JP2725377B2 - Recording liquid - Google Patents
Recording liquidInfo
- Publication number
- JP2725377B2 JP2725377B2 JP13423789A JP13423789A JP2725377B2 JP 2725377 B2 JP2725377 B2 JP 2725377B2 JP 13423789 A JP13423789 A JP 13423789A JP 13423789 A JP13423789 A JP 13423789A JP 2725377 B2 JP2725377 B2 JP 2725377B2
- Authority
- JP
- Japan
- Prior art keywords
- recording
- recording liquid
- water
- formula
- present
- 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
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、インクジェット記録用及び筆記用具用の記
録液に関する。Description: FIELD OF THE INVENTION The present invention relates to a recording liquid for ink jet recording and writing implements.
インクジェット記録方式は、記録時の騒音が少ないこ
と、大判のカラー化が容易であること、また、ランニン
グコストが安いという利点を有しており、ノンインパク
トプリンタとしての市場が確立されつつある。The ink jet recording method has the advantages of low noise at the time of recording, easy large-format colorization, and low running cost, and the market as a non-impact printer is being established.
インクジェット記録方式では臭気、消防上の危険性あ
るいは安全性の面から近時水性インクが主として使用さ
れている。これらの水性インクには粘度、表面張力等の
物性値が適当であること、ノズルを目詰まりさせないこ
と、保存安定性に優れること、の他着色画像の濃度が高
いこと、耐光性、耐水性、耐オゾン性に優れていること
等の性質が要求される。In recent years, aqueous inks have been mainly used in the ink jet recording system in view of odor, fire hazard, and safety. These aqueous inks have appropriate physical properties such as viscosity and surface tension, do not clog the nozzles, have excellent storage stability, have high density of other colored images, light resistance, water resistance, Properties such as excellent ozone resistance are required.
この様な水性インクにおける色材としては液媒体が水
性であることから水溶性染料が使用されているが、上記
の基本的要求のうち耐水性についてはほぼ満足されるも
のが提案されている。As a coloring material in such a water-based ink, a water-soluble dye is used because the liquid medium is water-based, and among the above-mentioned basic requirements, those which are almost satisfied with water resistance have been proposed.
しかし、このような水溶性染料を用いた場合、カーボ
ンブラックあるいは顔料に比べて、本質的に耐光性及び
耐オゾン性が劣るため、何らかの保護剤が必要となる。
このため例えば紫外線吸収剤、酸化防止剤あるいは1O2
クエンチャーを添加することが検討されており、例え
ば、特開昭62-106,971号、特開昭59-53,566号、特開昭5
9-53,567号、特開昭59-51,961号、特開昭54-85,804号、
特開昭54-68,303号、特開昭64-75282号に開示されてい
る。However, when such a water-soluble dye is used, since light resistance and ozone resistance are essentially inferior to carbon black or pigment, some protective agent is required.
For this reason, for example, UV absorbers, antioxidants or 1 O 2
Addition of a quencher has been considered, for example, JP-A-62-106,971, JP-A-59-53,566, JP-A-5
No. 9-53,567, JP-A-59-51,961, JP-A-54-85,804,
These are disclosed in JP-A-54-68303 and JP-A-64-75282.
しかしながらこれらの記録液は、上記問題点に関し、
十分な効果が得られなかったり、あるいは効果が得られ
てもノズル先端において目詰まりし易くなるといった大
きな欠陥を併有している。However, these recording liquids are related to the above problems,
There is also a large defect that a sufficient effect cannot be obtained, or even if the effect is obtained, the nozzle tip is easily clogged.
本発明はとりわけ耐光性及び耐オゾン性に優れた印字
を得ることができる記録液の提供を目的とするものであ
る。An object of the present invention is to provide a recording liquid capable of obtaining a print excellent in light resistance and ozone resistance.
