JP3949822B2 - Oil-based ink composition for ballpoint pens - Google Patents

Description

【００１６】
表中の原料の内容を注番号に沿って説明する。
（１）バリファストブラック３８０６〔オリエント化学工業（株）製、Ｃ．Ｉ．ソルベントブラック２９〕
（２）スピロンバイオレットＣＲＨ〔保土谷化学工業（株）製、Ｃ．Ｉ．ソルベントバイオレット８−１〕
（３）バリファストイエローＡＵＭ〔オリエント化学工業（株）製、Ｃ．Ｉ．ベーシックイエロー２の染料とＣ．Ｉ．アシッドイエロー４２の染料との造塩体染料〕
（４）スピロンレッドＣＧＨ〔保土谷化学工業（株）製、Ｃ．Ｉ．ベーシックレッド１の染料の有機酸塩〕
（５）スピロンイエローＣ２ＧＨ〔保土谷化学工業（株）製、Ｃ．Ｉ．ベーシックイエロー２の染料の有機酸塩〕
（６) ケトンホルムアルデヒド樹脂誘導体（ドイツ国ヒュルス社製、商品名：シンセテックレジンＳＫ）
（７）α−及びβ−ピネン・フェノール重縮合物〔ヤスハラケミカル（株）製、商品名：ＹＳポリスターＳ１４５、α−ピネンを主成分とするテルペン（β−ピネンが少量含まれる）とフェノールの共重合体、分子量１０５０、ガラス転移温度８７℃、比重１．０４、軟化点（環球法）１４５℃〕
（８）ポリビニルピロリドン〔ドイツ国ＢＡＳＦ社製、商品名：ルビスコールＫ−９０）
（９）ポリビニルブチラール〔積水化学工業（株）製、商品名：エスレックＢＭ−１〕
（10）キレート剤Ａ
【化４】

