JPS624763A - Recording fluid - Google Patents

Recording fluid

Info

Publication number
JPS624763A
JPS624763A JP14599985A JP14599985A JPS624763A JP S624763 A JPS624763 A JP S624763A JP 14599985 A JP14599985 A JP 14599985A JP 14599985 A JP14599985 A JP 14599985A JP S624763 A JPS624763 A JP S624763A
Authority
JP
Japan
Prior art keywords
recording
liquid
dye
water
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.)
Granted
Application number
JP14599985A
Other languages
Japanese (ja)
Other versions
JPH0343312B2 (en
Inventor
Masatsune Kobayashi
小林 正恒
Takeshi Sakaeda
栄田 毅
Shoji Koike
祥司 小池
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Canon Inc filed Critical Canon Inc
Priority to JP14599985A priority Critical patent/JPS624763A/en
Publication of JPS624763A publication Critical patent/JPS624763A/en
Publication of JPH0343312B2 publication Critical patent/JPH0343312B2/ja
Granted legal-status Critical Current

Links

Landscapes

  • Ink Jet (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

PURPOSE:To provide a recording fluid which as excellent stability, long-term shelf stability and fixation to agents to be recorded, does not cause clogging and is suitable for use in ink jet recording, containing a recording agent contg. a dye and a solvent for use in dissolving or dispersing it as main components. CONSTITUTION:A recording agent (A) which is a component capable of forming an image contg. 0.05-1.0% (by weight based on the entire quantity of recording soln; the same applied hereinbelow) at last one dye of the formula (wherein 45mol% or less of M is H and 55 mol% or more of M is Li or K) is dissolved or dispersed in a solvent system (B) consisting of 10-80% polyhydric alcohol(a 2-6C alkylene glycol), optionally, 10-70% water-soluble or. solvent (e.g. methyl alcohol) and 30-90% water.

Description

【発明の詳細な説明】 産業上の利用分野〕 本発明は、インクによる記録に用いる新規な記録液、特
に記録手段に目詰まりを生じさせることがなく、なかで
も記録ヘッドに設けられた微細な吐出口(吐出オリアイ
ス)から記録液を吐出させ、液滴として飛翔させて記録
を行う記録方式に適した記録液に関する。
Detailed Description of the Invention [Field of Industrial Application] The present invention is directed to a novel recording liquid used for ink recording, which does not cause clogging in the recording means, and in particular, to a new recording liquid that does not cause clogging of the recording means, and in particular, a new recording liquid that is used for ink recording. The present invention relates to a recording liquid suitable for a recording method in which recording is performed by ejecting the recording liquid from an ejection port (ejection orifice) and flying it as droplets.

従来の技術〕 従来から、紙等の被記録材て記録を行う記録手段として
の筆記具(万年筆、フェルトベン等)には、インクとし
て、各種の染料を水又は有機溶剤に溶解、させたものが
使用されている。
[Prior Art] Traditionally, writing instruments (fountain pens, felt pens, etc.) used as recording means for recording on recording materials such as paper have used inks made by dissolving various dyes in water or organic solvents. It is used.

また、ピエゾ振動子による振動あるいけ高電圧印加によ
る静電引力等により、記録ヘッド内の液体を吐出オリフ
ィスから吐出させて記録を行なう所謂インクジェット記
録方式に於いても、各種の染料を水又は有機溶剤等に溶
解させた組成物が使用されることが知られている。しか
し、一般o万年筆、フェルトペンのような文具用インク
に比べると、インクジェット用記録液は、多くの特性で
一層厳密な条件が要求される。
In addition, in the so-called inkjet recording method, in which recording is performed by ejecting the liquid in the recording head from the ejection orifice using vibrations by a piezo vibrator or electrostatic attraction due to the application of high voltage, various dyes are mixed with water or organic It is known that a composition dissolved in a solvent or the like is used. However, compared to inks for stationery such as general fountain pens and felt-tip pens, inkjet recording liquids require more stringent conditions in many characteristics.

このようなインクジェット記録法は、所謂インクと称さ
れる記録液の液滴(ドロブレット)を飛翔させ、これを
被記録材に付着させて記録を行なうものである。かかる
記録液は、記録剤(染料又は顔料が用いられる)及びこ
れを溶解又は分散する液媒体(水又は各種有機溶剤ある
いけこれらの混合物が用いられる)を基本成分とし、ま
た必要に応じて各種添加剤が添加されている。
In such an inkjet recording method, recording is performed by causing droplets of a recording liquid called ink to fly and attaching them to a recording material. The basic components of such a recording liquid include a recording agent (dye or pigment is used) and a liquid medium for dissolving or dispersing it (water or various organic solvents or mixtures thereof are used), and various additives are added as necessary. Additives are added.

従来、この種の記録液として、例えば特公昭50−83
61号公報、特公昭51−40484号公報、特公昭5
2−13126号公報、特公昭52−13127号公報
、特開昭50−95008号公報に示されるように、各
種染料又は顔料を水系又は非水系溶媒に溶解又は分散さ
せたものが知られている。
Conventionally, as this type of recording liquid, for example, Japanese Patent Publication No. 50-83
Publication No. 61, Special Publication No. 51-40484, Special Publication No. 5
As shown in Japanese Patent Publication No. 2-13126, Japanese Patent Publication No. 52-13127, and Japanese Patent Application Laid-Open No. 50-95008, there are known dyes or pigments in which various dyes or pigments are dissolved or dispersed in aqueous or non-aqueous solvents. .

