JPS6224471B2 - - Google Patents
Info
- Publication number
- JPS6224471B2 JPS6224471B2 JP9851779A JP9851779A JPS6224471B2 JP S6224471 B2 JPS6224471 B2 JP S6224471B2 JP 9851779 A JP9851779 A JP 9851779A JP 9851779 A JP9851779 A JP 9851779A JP S6224471 B2 JPS6224471 B2 JP S6224471B2
- Authority
- JP
- Japan
- Prior art keywords
- ink
- water
- dyes
- viscosity
- black
- 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
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000975 dye Substances 0.000 claims description 19
- 239000000982 direct dye Substances 0.000 claims description 8
- UZZFFIUHUDOYPS-UHFFFAOYSA-L disodium 4-amino-3,6-bis[[4-[(2,4-diaminophenyl)diazenyl]phenyl]diazenyl]-5-oxido-7-sulfonaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Nc1ccc(N=Nc2ccc(cc2)N=Nc2c(N)c3c(O)c(N=Nc4ccc(cc4)N=Nc4ccc(N)cc4N)c(cc3cc2S([O-])(=O)=O)S([O-])(=O)=O)c(N)c1 UZZFFIUHUDOYPS-UHFFFAOYSA-L 0.000 claims description 8
- 238000004811 liquid chromatography Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004040 coloring Methods 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 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 3
- 239000000980 acid dye Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 3
- 229950006389 thiodiglycol Drugs 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- -1 D-sorbitan Chemical compound 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009967 direct dyeing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HCJLVWUMMKIQIM-UHFFFAOYSA-M sodium;2,3,4,5,6-pentachlorophenolate Chemical compound [Na+].[O-]C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl HCJLVWUMMKIQIM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
(産業上の利用分野)
本発明は、筆記具用、記録計用として、溶解性
が良好であり、経時的粘度変化の極めて少ない水
性黒色インキの製造方法に関するものである。
(従来の技術及びその問題点)
従来一般に、筆記具用、記録計用などの水性黒
色インキの着用原料としては、インキとした際の
経時安定性を保持する為に、酸性染料、塩基性染
料が使用されていたが、酸性染料を使用した場
合、被筆記面、例えば紙に対し、直接の染着性が
ない為、筆跡の耐水性が劣り、又、塩基性染料を
使用した場合は、前記酸性染料使用の場合と同様
に筆跡の耐水性が劣ることと、溶解のため強酸を
使用しなければならないことによりPHが著しく低
くなり、その為筆記具材質、具体的にはインキと
接触する部分の材質を限定しなければならないと
いう問題があつた。
よつて、筆跡の耐水性を向上せしめる為のみで
あれば、直接の染着性を有する直接染料が好まし
いこととなるが、直接染料は、ペーパークロマト
グラフイー、薄層クロマトグラフイーなどの分析
結果より理解されるように数種の色素成分から成
つており、この各色素成分の成分割合は合成時の
条件のわずかな差違により異なり、同一製品であ
つてもロツト間の差異を生じていた。この為、イ
ンキとした場合、経時的な変化、特に粘度の上昇
を生ずるものが発生し、筆記時にインキ切れ
(線、文字を書く時、インキの吐出がなく途中で
筆記できなくなることを言う)が生ずるという問
題があり、この問題は、水性インキ使用のボール
ペンなどのような筆記具においてより顕著なもの
であつた。
(問題点を解決するための手段)
そこで、本発明者等は、長期に亘り種々研究の
結果、基本的には、直接染料の中でも特に耐水
性、溶解性などの良好な染料を使用すると共に、
該染料中に含まれる色素成分の量的バランスを液
体クロマトグラフイーにより測定し、色素成分
中、特に量の多い二つの成分の構成比がある条件
を満足するような染料を使用すれば経時的に安定
であるとの知見に基づきなされたものである。即
ち、本発明はC・I・ダイレクトブラツク19タイ
プの直接染料について、液体クロマトグラフイー
によりそのピーク比を測定し、該ピーク比の測定
値が1.0以下である染料を着色原料として使用す
ることを特徴とする水性黒色インキの製造方法を
要旨とするものである。
以下本発明を詳細に説明する。
本発明に於ける「ピーク比の測定値が1.0以
下」とは次のことをいう。
C・I・ダイレクトブラツク19タイプの染料
は、推定の域を出ないが、
と、
とが色素成分の主な成分と考えられ(但し、H酸
は何れも1−アミノ−8−ナフトール−3・6−
ジスルホン酸−ナトリウムとする)、該染料の量
的バランスを液体クロマトグラフイー(例えば、
高速液体クロマトグラフイー)で測定してみる
と、添付図のa乃至cのような状態となる。即
ち、Aのピークにおいては、前記の成分のピー
クと推考され、又、Bのピークにおいては、前記
の成分のピークと推考されるが、前記の物質
に比し前記の物質はその分子量も大きく、溶解
性が悪い為、該物質の成分量が少ない染料が好ま
しいこととなる。よつて、「ピーク比の測定値が
1.0以下」とはB/Aが1.0以下のことを意味する
ものであり、図においては、aのような状態を示
すことをいうものである。
直接染料中、ダイレクトブラツク19タイプの染
料を使用する理由は、該タイプの染料は他のタイ
プの直接染料に比し、耐水性、溶解性、配色など
を考慮した場合優れている為である。又、該タイ
プの染料の具体例としては、日本化薬(株)製のカヤ
セツトブラツク007、オリエント化学工業(株)製の
ウオーターブラツク100−L、住友化学工業(株)製