（11）キレート剤Ｂ
【化５】

【００１７】
各実施例及び比較例のボールペン用油性インキ組成物を直径０．４mmのボールを抱持するステンレススチール製チップ（ボールとチップの間隙が６〜１０μｍ）がポリプロピレン製パイプの一端に嵌着されたボールペンレフィルに充填した後、前記ボールペンレフィルを軸筒に組み込み、油性ボールペンを各５本ずつ得た。
尚、前記油性ボールペンは、各実施例と比較例のインキを用いて作成し、以下のテストを行った。
（１）筆記試験
紙面上にゴマ油を塗布した後、各油性ボールペンを用いて筆記し、その筆跡を調べた。
（２）経時試験
各油性ボールペンを５０℃で１カ月間放置した後、紙面上に筆記した。
【００１８】
テスト結果を表３に示す。
【表３】
【００１９】
表中の記号の内容を以下に説明する。
（１）筆記試験
○：良好な筆跡が得られた。
△：若干筆跡が途切れる
×：筆跡の途切れが激しい、或いは、筆記できない。
（２）経時試験
○：良好な筆跡が得られた。
×：良好な筆跡が得られるものの、筆跡の濃度が薄い。
尚、前記試験は油性ボールペン５本中３本以上が該当する評価を記した。
【００２０】
【発明の効果】
本発明は、前記キレート剤をインキ中に添加することによって、紙面上に途切れのない良好な筆跡を形成することができ、しかも、筆記不良を起こすことがないボールペン用油性インキ組成物を提供することができる。
【表２】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an oil-based ink composition for ballpoint pens.
[0002]
[Prior art]
Conventional ballpoint pens using oil-based inks have good handwriting robustness, but in order to prevent ink from dripping from the gap between the ball and the tip when the tip is in a downward state, that is, an inverted state, Is set to a high viscosity of several thousand to several tens of thousands mPa · s at room temperature. For this reason, oil-based ballpoint pens generally have a heavy writing feeling and less ink output, and therefore tend to have a lower handwriting density than water-based ballpoint pens.
The oil-based ballpoint pen rolls when the ball held by the tip of the ballpoint pen contacts the paper surface, and the film of the oil-based ink attached to the ball is transferred to the paper surface to form a handwriting. Therefore, when writing, it is necessary to form a film of oil-based ink continuously on the ball, and to transfer the ink film onto the paper surface continuously.
However, when a layer containing oil or fat is formed on the paper surface by touch or the like, the ball is difficult to roll on the paper surface, and the ball does not rotate in the chip while one point of the ball is in contact with the paper surface. Since the writing state occurs, there is a problem that ink is not transferred to the paper surface and the handwriting is interrupted.
[0003]
[Problems to be solved by the invention]
The present invention is intended to solve the above-described problems, that is, to provide an oil-based ink composition for ballpoint pens capable of forming a good handwriting without interruption.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to eliminate the disadvantages of the above-described ball-point pen oil-based ink, the present inventor obtained a good result by adding a specific chelating agent to the ball-point pen-based oil-based ink containing a colorant, an organic solvent, and a resin. Found that good handwriting and writing performance can be obtained.
That is, the present invention requires a colorant, an organic solvent, a resin, and an oil-based ink composition for ballpoint pens containing one or more chelating agents represented by the following general formulas (1) to (3).
[Chemical 1]
(Wherein X represents an alkali metal such as Na or K, an ammonium group, an alkyl or alkenyl amine having 3 to 18 carbon atoms, or an alkanolamine such as monoethanolamine or diethanolamine)
[Chemical 2]
(Wherein X represents an alkali metal such as Na or K, an ammonium group, an alkyl or alkenyl amine having 3 to 18 carbon atoms, or an alkanolamine such as monoethanolamine or diethanolamine)
[Chemical 3]
(Wherein X represents an alkali metal such as Na or K, an ammonium group, an alkyl or alkenyl amine having 3 to 18 carbon atoms, or an alkanolamine such as monoethanolamine or diethanolamine)
Furthermore, it is a requirement to contain 0.1 to 10% by weight of one or more of the chelating agents represented by the general formulas (1) to (3).
[0005]
It is unclear why by adding the chelating agent represented by the general formulas (1) to (3) to the ink, a good handwriting can be formed even if a layer containing oil and fat is present on the paper surface. However, since the balls used for ballpoint pens are generally made of metal, the ink containing the chelating agent easily forms an ink film on the surface of the balls. Phenomenon that the film formation ability is excellent and the film formation and transfer to the paper surface are repeated continuously, so that the ball stops rotating in the chip while one point of the ball is in contact with the paper surface, and the ink transfer is hindered. It is assumed that good handwriting can be obtained.
The chelating agents represented by the general formulas (1) to (3) are added in an amount of 0.1 to 10% by weight, preferably 0.5 to 7.0% by weight, based on the total amount of ink.
If the amount is less than 0.1% by weight, it is difficult to obtain good handwriting. If the amount exceeds 10% by weight, the dissolution of various additives is hindered. It becomes difficult to obtain handwriting.
[0006]
Examples of the dye used as the colorant include organic solvent-soluble dyes classified as solvent dyes in the color index.
As a specific example of the solvent dye,
Bali First Black 3806 (CI Solvent Black 29), 3807 (Trimethylbenzylammonium salt of CI Solvent Black 29 dye), Spirit Black SB (CI Solvent Black 5), Spiron Black GMH (CI Solvent Black 43), Bali First Red 1308 (Salt salt of CI Basic Red 1 dye and CI Acid Yellow 23 dye), Bali First Yellow AUM (CI Basic Black) Salt of yellow 2 dye and CI acid yellow 42 dye), spiron yellow C2GH (organic acid salt of CI basic yellow 2 dye), spirone violet CRH (CI solvent) Violet 8-1), Bali First Violet 1701 ( XI Basic Violet 1 and CI Acid Yellow 42 dye salt), Spiron Red CGH (organic acid salt of CI Basic Red 1 dye), Spiron Pink BH (CI Solvent Red 82) ), Nigrosine base EX (CI Solvent Black 7), oil blue 613 (CI Solvent Blue 5), neozapon blue 808 (CI Solvent Blue 70), and the like.
[0007]
Examples of pigments include inorganic pigments such as carbon black and titanium dioxide pigments, azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, selenium pigments, organic pigments such as quinacridone pigments, metallic pigments such as gold and silver, fluorescent pigments, pearls Examples thereof include pigments and phosphorescent pigments.
The colorant may be used alone or in combination of two or more, and is used in the range of 3 to 40% by weight in the ink composition.
[0008]
As the organic solvent, a high-boiling organic solvent having a boiling point of 150 ° C. or higher at normal pressure is suitably used. For example, benzyl alcohol, ethylene glycol monophenyl ether (phenyl glycol), benzyl glycol, dipropylene glycol monomethyl ether, etc. These organic solvents are mentioned.
The organic solvent may be used alone or in combination of two or more, and is used in the range of 40 to 80% by weight in the ink composition.
[0009]
Furthermore, the oil-based ink for ballpoint pens may be added with a resin for the purpose of suppressing bleeding of handwriting on paper, improving fixability, and imparting fastness.
Specifically, ketone resin, amide resin, N-vinylacetamide resin, alkyd resin, rosin modified resin, rosin modified phenol resin, phenol resin, xylene resin, polyvinyl butyral resin, polyvinyl pyrrolidone, α- and β-pinene / phenol Examples thereof include polycondensation resins.
These resins may be used alone or in combination of two or more, and are used in the range of 0.4 to 40% by weight, preferably 1 to 25% by weight in the ink composition.
[0010]
Further, as a lubricant, higher fatty acid, phosphate ester lubricant such as phosphate ester of polyoxyethylene alkyl ether and phosphate ester of polyoxyethylene alkyl aryl ether, nonionic surfactant having a long chain alkyl group, polyether modified silicone Oils and the like can also be added. In particular, thiophosphite triesters such as thiophosphite tri (alkoxycarbonylmethyl ester) and thiophosphite tri (alkoxycarbonylethyl ester), and oleic acid are most preferably used.
Of the thiophosphite triesters, specifically, thiophosphite tris (2-octyloxycarbonylethyl ester) is preferably used.
[0011]
If desired, wax such as carnauba wax, candelilla wax, rice wax, beeswax, beeswax, ozokerite, ceresin, montan wax, montanic acid wax, montan ester wax, etc., N-vinylacetamide or N-methyl-N-vinylacetamide Combined, N-vinylacetamide or N-methyl-N-vinylacetamide and (meth) acrylic acid, sodium (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylaminoethyl (Meth) acrylate, trimethylaminoethyl chloride (meth) acrylate, acrylamide, sulfopropylacrylamide, sulfobutylacrylamide, sodium sulfopropylacrylamide, sodium sulfobutylacrylamide, acrylonitrile, ethyl vinyl ether, methyl vinyl ketone, ethyl Vinyl ketone, vinyl acetate, sodium allyl sulfonate, N-vinyl-2-pyrrolidone, maleic acid, sodium maleate, itaconic acid, sodium itaconate copolymer, and the like can also be added.
[0012]
The oil-based ink composition for ballpoint pens of the present invention preferably has a relatively low viscosity of 1 to 10 Pa · s, good ink discharge, and a dark handwriting.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The oil-based ink for ballpoint pens is prepared by adding other components into an organic solvent and stirring and dissolving while heating as necessary.
[0014]
【Example】
The compositions of the inks of Examples 1 to 4 and Comparative Examples 1 to 4 are shown. In addition, the numerical value of a composition in a table | surface shows a weight part.
[0015]
[Table 1]