この種の記録液の好ましい条件としては、1)吐出条件
(圧電素子の駆動電圧、駆動周波数、オリアイスの形状
と材質、オリフィス径等)にマツチングした液物性(粘
度、表面張力、電導度等)を有していること。
Preferred conditions for this type of recording liquid include: 1) liquid physical properties (viscosity, surface tension, conductivity, etc.) that match the ejection conditions (piezoelectric element drive voltage, drive frequency, orifice shape and material, orifice diameter, etc.); have.

2)長期保存に対して、安定で目詰ま袷を起さないこと
2) Stable and free from clogging during long-term storage.

3)被記録材(紙、フィルム等)に対して、定着が速く
、ドツトの周辺が滑らかでにじみが小さいこと。
3) Fixation is fast on the recording material (paper, film, etc.), and the dot periphery is smooth and there is little bleeding.

4)印字された画像の色調が鮮明で、濃度が高いこと。4) The color tone of the printed image is clear and the density is high.

5)印字された画像の耐水性、耐光性が優れていること
5) The printed image has excellent water resistance and light resistance.

6)記録液が周辺材料(蓉器、連結チューブ、シール材
等)を侵さないこと。
6) The recording liquid should not corrode surrounding materials (coils, connecting tubes, sealing materials, etc.).

7)臭気、毒性、引火性等の安全性に優れたものである
こと。
7) It must be safe in terms of odor, toxicity, and flammability.

等が挙げられる。etc.

上記のような諸特性を同時に満足させることは相当に困
難であり、前記の先行技術はこの点で不満足なものであ
った。
It is quite difficult to simultaneously satisfy the above characteristics, and the prior art described above was unsatisfactory in this respect.

かかる目的の記録に適する記録液は、前記のように基本
的には染料とその溶媒とから組成されるものであるから
、上記記録液の特性は染料及び液媒体として用いられる
成分の有する固有の性質に左右されるところが大きい。
A recording liquid suitable for recording for such purposes is basically composed of a dye and its solvent as described above, so the characteristics of the recording liquid described above depend on the inherent properties of the dye and the components used as the liquid medium. Much depends on nature.

したがって、記録液が上記諸特性を具備するよう染料及
び液媒体を選択することはかかる技術分野に於いて極め
て重要な技術である。
Therefore, selecting a dye and a liquid medium so that the recording liquid has the above-mentioned properties is an extremely important technique in this technical field.

なかでも、黄色染料を用いた記録液に於ては、前述した
特性を全て十分に満足させるようなものはいまだ知れら
れていない。
Among these, there is no known recording liquid that fully satisfies all of the above-mentioned characteristics among recording liquids using yellow dye.

すなわち、主に、無機塩類の析出による記録液吐出口の
目詰まり防止効果、記録液の安定性、特に筆記具に於る
金属からなる構成部材の腐蝕防止効果を高めるために、
染料中に含まれる例えば、N a C/ 、 Na 2
804等の無機塩、Ca”+等のイオン等を、限外濾過
、イオン交換樹脂による処理または種々の有機溶、剤に
よる処理、あるいはこれらに塩析、酸析等の処理を併用
した方法によって、例えば染料中のNaC1!量が5重
量%以下、Na2SO4が1重量%以下となるように染
料から除去することが行なわれている。
That is, mainly to improve the effect of preventing clogging of the recording liquid discharge port due to the precipitation of inorganic salts, the stability of the recording liquid, and especially the effect of preventing corrosion of the metal components of the writing instrument.
For example, Na C/, Na 2 contained in the dye
Inorganic salts such as 804, ions such as Ca"+, etc. are removed by ultrafiltration, treatment with ion exchange resins, treatment with various organic solvents and agents, or a combination of these with treatments such as salting out and acid precipitation. For example, the amount of NaC1! in the dye is reduced to 5% by weight or less, and the amount of Na2SO4 in the dye is reduced to 1% by weight or less.

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

ところが、このような処理をC,1,ダイレクトイエロ
ー86及び、その誘導体に代表される黄色染料に行なう
と、染料自体の化学的、物理的特性が変化してしまい、
特に、上記の目的に反して、このような染料を用いた記
録液の安定性、長期保存性はかなり悪化することが認め
られた。
However, when such treatment is applied to yellow dyes such as C,1, Direct Yellow 86 and its derivatives, the chemical and physical properties of the dye itself change.
In particular, contrary to the above-mentioned purpose, it has been found that the stability and long-term storage stability of recording liquids using such dyes are considerably deteriorated.

これは、記録液の液媒体としては、従来水または水と水
溶性の各種有機溶剤との混合物が使用されてきたが、上
記記録液の特性を比較的全般にわたって満足する記録液
を形成できる液媒体として、水とエチレングリコール、
ジエチレングリコール等のグリコール類との混合物が好
適に使用されており、このような液媒体に対する上記処
理後の黄色染料の著しい溶解性の低下に起因していると
考えられる。
Conventionally, water or a mixture of water and various water-soluble organic solvents have been used as the liquid medium for the recording liquid, but a liquid that can form a recording liquid that satisfies relatively all of the above characteristics of the recording liquid has been developed. water and ethylene glycol as medium;
A mixture with glycols such as diethylene glycol is preferably used, and this is thought to be due to a significant decrease in the solubility of the yellow dye after the above treatment in such a liquid medium.