本発明は水溶性染料、水性媒体並びに下記一般式
〔Ｉ〕 （式中Ｒは−CH2COOH基、−CH2SO3H基又は下記一般式
〔II〕 C2H4Oｎ…… 〔II〕 （式中、ｎは１〜10を表わす。） で示されるポリオキシエチレン基を表わす。） で示される化合物を含有する記録液を要旨とするもので
ある。The present invention relates to a water-soluble dye, an aqueous medium and the following general formula (I) (Wherein R -CH 2 COOH group, in -CH 2 SO 3 H group or the following formula (II) C 2 H 4 O n ...... (II) (wherein, n in represents 1 to 10.) A recording liquid containing a compound represented by the formula:
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明に使用する水溶性染料としては、アゾ系、アン
トラキノン系、及びフタロシアニン系の直接染料及び酸
性染料が挙げられ、例えばC.I.Direct Black-17、−1
9、−22、−32、−51、−80、−91、−151及び−154、
C.I.Direct Blue-86及び−199、C.I.Direct Red-80、C.
I.Direct Yellow-86及び−142、C.I.Acid Black-2、−2
4、−26、−48、−52、−63、−172、−194及び−208、
C.I.Acid Blue-9、185及び−254、C.I.Acid Red-8、−3
5、−37及び−257、C.I.Acid Yeloow-23及び−49及びC.
I.Food Black-2等が挙げられる。Examples of the water-soluble dye used in the present invention include azo-based, anthraquinone-based, and phthalocyanine-based direct dyes and acid dyes, for example, CIDirect Black-17, -1
9, -22, -32, -51, -80, -91, -151 and -154,
CIDirect Blue-86 and -199, CIDirect Red-80, C.I.
I.Direct Yellow-86 and -142, CIAcid Black-2, -2
4, -26, -48, -52, -63, -172, -194 and -208,
CIAcid Blue-9, 185 and -254, CIAcid Red-8, -3
5, -37 and -257, CIAcid Yeloow-23 and -49 and C.
I. Food Black-2 and the like.
上記水溶性染料の含有量としては記録液全重量に対し
て0.2〜12％の範囲、好ましくは２〜８％の範囲が挙げ
られる。The content of the water-soluble dye is in the range of 0.2 to 12%, preferably 2 to 8%, based on the total weight of the recording liquid.
本発明の水性媒体としては、水の他に例えばエチレン
グリコール、プロピレングリコール、ブチレングリコー
ル、ジエチレングリコール、トリエチレングリコール、
ポリエチレングリコール（＃200）、ポリエチレングリ
コール（＃400）、グリセリン、Ｎ−ミチル−ピロリド
ン、Ｎ−エチル−ピロリドン、Ｎ−ビニル−ピロリド
ン、1,3−ジメチル−イミダゾリジノン、エチレングリ
コールモノアリルエーテル、エチレングリコールモノメ
チルエーテル、ジエチレングリコールモノメチルエーテ
ル、ジエチレングリコールモノブチルエーテル等を含有
しているのが好ましく、水性媒体の含有量としては、記
録液全重量に対し、63〜98.8重量％の範囲が挙げられ
る。As the aqueous medium of the present invention, in addition to water, for example, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol (# 200), polyethylene glycol (# 400), glycerin, N-mityl-pyrrolidone, N-ethyl-pyrrolidone, N-vinyl-pyrrolidone, 1,3-dimethyl-imidazolidinone, ethylene glycol monoallyl ether, It preferably contains ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and the like, and the content of the aqueous medium is in the range of 63 to 98.8% by weight based on the total weight of the recording liquid.
前記一般式〔Ｉ〕におけるＲとしては−CH2‐SO3H
−CH2COOHの他、下記一般式〔II〕 C2H4Oｎ…… ……〔II〕 （式中ｎは１〜10を表わす。） で示されるポリオキシエチレン基である。尚前記一般式
〔Ｉ〕で示される化合物は４−アミノ−2,2,6,6−テト
ラメチルピペリジンとヒドロキシメタンスルホン酸とを
反応させるか、あるいは下記一般式〔III〕 X-CH2COOH ……〔III〕 （式中ＸはCl原子又はBr原子を表わす。）で示されるハ
ロゲノ酢酸とを反応させるか、あるいは又、エチレンオ
キサイドとを反応させることによって容易に得られる。In the general formula [I], R represents —CH 2 —SO 3 H
Other -CH 2 COOH, a polyoxyethylene group represented by the following general formula [II] C 2 H 4 O n ...... ...... [II] (wherein n representing 1 to 10.) Represented by. The compound represented by the general formula [I] is obtained by reacting 4-amino-2,2,6,6-tetramethylpiperidine with hydroxymethanesulfonic acid, or by reacting the following general formula [III] X-CH 2 COOH ... [III] It is easily obtained by reacting with halogenoacetic acid represented by the formula (X represents a Cl atom or a Br atom) or by reacting with ethylene oxide.