のスミライトブラツクGコンク、ダイワ化成(株)製
のダイワブラツク#6000、中央合成(株)製のインク
ブラツクSP230などが挙げられる。
次に、上記C・I・ダイレクトブラツク19タイ
プのピーク比を測定する液体クロマトグラフイー
の条件であるが、高速液体クロマトグラフイーを
例にとつて述べれば、その測定条件は、
カラム:パーマフエイズAA×2.1m/mφ×
1m
移動相 1液 純水
2液 50%MeOH/50%
0.4MNaClO4/
0.005MNa2B4O7
濃度勾配溶出法(2液0→100%5
%/min)
検出波長 520nm及び630nm(ナ
ノメーター)
カラム:ヌクレオジル2.1m/mφ×25cm
移動層 1液 90%0.05MCH3COONa/10
%MeOH
2液 80%MeOH/19.9%純水/
0.1%トリエチルアミン
濃度勾配溶出法(2液0→100%3
%/min)
検出波長520nm及び630nm
カラム:ゾルバツクスODS4.6m/mφ×25
cm
以下前記と同じであればよく、更にカラムと
しては前記に限定されず逆相或いは陰イオン交換
樹脂ならばほとんど全てのカラムが使用できる。
又、高速液体クロマトグラフイー以外の液体クロ
マトグラフイーも使用できる。
前述した条件下、液体クロマトグラフイーに基
づきダイレクトブラツク19タイプの染料のピーク
比を測定し、その測定値が1.0以下の場合は、他
の素材と配合し、水性インキとされるが、他の素
材としては、水、水と相溶性を有するエチレング
リコール、ジエチレングリコール、チオジグリコ
ール、エチレングリコールモノメチルエーテル、
エチレングリコールモノブチルエーテルアセテー
ト、ジエチレングリコールモノメチルエーテル、
ホルムアミド、D−ソルビツト、ソルビタン、ア
セチン、グリセリンなどの水溶性有機溶剤があ
り、その他、染料の可溶化剤、ホルマリン、ペン
タクロロフエノールナトリウム、フエノールなど
の如き防腐剤、インキ組成に濡れの作用を付加す
る為に、各種の界面活性剤、金属の腐触防止の為
に、ベンゾトリアゾール、エチレンジアミン四酢
酸塩などの防錆剤も適宜添加使用できる。
インキはこれらの素材を使用対象物の機能及び
必要特性などにより適宜選択し、配合溶解する簡
単な操作で製造し得るが、適度の加熱と撹拌によ
つて、よりインキが作り易くなる。
(作用)
本発明に係る方法により得られる水性黒色イン
キが、良好な耐水性を示しつつ、かつ経時安定
性、特に経時的粘度変化に対する安定性が優れて
いるのは、前述したように、着色原料であるC・
I・ダイレクトブラツク19タイプの直接染料の主
な色素成分である前記ととの配合バランスが
良好である、即ち、溶解性の悪い前記の成分量
が少ないものを使用したためであると推察され
る。
(実施例)
以下、本発明の実施例を筆記具用インキについ
て説明するが、本発明のインキは、これらの実施
例に限定されるものではない。尚、実施例中部と
あるのは重量部を示す。
使用した染料の名称及び該染料を(株)島津製作所
製の島津高速液体クロマトグラフイー(島津−デ
ユポンLC−1)により測定したピーク比を以下
の表1に示す。尚、測定条件は、
カラム:ゾルバツクスODS4.6m/mφ×25cm
移動相;1液90%0.05MCH3COONa/10%MeOH
2液80%MeOH/19.9%純水/0.1%トリエチ
ルアミン
濃度勾配溶出法(2液0→100%3%/min)
検出波長:520nm
である。
(Field of Industrial Application) The present invention relates to a method for producing a water-based black ink for use in writing instruments and recorders, which has good solubility and exhibits extremely little change in viscosity over time. (Prior art and its problems) In general, acid dyes and basic dyes have been used as raw materials for water-based black ink for writing instruments, recorders, etc. in order to maintain stability over time when the ink is made. However, when acid dyes are used, the water resistance of handwriting is poor because they do not have direct dyeing properties on the writing surface, such as paper, and when basic dyes are used, As with the use of acid dyes, the water resistance of the handwriting is poor, and the need to use strong acids for dissolution results in a significantly lower PH. There was a problem in that the materials had to be limited. Therefore, if the purpose is only to improve the water resistance of handwriting, it is preferable to use direct dyes that have direct dyeability. As can be understood, it consists of several types of pigment components, and the proportions of each pigment component vary due to slight differences in the conditions during synthesis, resulting in differences between lots even if they are the same product. For this reason, when ink is used, changes occur over time, especially those that cause an increase in viscosity, and ink runs out when writing (when writing lines or letters, the ink does not eject and it becomes impossible to write halfway). This problem is more pronounced in writing instruments such as ballpoint pens that use water-based ink. (Means for Solving the Problems) Therefore, as a result of various long-term research, the present inventors basically decided to use dyes that have particularly good water resistance and solubility among direct dyes, and ,