而して本発明は、鋭意検討の結果、かかる目的に用いる
記録液に好適であり、特に、主として水とグリコール類
との混合物からなる液媒体に対する溶解性が優れ、目詰
り等の原因となる無機塩類含有量の少ない染料を見出す
ことにより完成されたものである。
As a result of extensive studies, the present invention has been found to be suitable for recording liquids used for such purposes, and in particular has excellent solubility in liquid media mainly consisting of a mixture of water and glycols, which may cause clogging, etc. It was completed by finding a dye with a low content of inorganic salts.

一般式(A)で示される構造の染料は、色相、耐光性、
耐水性等の基本特性に優れているものとして注目されて
いたが、記録液溶媒に対する溶解性、記録液の保存性に
欠陥を有していたので、実用に供するのをひかえてとい
う現実があった。
The dye having the structure represented by the general formula (A) has hue, light resistance,
Although it was attracting attention as having excellent basic properties such as water resistance, it had defects in solubility in the recording liquid solvent and storage stability of the recording liquid, so the reality was that it was put on hold for practical use. Ta.

これらの問題を本発明による改善で解決することができ
たのである。
These problems could be solved by the improvements made by the present invention.

〔問題点を解決するための手段〕[Means for solving problems]

上記の目的は、以下の本発明によって達成される。 The above object is achieved by the present invention as follows.

すなわち、本発明の記録液は、偉を形成する成分である
記録剤と、この記録剤を溶解又は分散するための少なく
とも水及びグリコール類を含有しだ液媒体とを主体とし
て組成される記録液に於いて、記録剤として下記一般式
(A);(式中、Mけ、H,Li、Kから選ばれる少な
くとも一種からなる元素を示す)で表わされる染料の少
なくとも1種を含有し、かつ前記一般式゛(A)中に表
わされるMけ、その全量の55モル%以上がLi又はK
の何れかから選ばれる1種+あるととを特徴とする。
That is, the recording liquid of the present invention is a recording liquid mainly composed of a recording agent which is a component forming a grain, and a saliva medium containing at least water and glycols for dissolving or dispersing this recording agent. The recording agent contains at least one dye represented by the following general formula (A); (wherein represents at least one element selected from M, H, Li and K); 55 mol% or more of the total amount of M represented in the general formula (A) is Li or K.
It is characterized by one type selected from any of the following.

〔作 用〕[For production]

本発明の記録液を組成する液媒体は、核液媒体に対して
80重量に以下の水が含有されているものであることが
好ましい。
The liquid medium constituting the recording liquid of the present invention preferably contains water in an amount equal to or less than 80% by weight of the core liquid medium.

本発明の記録液には、記録剤成分としての上記一般式(
A)で表わされる染料の少なくとも一種と、液媒体とし
て、少なくとも水と、特に目詰まり防止上効果的なグリ
コール類とを含有した液媒体が用いられる。
The recording liquid of the present invention has the above general formula (
A liquid medium containing at least one of the dyes represented by A), at least water, and glycols, which are particularly effective in preventing clogging, is used.

本発明の記録液を組成する液媒体に含有させることので
きるグリコール類としては、ポリエチレンクリコール、
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
チレングリコミル、トリエチレングリコール、1,2.
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2〜6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エーテル、ジエ
チレングリコールメチル(またはエチル)エーテル、ト
リエチレングリコールモノメチル(またはエチル)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等を
挙げることができ、これらの一種以上を液媒体成分とし
て使用することができる。
Examples of glycols that can be contained in the liquid medium constituting the recording liquid of the present invention include polyethylene glycol,
Polyalkylene glycols such as polypropylene glycol; ethylene glycol, propylene glycol, butylene glycomyl, triethylene glycol, 1,2.
Alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms, such as 6-hexandriol, thiodiglycol, hexylene glycol, diethylene glycol:
Glycerin; Examples include lower alkyl ethers of polyhydric alcohols such as ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, and triethylene glycol monomethyl (or ethyl) ether, and one or more of these can be used as a liquid medium component. can be used.

記録液中の上記グリコール類の含有希け、一般には記録
液全重量に対して重量%で10〜70に、好ましくけ2
0〜60X1よ)好ましくは25〜40Xの範囲とされ
る。
The content of the above-mentioned glycols in the recording liquid is generally 10 to 70% by weight based on the total weight of the recording liquid, preferably 2.
0 to 60X1), preferably 25 to 40X.