尚、上記一般式〔Ｉ〕で示される化合物の含有量は記
録液全重量に対して0.5〜10重量％の範囲で使用され
る。The content of the compound represented by the general formula [I] is used in the range of 0.5 to 10% by weight based on the total weight of the recording liquid.
本発明の記録液のpHは、必要に応じてアルカリ金属水
酸化物、水酸化アンモニウム等の塩基性化合物を用いて
通常６〜８に調整される。あるいは前記一般式〔Ｉ〕の
化合物の−CH2COOH、−CH2SO3Hの基が反応後アルカリ金
属塩、アンモニウム塩等で得られた場合は、そのまま本
発明の記録液に用いてもよい。The pH of the recording liquid of the present invention is usually adjusted to 6 to 8 by using a basic compound such as an alkali metal hydroxide or ammonium hydroxide as needed. Or -CH 2 COOH the compound of formula (I), when the group -CH 2 SO 3 H is reacted alkali metal salts, obtained in ammonium salt, be used as the recording liquid of the present invention Good.
さらに本発明の記録液は記録液全重量に対し、0.5〜2
0重量％の界面活性剤を添加することにより印字後の速
乾性及び印字品位を改良することができる。Further, the recording liquid of the present invention is 0.5 to 2 parts by weight based on the total weight of the recording liquid.
By adding 0% by weight of a surfactant, quick drying after printing and print quality can be improved.
本発明を以下の実施例で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。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
実施例１ 上記の各成分を容器の中で充分混合溶解し、水酸化ナ
トリウムでpHを７に調整し、孔径１μのテフロンフィル
ターで加圧過したのち、真空ポンプ及び超音波を用い
て脱気処理し記録液を調製した。Example 1 The above components are mixed and dissolved sufficiently in a container, adjusted to pH 7 with sodium hydroxide, pressurized and filtered with a Teflon filter having a pore size of 1μ, and then deaerated using a vacuum pump and ultrasonic waves, and recorded. A liquid was prepared.
得られた記録液を用いて、インクジェットプリンター
（商品名HG-4800、エプソン株式会社製造）でインクジ
ェット記録を行ない、下記（ａ）〜（ｄ）の方法に従っ
て、インクジェット記録に関する評価を行った。Using the obtained recording liquid, ink jet recording was performed with an ink jet printer (trade name: HG-4800, manufactured by Epson Corporation), and the ink jet recording was evaluated according to the following methods (a) to (d).
（ａ）記録液の長期保存性：記録液をガラス容器に密閉
し、10℃と60℃で６ケ月間保存したのちでも不溶分の析
出は認められず、液の物性や色調にも変化がなかった。(A) Long-term storage of the recording solution: Even after the recording solution was sealed in a glass container and stored at 10 ° C and 60 ° C for 6 months, no precipitation of insolubles was observed, and there was no change in the physical properties or color tone of the solution. Did not.
（ｂ）吐出安定性：室温、５℃、40℃の雰囲気中でそれ
ぞれ24時間の連続吐出を行なったが、いずれの条件でも
終始安定した高品質の記録が行なえた。(B) Ejection stability: Continuous ejection was performed for 24 hours in an atmosphere of room temperature, 5 ° C., and 40 ° C., and stable high-quality recording was always performed under any conditions.
（ｃ）吐出応答性:2秒毎の間欠吐出と２カ月間放置後の
吐出について調べたが、いずれの場合もオリレフィス先
端での目詰まりがなく安定で均一に記録された。(C) Discharge responsiveness: Intermittent discharge every 2 seconds and discharge after leaving for 2 months were examined. In each case, recording was stable and uniform without clogging at the tip of the orifice.
（ｄ）記録画像の品質：記録された画像は濃度が高く鮮
明であった。室内光に３カ月さらしたのちの濃度の低下
率は１％以下であり、また、キセノンフェードメーター
（スガ試験機（株）製造）により100時間露光後の濃度
の低下率は７％と低かった。(D) Quality of recorded image: The recorded image was high in density and clear. The density reduction rate after exposure to room light for 3 months was 1% or less, and the density reduction rate after exposure for 100 hours with a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) was as low as 7%. .