The quantitative balance of the pigment components contained in the dye is measured by liquid chromatography, and if a dye is used that satisfies a certain condition for the composition ratio of two components with particularly large amounts among the pigment components, This was done based on the knowledge that it is stable. That is, the present invention measures the peak ratio of C.I.Direct Black 19 type direct dyes by liquid chromatography, and uses dyes with a measured peak ratio of 1.0 or less as coloring raw materials. The gist of this paper is a method for producing a characteristic water-based black ink. The present invention will be explained in detail below. In the present invention, "the measured value of the peak ratio is 1.0 or less" means the following. The C.I. Direct Black 19 type dye is only a guess, but and, is considered to be the main component of the pigment component (however, H acid is 1-amino-8-naphthol-3,6-
disulfonic acid-sodium), the quantitative balance of the dye was determined by liquid chromatography (e.g.
When measured using high performance liquid chromatography (high performance liquid chromatography), the results are as shown in a to c in the attached diagram. That is, the peak of A is assumed to be the peak of the above component, and the peak of B is assumed to be the peak of the above component, but the molecular weight of the above substance is also larger than that of the above substance. Since the solubility is poor, it is preferable to use a dye containing a small amount of the substance. Therefore, if the measured value of the peak ratio is
"1.0 or less" means that B/A is 1.0 or less, and in the figure, it means a state like a. Among the direct dyes, the reason for using Direct Black 19 type dye is that this type of dye is superior to other types of direct dyes in terms of water resistance, solubility, color arrangement, etc. Specific examples of this type of dye include Kayaset Black 007 manufactured by Nippon Kayaku Co., Ltd., Water Black 100-L manufactured by Orient Chemical Co., Ltd., and Sumilite Black manufactured by Sumitomo Chemical Co., Ltd. Examples include G-conc, Daiwa Black #6000 manufactured by Daiwa Kasei Co., Ltd., and Ink Black SP230 manufactured by Chuo Gosei Co., Ltd. Next, regarding the conditions for liquid chromatography to measure the peak ratio of the C.I.Direct Black 19 type mentioned above, taking high performance liquid chromatography as an example, the measurement conditions are: Column: Permaphase AA ×2.1m/mφ×
1m Mobile phase 1 liquid Pure water 2 liquid 50%MeOH/50%
0.4MNaClO4/
0.005MNa 2 B 4 O 7 concentration gradient elution method (2 liquids 0 → 100% 5
%/min) Detection wavelength 520nm and 630nm (nanometer) Column: Nucleosil 2.1m/mφ x 25cm Mobile phase 1 liquid 90% 0.05MCH 3 COONa/10
%MeOH 2 liquid 80%MeOH/19.9% pure water/
0.1% triethylamine concentration gradient elution method (2 liquids 0 → 100% 3
%/min) Detection wavelength 520nm and 630nm Column: Zolbax ODS4.6m/mφ×25
cm or less may be the same as above, and the column is not limited to those mentioned above, and almost any column can be used as long as it is a reversed phase or anion exchange resin.