本発明の記録液は、液媒体成分として上記グリコール類
の他に、記録液の特性をより良好とするために所望に応
じて水溶性有機溶剤である、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−メチルアルコール、5ea−7’チルア
ルコール、tert−7’チルアルコール、イソブチル
アルコール等の炭素al〜4の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/l/ コー/L/ 等
のケトンまたけケトンアルコール類;テトラヒドロフラ
ン、ジオキサン等のエーテル類、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の
含窒素複素環式ケトン類等の一種以上が添加されている
ものであっても良い。
In addition to the above-mentioned glycols as liquid medium components, the recording liquid of the present invention may optionally contain a water-soluble organic solvent such as methyl alcohol, ethyl alcohol, or n-propyl alcohol in order to improve the properties of the recording liquid. , isopropyl alcohol, n-methyl alcohol, 5ea-7′ methyl alcohol, tert-7′ methyl alcohol, isobutyl alcohol, and other carbon Al-4 alkyl alcohols;
Amides such as dimethylformamide and dimethylacetamide; ketone alcohols such as acetone and diacetone a/l/co/l/; ethers such as tetrahydrofuran and dioxane; N-methyl-2-pyrrolidone and 1,3-dimethyl One or more types of nitrogen-containing heterocyclic ketones such as -2-imidazolidinone may be added.

記録液中の上記グリコール類をも含めた水溶性有機溶剤
の含有量は、一般には記録液全重量に対して重fXで1
0〜70X、好゛ましくけ20〜60%、よυ好ましく
け30〜55%の範囲とされる。
Generally, the content of water-soluble organic solvents including the above-mentioned glycols in the recording liquid is 1 in fX based on the total weight of the recording liquid.
The range is 0 to 70X, preferably 20 to 60%, more preferably 30 to 55%.

この時の水の含有量は、上記溶剤成分の種類、その組成
ある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、記録液全重量に対して一般に30〜90
%、好ましくけ40〜80%、より好ましくけ45〜8
ONの範囲とされる。
The water content at this time is determined within a wide range depending on the type of solvent component, its composition, or the desired properties of the recording liquid, but is generally 30 to 90% of the total weight of the recording liquid.
%, preferably 40-80%, more preferably 45-8
It is assumed to be in the ON range.

本発明の記録液に使用される染料は、前記一般式(A)
で示される染料の少なくとも工種からなり、特に後に述
べる組成の水及びグリコール類が含有されだ液媒体に対
する良好な溶解性を示すものである。
The dye used in the recording liquid of the present invention has the general formula (A).
It is composed of at least the types of dyes shown in the following, and shows good solubility in a saliva medium containing water and glycols having the composition described later.

一般に、前記一般式(A)で示される染料は、該染料の
有するMに占めるLi又けKの割合によって、特に液媒
体の成分として含まれる水に対する溶解性が大きく変化
する。従って、上記のような組成の液媒体を用いる本発
明の記録液に使用される染料は、該染料の有するMの全
量のうちの55モル%以上がLi又FiKから選ばれる
1種であることが望ましい。
Generally, the solubility of the dye represented by the general formula (A) in water, which is contained as a component of the liquid medium, changes greatly depending on the ratio of Li or K to M in the dye. Therefore, in the dye used in the recording liquid of the present invention using a liquid medium having the above composition, 55 mol% or more of the total amount of M contained in the dye should be one selected from Li or FiK. is desirable.

このような本発明の記録液を形成することができる染料
は、C,1,ダイレクトイエロー86及びその誘導体を
出発物質として生成することができる。
The dye that can form the recording liquid of the present invention can be produced using C,1, Direct Yellow 86 and its derivatives as starting materials.

すなわち、C,1,ダイレクトイエロー86及びその誘
導体からなる黄色染料から、限外濾過、イオン交換樹脂
による処理又は種々の有機溶剤による処理、あるいはこ
れらに塩析、酸析等の処理を併用した方法によって、N
aC/ 、 Na2804 。
That is, a method using a yellow dye consisting of C,1, Direct Yellow 86 and its derivatives, ultrafiltration, treatment with an ion exchange resin, treatment with various organic solvents, or a combination of these with treatments such as salting out and acid precipitation. By N
aC/, Na2804.

LiOH、KOH及びカルシウムイオン等の無機成分を
除去し、次に種々の分析法により、染料分子中の目的と
する元素であるLi又iKの含有量を定量し、゛例えば
、染料水溶液中に、その目的に応じてLiOH又はKO
Hを添加するなどして造塩させ、不足分を補充する等の
方法により、各々目的とする成分(各々Liの場合、K
の場合がある)のM全量に対する割合を所定の値に制御
して生成することができる。
Inorganic components such as LiOH, KOH, and calcium ions are removed, and then the content of Li or iK, which is the target element in the dye molecule, is determined by various analytical methods. LiOH or KO depending on the purpose
By adding H, etc. to form salt and replenishing the shortage, each desired component (in the case of Li, K
) can be generated by controlling the ratio of M to the total amount to a predetermined value.

本発明に於て、目的とする元素(例えばLi。In the present invention, the target element (for example, Li.

K)のM全量に対する割合は、例えば原子吸光分析法等
を用いて測定されるものである。
The ratio of K) to the total amount of M is measured using, for example, atomic absorption spectrometry.

本発明の記録液に於て、前記一般式(A)で示された染
料の含有量は、液媒体の種類、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%で0.05〜1.ON、好ましくは0.05
〜6%、より好ましくけ0.05〜4%の範囲とされる
。該染料は、もちろん単独で若しくは二種以上を組み合
わせて、あるいけ他の直接染料、酸性染料を併用して使
用することができる。
In the recording liquid of the present invention, the content of the dye represented by the general formula (A) is determined depending on the type of liquid medium, the characteristics required of the recording liquid, etc. 0.05 to 1% by weight based on the total weight of the liquid. ON, preferably 0.05
The range is preferably 0.05 to 4%, more preferably 0.05 to 4%. Of course, these dyes can be used alone or in combination of two or more, or in combination with other direct dyes or acid dyes.