又、オゾン12ppmを含有する空気中に90分間曝露した
際の変退色ΔＥ＊を前後の色差としてJIS Z8730により
求めたところ、３と小さいものであった。Further, when the discoloration and discoloration ΔE * when exposed to air containing 12 ppm of ozone for 90 minutes was determined by JIS Z8730 as the color difference between before and after, it was as small as 3.
比較例１ を含まない点を除いては同一組成の記録液を作製し、実
施例１と同様の評価を行った。その結果、オゾン曝露に
よる変退色ΔＥ＊が15と大きいものであった。Comparative Example 1 A recording liquid having the same composition was prepared except that the recording liquid was not included, and the same evaluation as in Example 1 was performed. As a result, the discoloration / fading ΔE * due to ozone exposure was as large as 15.
実施例２ 実施例１と同様にして上記組成の記録液を調製し、
（ａ）〜（ｄ）の検討を行った結果、いずれも良好な結
果を得た。Example 2 A recording liquid having the above composition was prepared in the same manner as in Example 1,
As a result of the examination of (a) to (d), good results were obtained in all cases.
実施例３〜６ 実施例１の方法に準じて、下記第１表に記載の組成か
ら成る記録液を調製し、（ａ）〜（ｄ）の方法に従っ
て、評価を行なった結果、いずれも良好であった。Examples 3 to 6 According to the method of Example 1, recording liquids having the compositions shown in Table 1 below were prepared and evaluated according to the methods (a) to (d). Met.
〔発明の効果〕 本発明の記録液は、インクジェット記録用、筆記用具
用等として用いられる。 [Effects of the Invention] The recording liquid of the present invention is used for ink-jet recording, writing implements and the like.
特に、インクジェット記録に用いた場合記録特性（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）、保護安定性、記録画像の耐光性、耐オゾン
性、耐候性、耐水性等いずれも良好であり、とりわけ、
耐光性及び耐オゾン性に優れた印字を得ることができ、
非常に有用である。In particular, when used in inkjet recording, recording characteristics (signal response, stability of droplet formation, ejection stability, continuous recording for a long time), protection stability, light resistance of recorded images, ozone resistance, weather resistance , Water resistance etc. are all good,
Printing with excellent light fastness and ozone resistance can be obtained,
Very useful.
Claims (1)
〔Ｉ〕 （式中、Ｒは−CH2COOH基、−CH2SO3H基又は下記一般式
〔II〕 C2H4OｎＨ ……〔II〕 （式中ｎは１〜10を表わす。） で示されるポリオキシエチレン基を表わす。） で示される化合物を含有することを特徴とする記録液。1. A water-soluble dye, an aqueous medium and the following general formula [I] (Wherein, R -CH 2 COOH group, -CH 2 SO 3 H group or the following formula (II) C 2 H 4 O n H ...... [II] (wherein n represents 1 to 10.) And a polyoxyethylene group represented by the formula :) A recording liquid comprising a compound represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13423789A JP2725377B2 (en) | 1989-05-27 | 1989-05-27 | Recording liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13423789A JP2725377B2 (en) | 1989-05-27 | 1989-05-27 | Recording liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02311571A JPH02311571A (en) | 1990-12-27 |
| JP2725377B2 true JP2725377B2 (en) | 1998-03-11 |
Family
ID=15123627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13423789A Expired - Fee Related JP2725377B2 (en) | 1989-05-27 | 1989-05-27 | Recording liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2725377B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05255627A (en) * | 1992-03-11 | 1993-10-05 | Kanebo Ltd | Ink for ink jet printing |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4413096A (en) | 1981-04-13 | 1983-11-01 | Ciba-Geigy Corporation | α-Olefin copolymers containing pendant hindered amine groups |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58125767A (en) * | 1982-01-21 | 1983-07-26 | Ricoh Co Ltd | Ink for jet recording |
-
1989
- 1989-05-27 JP JP13423789A patent/JP2725377B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4413096A (en) | 1981-04-13 | 1983-11-01 | Ciba-Geigy Corporation | α-Olefin copolymers containing pendant hindered amine groups |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02311571A (en) | 1990-12-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |