈ＿２）＿ｍＮＨ−Ｒ＿７（ｍは２〜６の整数）を、Ｒ
＿３は−ＯＨ、−ＮＲ＿４Ｒ＿５又はアルコキシ基を、
Ｒ＿４及びＲ＿５は夫々独立して−（ＣＨ＿２ＣＨ＿２
Ｏ）＿ｎ−Ｒ＿５又は−（ＣＨ＿２ＣＨＯＨ）＿ｎ−Ｒ
＿６（ｎは０〜４の整数）を、Ｒ＿６は水素原子、メチ
ル基又はメチロール基を、Ｒ＿７はスルホン酸基又はア
ルコキシ基で置換されてもよいフェニルスルホニル基又
はフェニルアセチル基を、Ｑは ▲数式、化学式、表等があります▼又は▲数式、化学式
、表等があります▼を、 Ｒ＿８〜Ｒ＿１＿４は夫々独立してＲ＿１で示した原子
団のうちのいずれかを表す。）(1) A recording liquid containing a recording agent, water, and a water-soluble organic solvent as essential components, characterized in that the recording agent contains a compound having a structure represented by the following general formula (A). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) (However, in the formula, Metal salt to ammonium salt, l is 1 or 2, R_1 is a hydrogen atom, alkyl group, sulfonic acid group, or alkylamido group, R_2 is a phenoxy group or anilino group that may be substituted with a sulfonic acid group or an alkoxy group. or -NH(C
H_2)_mNH-R_7 (m is an integer from 2 to 6), R
_3 is -OH, -NR_4R_5 or an alkoxy group,
R_4 and R_5 are each independently −(CH_2CH_2
O)_n-R_5 or -(CH_2CHOH)_n-R
_6 (n is an integer of 0 to 4), R_6 is a hydrogen atom, methyl group or methylol group, R_7 is a phenylsulfonyl group or phenylacetyl group which may be substituted with a sulfonic acid group or an alkoxy group, Q is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R_8 to R_1_4 each independently represent one of the atomic groups shown by R_1. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022095A JPH03229770A (en) | 1990-02-02 | 1990-02-02 | Recording fluid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022095A JPH03229770A (en) | 1990-02-02 | 1990-02-02 | Recording fluid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03229770A true JPH03229770A (en) | 1991-10-11 |
Family
ID=12073316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022095A Pending JPH03229770A (en) | 1990-02-02 | 1990-02-02 | Recording fluid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03229770A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6858069B2 (en) | 2001-10-26 | 2005-02-22 | Seiko Epson Corporation | Black aqueous ink composition, ink jet recording process using the same, and recorded matter |
| US7094279B2 (en) | 2003-11-25 | 2006-08-22 | Seiko Epson Corporation | Black water-based ink composition |
-
1990
- 1990-02-02 JP JP2022095A patent/JPH03229770A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6858069B2 (en) | 2001-10-26 | 2005-02-22 | Seiko Epson Corporation | Black aqueous ink composition, ink jet recording process using the same, and recorded matter |
| US7094279B2 (en) | 2003-11-25 | 2006-08-22 | Seiko Epson Corporation | Black water-based ink composition |
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