Moreover, liquid chromatography other than high-performance liquid chromatography can also be used. Under the conditions described above, the peak ratio of Direct Black 19 type dye is measured based on liquid chromatography. If the measured value is 1.0 or less, it is mixed with other materials and is considered to be a water-based ink, but other materials Materials include water, ethylene glycol, diethylene glycol, thiodiglycol, ethylene glycol monomethyl ether, which are compatible with water.
Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether,
There are water-soluble organic solvents such as formamide, D-sorbitan, sorbitan, acetin, and glycerin, as well as dye solubilizers, preservatives such as formalin, sodium pentachlorophenol, and phenol, and additives that add wetting effects to the ink composition. In order to do this, various surfactants and rust preventive agents such as benzotriazole and ethylenediaminetetraacetate may be added as appropriate to prevent corrosion of metals. Ink can be manufactured by simply selecting these materials according to the function and required characteristics of the object to be used, blending and dissolving them, but the ink can be manufactured more easily by appropriate heating and stirring. (Function) The water-based black ink obtained by the method of the present invention exhibits good water resistance and has excellent stability over time, especially stability against changes in viscosity over time. The raw material C.
This is presumed to be due to the fact that the blending balance between the above and the main pigment components of the Direct Black 19 type direct dye was good, that is, a small amount of the components with poor solubility was used. (Examples) Hereinafter, examples of the present invention will be described with respect to ink for writing instruments, but the ink of the present invention is not limited to these examples. In addition, "Example Middle" indicates parts by weight. The names of the dyes used and the peak ratios of the dyes measured using Shimadzu High Performance Liquid Chromatography (Shimadzu-Dupont LC-1) manufactured by Shimadzu Corporation are shown in Table 1 below. The measurement conditions are as follows: Column: Zolbax ODS 4.6 m/mφ x 25 cm Mobile phase: 1 part 90% 0.05 MCH 3 COONa/10% MeOH 2 parts 80% MeOH/19.9% pure water/0.1% triethylamine concentration gradient elution method ( 2 liquids 0 → 100% 3%/min) Detection wavelength: 520nm.
【表】
実施例 1
カヤセツトブラツク(表1中のNo.1)
……9.0部
エチレングリコール ……20.0〃
チオジグリコール ……10.0〃
ホルマリン ……1.0〃
水 ……60.0〃
上記の各成分中、エチレングリコール、チオジ
グリコール、水を先づ混合し、次いで残りの成分
を混合溶液中に加え、約1時間、40〜50℃に加温
しながら撹拌してインキとした。該インキの粘度
を東京計器(株)製のB型粘度計で測定(25℃)し
(この際の粘度を以下初粘度という)、次に、イン
キを市販の水性インキ使用のボールペンと同様の
筆記具に充填し、50℃、湿度30%の条件下に10日
間放置して後、筆記テスト(以下筆記テストとい
う)を行なうと共に前記と同様粘度を測定し(こ
の際の粘度を以下10日後粘度という)た。
実施例 2〜7
染料のみ、前記表1中のNo.2〜7とし、その他
は実施例1と同様の操作をしインキを得た。該イ
ンキについても、実施例1と同様に初粘度、10日
後粘度、筆記テストを行なつた。
(効果)
実施例1〜7の初粘度、10日後粘度、筆記テス
ト結果を使用した染料のピークと並記すれば以下
の表2のとおりである。[Table] Example 1 Kayase set black (No. 1 in Table 1)
...9.0 parts Ethylene glycol ...20.0〃 Thiodiglycol ...10.0〃 Formalin ...1.0〃 Water ...60.0〃 Among the above ingredients, first mix ethylene glycol, thiodiglycol and water, then add the remaining The components were added to the mixed solution and stirred while heating to 40 to 50° C. for about 1 hour to prepare an ink. The viscosity of the ink was measured (25°C) using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. (the viscosity at this time is referred to as the initial viscosity hereinafter), and then the ink was heated in the same manner as a commercially available ballpoint pen using water-based ink. After filling a writing instrument and leaving it for 10 days at 50℃ and 30% humidity, a writing test (hereinafter referred to as writing test) was conducted and the viscosity was measured in the same manner as above (the viscosity at this time was referred to as the viscosity after 10 days). ). Examples 2 to 7 Inks were obtained by carrying out the same operations as in Example 1, except that dyes were used as Nos. 2 to 7 in Table 1 above. The ink was also tested for initial viscosity, viscosity after 10 days, and writing tests in the same manner as in Example 1. (Effects) The initial viscosity, viscosity after 10 days, and writing test results of Examples 1 to 7 are listed in Table 2 below, along with the peaks of the dyes used.