このような成分から調製される記録液は、それ自体で万
年筆、水性ボールペン、フェルトベン等の筆記具用記録
液として使用した場合、被記録材への定着性、あるいは
記録画僧の、耐光性、耐候性、耐水性等のいずれもバラ
ンスのとれた優れたものであるだけでなく、好適な液媒
体と染料との組み合わせからなり、特に染料の液媒体に
対する溶解性に優れ、従来の記録液に認められた安定性
、長期放置後のペン先等の記碌′液吐出口に於る染料の
析出がなく、目詰まりを生じない優れた記録液である。
When a recording liquid prepared from such components is used as a recording liquid for writing instruments such as fountain pens, water-based ballpoint pens, felt pens, etc., it has poor fixability to recording materials, light resistance, Not only does it have excellent weather resistance and water resistance, but it also has a suitable combination of liquid medium and dye. It is an excellent recording liquid with recognized stability, no precipitation of dye at the recording liquid discharge port of the pen tip, etc. after long-term storage, and no clogging.

また、インクジェット記録用として使用した場合でも、
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、長期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、ある込は記録
画偉の、耐光性、耐候性、耐水性等のいずれもバランス
のとれた優れたものであり、特に、これらの特性の中で
も、安定性、長期保存性に優れ、吐出オリフィスの目詰
りを起さない等の点で従来の記録液に対し明確な優位性
を示す。
Also, even when used for inkjet recording,
Recording characteristics (signal response, stability of droplet formation, ejection stability, long-term continuous recording performance, ejection stability after a long period of recording interruption), storage stability, fixation to recording material, etc. It has excellent, well-balanced properties such as light resistance, weather resistance, water resistance, etc. of recording materials.Among these properties, it has excellent stability and long-term storage, and has excellent It has clear advantages over conventional recording liquids in that it does not cause clogging.

なお、本発明の記録液に於ては、このような特性を更に
改善するために、従来から知られている各種添加剤を更
に含有させてもよい。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節剤:カチオン、ア
ニオン又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でき
る。
The recording liquid of the present invention may further contain various conventionally known additives in order to further improve such characteristics. 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 buffers; antifungal agents etc. can be mentioned.

なお、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.

本発明によれば、粘度、表面張力等の物性値が適正範囲
内にあり、万年筆に於るペン先やインクジェット記録装
置に於る微細なオリフィス等の記録液吐出口を目詰まり
させず、十分に高い濃度の記録画僧を与え、保存中に物
性値変化あるいは固形分の析出を生ずることなく、被記
録材の種類を制限せずに種々の部材に記録が行え、定着
速度が大きく、耐水性、耐光性、耐摩耗性及び解像度の
優れた画偉を与える記録液が得られる。
According to the present invention, physical property values such as viscosity and surface tension are within appropriate ranges, and the recording liquid ejection openings such as the nib of a fountain pen or the fine orifice of an inkjet recording device are not clogged and are sufficiently It provides high-density recording materials, does not change physical properties or precipitate solids during storage, can record on a variety of materials without limiting the type of recording material, has a high fixing speed, and is water resistant. A recording liquid is obtained which gives an image with excellent properties, light fastness, abrasion resistance and resolution.

本発明を、以下の実施例により更に詳細に説明する。The present invention will be explained in more detail by the following examples.

実施例1〜3 市販染料カヤクダイレクトイエロー&スペシャル(C,
1,ダイレクトイエロー86、日本化薬(株)製)を4
00?溶解させた水溶液を81作成し、攪拌しながら沈
澱物が充分生じるまで塩酸を添加(酸析処理)する。
Examples 1-3 Commercially available dye Kayaku Direct Yellow & Special (C,
1. Direct Yellow 86 (manufactured by Nippon Kayaku Co., Ltd.) 4
00? An aqueous solution is prepared, and hydrochloric acid is added thereto while stirring until a sufficient amount of precipitate is formed (acid precipitation treatment).

生じた沈澱物を戸別し、充分に水洗I−だ後乾燥物Aを
得た。得られた乾燥物を原子吸光光度計で測定し、Na
が含オれていないか、もしくけ無視できる程度であるこ
とを確認する。
The resulting precipitate was taken from house to house, thoroughly washed with water, and dried product A was obtained. The obtained dried product was measured with an atomic absorption spectrophotometer, and the Na
Confirm that there are no errors, or that they are negligible.

次に、上記の乾燥物Aをビーカー3個に102ずつ秤量
して入れる。これらビーカー中の試料をそれぞれ試料1
. Il、 IIIとする。各試料に水酸化リチウム水
溶液を攪拌しながら添加する。
Next, the above dried material A is weighed and put into 3 beakers in 102 portions. Each sample in these beakers is sample 1.
.. Il, III. Add lithium hydroxide aqueous solution to each sample while stirring.