[0016]
The contents of the raw materials in the table are explained according to the note numbers.
(1) Balifast Black 3806 [Orient Chemical Co., Ltd., C.I. I. Solvent Black 29)
(2) Spiron Violet CRH [Hodogaya Chemical Co., Ltd., C.I. I. Solvent Violet 8-1]
(3) Varifast Yellow AUM [Orient Chemical Co., Ltd., C.I. I. Basic Yellow 2 dye and C.I. I. Salt-form dye with acid yellow 42 dye)
(4) Spiron Red CGH [manufactured by Hodogaya Chemical Co., Ltd., C.I. I. Organic acid salt of Basic Red 1 dye]
(5) Spiron yellow C2GH [Hodogaya Chemical Co., Ltd., C.I. I. Organic acid salt of basic yellow 2 dye]
(6) Ketone formaldehyde resin derivative (manufactured by Huls, Germany, trade name: Synthetech Resin SK)
(7) α- and β-pinene / phenol polycondensate (manufactured by Yasuhara Chemical Co., Ltd., trade name: YS Polyster S145, terpene containing α-pinene as a main component (containing a small amount of β-pinene) and phenol Polymer, molecular weight 1050, glass transition temperature 87 ° C., specific gravity 1.04, softening point (ring and ball method) 145 ° C.]
(8) Polyvinylpyrrolidone [made by BASF Germany, trade name: Rubiscol K-90]
(9) Polyvinyl butyral [Sekisui Chemical Co., Ltd., trade name: ESREC BM-1]
(10) Chelating agent A
[Formula 4]

(11) Chelating agent B
[Chemical formula 5]

[0017]
Stainless steel tips (ball-to-tip gaps of 6 to 10 μm) holding the ball of 0.4 mm in diameter were mounted on one end of a polypropylene pipe for the oil-based ink composition for ballpoint pens of each example and comparative example. After filling the ballpoint pen refill, the ballpoint pen refill was incorporated into a shaft tube to obtain five oil-based ballpoint pens each.
In addition, the said oil-based ball-point pen was created using the ink of each Example and a comparative example, and the following tests were done.
(1) After applying sesame oil on the writing test paper surface, writing was performed using each oil-based ballpoint pen, and the handwriting was examined.
(2) Aging test Each oil-based ballpoint pen was allowed to stand at 50 ° C. for 1 month and then written on the paper.
[0018]
Table 3 shows the test results.
[Table 3]
[0019]
The contents of the symbols in the table will be described below.
(1) Written test ○: Good handwriting was obtained.
Δ: The handwriting is slightly interrupted ×: The handwriting is severely interrupted or cannot be written.
(2) Aging test: Good handwriting was obtained.
X: Although good handwriting can be obtained, the handwriting density is low.
In addition, the said test described the evaluation which 3 or more out of 5 oil-based ball-point pens corresponded.
[0020]
【The invention's effect】
The present invention provides an oil-based ink composition for ballpoint pens that can form good handwriting without interruption on the paper surface by adding the chelating agent to the ink and that does not cause poor writing. be able to.
[Table 2]

Claims (2)

An oil-based ink composition for ballpoint pens containing one or more of colorants, organic solvents, resins, and chelating agents represented by the following general formulas (1) to (3).

(In the formula, X represents an alkali metal, an ammonium group, an alkyl or alkenylamine having 3 to 18 carbon atoms, or an alkanolamine)

(In the formula, X represents an alkali metal, an ammonium group, an alkyl or alkenylamine having 3 to 18 carbon atoms, or an alkanolamine)

(In the formula, X represents an alkali metal, an ammonium group, an alkyl or alkenylamine having 3 to 18 carbon atoms, or an alkanolamine) The oil-based ink composition for ball-point pens according to claim 1, comprising 0.1 to 10% by weight of one or more of the chelating agents represented by the general formulas (1) to (3).