【表】
部分的に筆跡がカスレることを、良とは切
れ並びにカスレが生じないことを示す。
これら各実施例より、ピーク比が1.0以下の染
料を使用した実施例3、5、7のインキは、初粘
度と10日後粘度に差がほとんどなく、又、筆記テ
ストにおいても良好な結果を示すが、ピーク比が
1.0以上の染料を使用した実施例1、2、4、6
のインキは、初粘度と10日後粘度に大きな差があ
り(10日後粘度は初粘度に比し増粘する)、又、
筆記テストにおいても切れたり、カスレたりする
ことがわかる。
以上本発明のインキは、実施例としてボールペ
ンへの適用例について説明したが、毛筆様筆記具
並びにその他毛細管を利用した筆記具、或いは記
録計用にも適用できるものである。[Table] Good indicates that the handwriting is partially blurred, and good indicates that there are no cuts or scratches.
From these Examples, the inks of Examples 3, 5, and 7 using dyes with a peak ratio of 1.0 or less have almost no difference between the initial viscosity and the viscosity after 10 days, and also show good results in the written test. However, the peak ratio is
Examples 1, 2, 4, 6 using dyes of 1.0 or more
There is a large difference between the initial viscosity and the viscosity after 10 days (the viscosity after 10 days is thicker than the initial viscosity), and
Even in the written test, it can be seen that there are cuts and scratches. The ink of the present invention has been described above with reference to an example of application to a ballpoint pen, but it can also be applied to a brush-like writing instrument, other writing instruments using capillary tubes, or recorders.
第1図はC・I・ダイレクトブラツク19タイプ
の直接染料を高速液体クロマトグラフイにより測
定した際の状態を示す概略図である。
FIG. 1 is a schematic diagram showing the state when C.I. Direct Black 19 type direct dye was measured by high performance liquid chromatography.
Claims (1)
染料について、液体クロマトグラフイーによりそ
のピーク比を測定し、該ピーク比の測定値が1.0
以下である染料を着色原料として使用することを
特徴とする水性黒色インキの製造方法。1 The peak ratio of C.I.Direct Black 19 type direct dye was measured by liquid chromatography, and the measured value of the peak ratio was 1.0.
A method for producing a water-based black ink, characterized in that the following dyes are used as coloring raw materials.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9851779A JPS5622370A (en) | 1979-07-31 | 1979-07-31 | Preparing aqueous black ink |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9851779A JPS5622370A (en) | 1979-07-31 | 1979-07-31 | Preparing aqueous black ink |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5622370A JPS5622370A (en) | 1981-03-02 |
JPS6224471B2 true JPS6224471B2 (en) | 1987-05-28 |
Family
ID=14221835
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9851779A Granted JPS5622370A (en) | 1979-07-31 | 1979-07-31 | Preparing aqueous black ink |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5622370A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59199765A (en) * | 1983-04-27 | 1984-11-12 | Canon Inc | Dye purification equipment |
DE3417411A1 (en) * | 1983-06-30 | 1985-01-03 | Canon K.K., Tokio/Tokyo | INK MAKING SYSTEM |
JP2527337B2 (en) * | 1987-09-30 | 1996-08-21 | ぺんてる株式会社 | Water-based black ink |
-
1979
- 1979-07-31 JP JP9851779A patent/JPS5622370A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5622370A (en) | 1981-03-02 |
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