この場合、各々の水酸化リチウム水溶液は水2001に
対して各々規定量の水酸化リチウムを溶解させたもので
あり、試料Iには0.31 F、試料■にけ0221、
試料■にけ0.2 Ofの水酸化リチウムを含有させた
In this case, each lithium hydroxide aqueous solution was prepared by dissolving a specified amount of lithium hydroxide in water 2001, and sample I had a concentration of 0.31 F, sample II had a concentration of 0.31 F,
Sample (2) contained 0.2 Of lithium hydroxide.

これらの試料1〜■の水溶液を各々充分攪拌した後、こ
れらを乾燥させて粉末化し、鷹1〜3の3種の染料を得
た。
The aqueous solutions of Samples 1 to 1 were sufficiently stirred, and then dried and powdered to obtain three types of dyes, Taka 1 to 3.

これら/161〜3の染料の含有するLi量を原子吸光
光度計で測定すると、染料構造中の全M量に占めるLi
の割合は、表1に示すとおりとなった。
When the amount of Li contained in these /161-3 dyes was measured using an atomic absorption spectrophotometer, it was found that the amount of Li in the total amount of M in the dye structure was
The ratio was as shown in Table 1.

表  1 次に、表1の各染料を、下記組成の液媒体に記録液中の
濃度が、3重葉%となるように加え、充分混合溶解させ
、これを孔径1μmのテフロン(商標名)製フィルター
で加圧濾過したのち、真空ポンプを用すて脱気処理し、
記録液とした。
Table 1 Next, each dye in Table 1 was added to a liquid medium having the composition shown below so that the concentration in the recording liquid would be 3%, thoroughly mixed and dissolved. After pressure filtration with a manufactured filter, deaeration treatment is performed using a vacuum pump,
It was used as a recording liquid.

く液媒体組成〉 イオン交換水(以後水と略す)  60重量部ジエチレ
ングリコール     40重量部得られた3種の記録
液のそれぞれを用いて、ピエゾ振動子によって記録液を
吐出させるオンデマンド型記録ヘッド(吐出オリアイス
径50μm1ピエゾ振動子駆動電圧60V、周波数4K
Hz)を有する記録装置によ妙、インクジェット記録を
実施し、特に従来の記録液について問題となっていた下
記の項目につき検討を行なった。得られた結果を表3に
示す。
Composition of liquid medium> Ion-exchanged water (hereinafter abbreviated as water) 60 parts by weight Diethylene glycol 40 parts by weight Using each of the three types of recording liquids obtained, an on-demand recording head (on-demand type recording head that ejects the recording liquid by a piezo vibrator) was prepared. Discharge oriice diameter 50 μm 1 Piezo vibrator drive voltage 60V, frequency 4K
Inkjet recording was carried out using a recording apparatus having a high frequency (Hz), and the following items, which had been problematic with conventional recording liquids, were particularly investigated. The results obtained are shown in Table 3.

(T1)記録液の長期保存性 記録液をガラス容器に密封し、−30℃と60℃で6力
月間保存したのち、不溶分の析出が認められたかどうか
を試駿し評価した。
(T1) Long-term storage stability of recording liquid The recording liquid was sealed in a glass container and stored at -30°C and 60°C for 6 months, and then tested and evaluated to see if precipitation of insoluble matter was observed.

不溶分の析出が認められなかった場合を(○)、不溶分
の析出が認められた場合を(×)とした。
The case where no precipitation of insoluble matter was observed was given as (○), and the case where precipitation of insoluble matter was observed was given as (x).

(T2)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。いずれの条件でも終始安定した高品
質の記録が行々えた場合を(○)、行えなかった場合を
(X)とした。また、その中間を(Δ)とした。
(T2) Discharge stability: Continuous discharge was performed for 24 hours in an atmosphere at room temperature, 5° C., and 40° C., respectively. Under any conditions, a case where stable high-quality recording was achieved from beginning to end was marked as (○), and a case where it was not possible was marked as (X). Moreover, the intermediate value was defined as (Δ).

(T3)吐出応答性; 記録装置を3力月間放置後作動させ、放置前後での2秒
ごとの間欠吐出に於る吐出状態について調べた。放置前
の安定で均一な吐出状態が放置後にも得られた場合を(
◎)、放置後の作動の初期に吐出に若干の乱れが認めら
れたが、数秒後には安定で均一吐出状態が得られた場合
を(○)、放置前の安定で均一な吐出状態が放置後に得
られなかった場合を(×)とした。
(T3) Ejection responsiveness: The recording device was operated after being left for 3 months, and the ejection state in intermittent ejection every 2 seconds before and after being left was examined. If the stable and uniform dispensing condition before being left is also obtained after being left unused (
◎), a slight disturbance in the discharge was observed in the initial stage of operation after being left unused, but a stable and uniform discharge condition was obtained after a few seconds (○), a case in which the stable and uniform discharge condition was maintained before being left unused. The case where it was not obtained later was marked as (x).

(T4)オリフィスの目詰まり; 記録装置を3力月間放置した後の、オリフィス先端を顕
微鏡を用いて観察し目詰まりが認められなかった場合を
(○)、わずかに認められた場合を(Δ)とし、完全に
ノズルをふさいでる場合を(X)とした。
(T4) Orifice clogging; After leaving the recording device unattended for 3 months, the orifice tip was observed using a microscope. No clogging was observed (○), and only slight clogging was observed (Δ). ), and the case where the nozzle was completely blocked was defined as (X).

(T5)記録画像の品質; 記録された画像は濃度が高く鮮明であり、室内光に3力
月さらしたのちの濃度の低下本は1%以下であり、また
、水中に1分間浸した場合の画像のにじみはきわめてわ
ずかであった場合を(○)、記録された画像は濃度が高
く鮮明でない場合、または画像が鮮明であるが室内光に
3力月間さらしたのちの濃度の低下高がIXを越え、ま
た、水中に1分間浸した場合の画像のにじみが顕著に認
められた場合を(×)とした。
(T5) Quality of recorded images: The recorded images have high density and are clear, and the density decrease is less than 1% after being exposed to indoor light for 3 months, and when immersed in water for 1 minute. (○) indicates that the image has very little blurring, while the recorded image has a high density and is not clear, or the image is clear but the density has decreased after being exposed to indoor light for 3 months. A rating of (x) was given when the image exceeded IX and significant blurring of the image was observed when immersed in water for 1 minute.

(T6)各種被記録材に対する定着性;下表に記載の被
記録材で印字15秒後印字部を指でこすり画偉ずれ、ニ
ジミの有無を判定した。画像ずれ、ニジミ等がなく優れ
た定着性を示した場合を(○)、画偉ずれ、ニジ比較例
1〜3 実施例1〜3において、乾燥物Aをさらに10?ずつ秤
量して、3個のビーカーに入れ、それぞれを試料ff、
V、Wとする。
(T6) Fixability on various recording materials: After 15 seconds of printing with the recording materials listed in the table below, the printed area was rubbed with a finger to determine the presence or absence of image displacement and bleeding. Excellent fixing performance without image shift, blurring, etc. is shown (○), image shift, blurring, etc. Comparative Examples 1 to 3 In Examples 1 to 3, dried material A was further added to 10? Weigh each sample, place it in three beakers, and add the sample ff,
Let them be V and W.

各試料に実施例1〜3と同様にして水酸化リチウムをそ
れぞれ0.18 t、 0.15 fSO,12tを含
有させ、3種の染料/164〜6を得た。これら/V、
4〜6の染料中のLLの割合を表2に示゛ す。
Each sample was made to contain 0.18 t and 12 t of lithium hydroxide in the same manner as in Examples 1 to 3, respectively, to obtain three types of dyes/164 to 6. These/V,
Table 2 shows the proportions of LL in dyes 4 to 6.

表  2 次に、表2に示す各染iを用いて実施例1〜3と同様に
して記録液を作成した。
Table 2 Next, recording liquids were prepared in the same manner as in Examples 1 to 3 using each dye i shown in Table 2.

得られた3種の記録液の各々を用いて実施例1〜3と同
様なテストを行った結果を表3に示す。
Table 3 shows the results of tests similar to those in Examples 1 to 3 using each of the three types of recording liquids obtained.

表  3 実施例4〜8 LiをKに代えたことを除き、実施例1〜3に述べたと
同様の方法で一般式(A)の染料構造中の全M量に対す
るに量の割合を変化させた染料層7〜9を調M(表4)
し、先の実施例で述べたと同様のテス) (Tl〜Ts
)を行った。その結果を表6に示す。
Table 3 Examples 4 to 8 The ratio of M to the total amount of M in the dye structure of general formula (A) was changed in the same manner as described in Examples 1 to 3, except that Li was replaced with K. Adjust dye layers 7 to 9 (Table 4)
and the same test as described in the previous example) (Tl~Ts
) was carried out. The results are shown in Table 6.

表  4 比較例4〜6 Li ′lr:Kに代えたことを除いて、比較例1〜3
と同様の方法で染料構造中の全Mtに対するに量の割合
を変化させた染料410〜12を作成(表5)し、先の
実施例と同様のテス)(Tl〜Ts)を行った。その結
果を表6に示す。
Table 4 Comparative Examples 4 to 6 Comparative Examples 1 to 3 except that Li'lr was replaced with K
Dyes 410 to 12 were prepared in the same manner as above (Table 5) in which the proportion of Mt to the total Mt in the dye structure was varied, and the same tests (Tl to Ts) as in the previous example were conducted. The results are shown in Table 6.

表  5 表  6 実施例7〜10 実施例1.2,4.5に於いて調整した記録液の各々を
個別にフェルトベンに充填し、これらの記録液を用いて
、中質紙〔白牡丹(商標名)、本州製紙(株)〕に筆記
し、記録された印字の耐水性を調べた。更に、キャップ
をけずして24時間放置した後のフェルトペンの年配性
を調べた。
Table 5 Table 6 Examples 7 to 10 Each of the recording liquids prepared in Examples 1.2 and 4.5 was individually filled into a felt tube, and these recording liquids were used to print medium-quality paper [White Botan]. (trade name), Honshu Paper Industries Co., Ltd.], and the water resistance of the recorded prints was examined. Furthermore, the aging of the felt-tip pens was examined after the caps were scratched off and the pens were left for 24 hours.

本実施例で使用された記録液は、いずれも記録された印
字が耐水性に優れ、24時間放置した後でも、ペン先に
染料等の析出が認められず、良好な記録性を示した。
All of the recording liquids used in this example had excellent water resistance, and even after being left for 24 hours, no precipitation of dye or the like was observed on the pen tip, indicating good recording performance.

Claims (2)

【特許請求の範囲】[Claims] (1)像を形成する成分である記録剤と、該記録剤を溶
解又は分散するための少なくとも水及び多価アルコール
類を含有した液媒体とを主体として組成される記録液に
於いて、記録剤として下記一般式(A) ▲数式、化学式、表等があります▼ (但し、式中、MはH、K、Liから選ばれる一種から
なる元素を示す) で表わされる染料の少なくとも1種を含有し、且つ、該
一般式(A)中のMは、その全量の55モル%以上がL
i又はKのいずれかから選ばれる1種であることを特徴
とする記録液。
(1) In a recording liquid mainly composed of a recording agent, which is a component for forming an image, and a liquid medium containing at least water and a polyhydric alcohol for dissolving or dispersing the recording agent, recording is possible. As an agent, at least one dye represented by the following general formula (A) ▲Mathematical formula, chemical formula, table, etc.▼ (However, in the formula, M represents an element selected from H, K, and Li) and 55 mol% or more of the total amount of M in the general formula (A) is L.
A recording liquid characterized by being one type selected from either i or K.
(2)該液媒体中に、該液媒体に対して80重量%以下
の水が含有されている特許請求の範囲第1項記載の記録
液。
(2) The recording liquid according to claim 1, wherein the liquid medium contains water in an amount of 80% by weight or less based on the liquid medium.
JP14599985A 1985-07-02 1985-07-02 Recording fluid Granted JPS624763A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP14599985A JPS624763A (en) 1985-07-02 1985-07-02 Recording fluid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP14599985A JPS624763A (en) 1985-07-02 1985-07-02 Recording fluid

Publications (2)

Publication Number Publication Date
JPS624763A true JPS624763A (en) 1987-01-10
JPH0343312B2 JPH0343312B2 (en) 1991-07-02

Family

ID=15397810

Family Applications (1)

Application Number Title Priority Date Filing Date
JP14599985A Granted JPS624763A (en) 1985-07-02 1985-07-02 Recording fluid

Country Status (1)

Country Link
JP (1) JPS624763A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5006128A (en) * 1988-08-26 1991-04-09 Sandoz Ltd. Substituted 2,4-di[4'-(disulfonaphth-2"-ylazo)phenylamino]-6-amino-1,3,5-triazines
US5374301A (en) * 1990-07-26 1994-12-20 Zeneca Limited Inks suitable for use in ink jet printing
EP0899288A3 (en) * 1997-08-29 2001-03-28 Taisei Chemical Industries Ltd Process for producing dispersion of functional compound
US7285160B2 (en) 2003-11-04 2007-10-23 Videojet Technologies Inc. Ink jet ink composition for wetness indication

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5578076A (en) * 1978-12-08 1980-06-12 Canon Inc Liquid medium for recording
JPS55120679A (en) * 1979-03-13 1980-09-17 Pentel Kk Oil ink
JPS55151070A (en) * 1979-05-14 1980-11-25 Canon Inc Recording liquid
JPS55151072A (en) * 1979-05-15 1980-11-25 Canon Inc Recording liquid
JPS562363A (en) * 1979-06-22 1981-01-12 Canon Inc Recording liquid
JPS5665059A (en) * 1979-10-31 1981-06-02 Pentel Kk Aqueous ink
JPS5751767A (en) * 1980-09-12 1982-03-26 Ricoh Co Ltd Water ink composition for ink jet recording
JPS58222167A (en) * 1982-06-21 1983-12-23 Ricoh Co Ltd Recording ink for ink jet

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5578076A (en) * 1978-12-08 1980-06-12 Canon Inc Liquid medium for recording
JPS55120679A (en) * 1979-03-13 1980-09-17 Pentel Kk Oil ink
JPS55151070A (en) * 1979-05-14 1980-11-25 Canon Inc Recording liquid
JPS55151072A (en) * 1979-05-15 1980-11-25 Canon Inc Recording liquid
JPS562363A (en) * 1979-06-22 1981-01-12 Canon Inc Recording liquid
JPS5665059A (en) * 1979-10-31 1981-06-02 Pentel Kk Aqueous ink
JPS5751767A (en) * 1980-09-12 1982-03-26 Ricoh Co Ltd Water ink composition for ink jet recording
JPS58222167A (en) * 1982-06-21 1983-12-23 Ricoh Co Ltd Recording ink for ink jet

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5006128A (en) * 1988-08-26 1991-04-09 Sandoz Ltd. Substituted 2,4-di[4'-(disulfonaphth-2"-ylazo)phenylamino]-6-amino-1,3,5-triazines
US5374301A (en) * 1990-07-26 1994-12-20 Zeneca Limited Inks suitable for use in ink jet printing
EP0899288A3 (en) * 1997-08-29 2001-03-28 Taisei Chemical Industries Ltd Process for producing dispersion of functional compound
US7285160B2 (en) 2003-11-04 2007-10-23 Videojet Technologies Inc. Ink jet ink composition for wetness indication

Also Published As

Publication number Publication date
JPH0343312B2 (en) 1991-07-02

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