JP4093953B2 - Water-based ink composition for ballpoint pen and water-based ballpoint pen using the same - Google Patents
Water-based ink composition for ballpoint pen and water-based ballpoint pen using the same Download PDFInfo
- Publication number
- JP4093953B2 JP4093953B2 JP2003411250A JP2003411250A JP4093953B2 JP 4093953 B2 JP4093953 B2 JP 4093953B2 JP 2003411250 A JP2003411250 A JP 2003411250A JP 2003411250 A JP2003411250 A JP 2003411250A JP 4093953 B2 JP4093953 B2 JP 4093953B2
- Authority
- JP
- Japan
- Prior art keywords
- ink
- water
- ballpoint pen
- ink composition
- ballpoint
- 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
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- 239000000049 pigment Substances 0.000 description 30
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Landscapes
- Pens And Brushes (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明はボールペン用水性インキ組成物及びそれを用いた水性ボールペンに関する。更に詳細には、ペン先を外気に長時間晒しても、ペン先の乾燥に起因するカスレや筆記不能の発生を抑えるような耐ドライアップ性(キャップオフ性能)及び垂れ下がり防止性能に優れたボールペン用水性インキ組成物及びそれを用いた水性ボールペンに関する。 The present invention relates to a water-based ink composition for ballpoint pens and a water-based ballpoint pen using the same. More specifically, a ballpoint pen with excellent dry-up resistance (cap-off performance) and dripping prevention performance that suppresses the occurrence of blurring and inability to write even when the pen tip is exposed to the outside air for a long time. The present invention relates to a water-based ink composition and a water-based ballpoint pen using the same.
従来より、ボールペン用水性インキをインキ収容管内に直接収容し、該インキの後端にインキ逆流防止体を備えたボールペンが多数市場に出回っている。そのうち、キャップを要しない構造のボールペン、所謂ノック式のボールペンにおいては、収容されるインキが比較的高い粘度であればインキの垂れ下がりをある程度防止できるものの、低粘度のインキを用いると垂れ下がりを生じ易くなる。
前記ボールペン用水性インキにおいては、更にキャップオフ性能が重要であり、ペン先乾燥防止剤として尿素及び/又はその誘導体の増量等が試みられてきた(例えば、特許文献1参照)。
しかしながら、尿素及び/又は尿素誘導体は吸水性能の高さがキャップオフ性能を発現させるため、これらのキャップオフ性能付与剤を過剰に添加したインキは高湿度条件下で放置した場合、ペン先部分において局部的に水分を吸収することになる。そのため、水性ボールペンにこのようなインキを適用した場合、水分吸収によりペン先部分のインキ粘度が低下し、インキがペン先部分に溜まる「垂れ下がり」、或いは溜まったインキが落下する「ボタ落ち」現象が発生してしまう。
In the water-based ink for ballpoint pens, cap-off performance is further important, and attempts have been made to increase the amount of urea and / or its derivative as a nib drying inhibitor (see, for example, Patent Document 1).
However, since urea and / or urea derivatives exhibit cap-off performance due to their high water-absorbing performance, inks with excessive addition of these cap-off performance-imparting agents will remain in the nib portion when left under high humidity conditions. Moisture is absorbed locally. Therefore, when such an ink is applied to a water-based ballpoint pen, the ink viscosity of the pen tip portion decreases due to moisture absorption, and the ink droops in the pen tip portion, or the “dropping” phenomenon in which the collected ink falls. Will occur.
本発明は前記問題を解決するものであって、即ち、垂れ下がりとキャップオフ性の相反する機能を満足させ、筆記性能に優れたボールペン用水性インキ組成物及びそれを用いた水性ボールペンを提供しようとするものである。 The present invention solves the above-mentioned problem, that is, an aqueous ink composition for ballpoint pens which satisfies the functions of drooping and cap-off properties and is excellent in writing performance, and an aqueous ballpoint pen using the same. To do.
本発明は、少なくとも水と、着色剤と、水溶性有機溶剤とからなるボールペン用水性インキ組成物において、エチレンとアクリル酸又はエチレンとメタクリル酸のコポリマーのワックスエマルジョンを含有してなるボールペン用水性インキ組成物を要件とする。
更には、前記ワックスエマルジョンの平均粒子径が0.1μm以下であること、前記ワックスエマルジョンをインキ組成物中0.1〜5.0重量%の範囲で含有してなること、前記着色剤が染料であること等を要件とする。
更には、前記ボールペン用水性インキ組成物を、ボールペンチップを直接又は中継部材を介して取り付けたインキ収容管内に直接充填し、且つ、インキ組成物後端面にインキ逆流防止体を配設した水性ボールペンを要件とする。
The present invention relates to an aqueous ink composition for ballpoint pens comprising at least water, a colorant and a water-soluble organic solvent, and an aqueous ink for ballpoint pens comprising a wax emulsion of a copolymer of ethylene and acrylic acid or ethylene and methacrylic acid. Require composition.
Furthermore, the average particle size of the wax emulsion is 0.1 μm or less, the wax emulsion is contained in the ink composition in the range of 0.1 to 5.0% by weight, and the colorant is a dye. It is a requirement.
Furthermore, the water-based ballpoint pen in which the water-based ink composition for a ballpoint pen is directly filled into an ink containing tube attached with a ballpoint pen tip directly or via a relay member, and an ink backflow prevention body is disposed on the rear end surface of the ink composition. Is a requirement.
本発明は、垂れ下がり防止効果とキャップオフ効果を共に備えた、筆記性能に優れたボールペン用水性インキ組成物及びそれを用いた水性ボールペンを提供できる。 INDUSTRIAL APPLICABILITY The present invention can provide a water-based ink composition for ballpoint pens that has both a sagging prevention effect and a cap-off effect and excellent writing performance, and a water-based ballpoint pen using the same.
本発明に用いられるワックスはエチレンとアクリル酸又はエチレンとメタクリル酸のコポリマーのワックスであるため、カルボン酸基を有してなり、特に乳化剤等の分散剤を添加することなく、水中で安定的に分散させることができる。
なお、キャップオフ性能については、ペン先で前記ワックスが析出して被膜を形成してインキの蒸発を抑制し、筆記時の衝撃により被膜が破壊されてインキ出が回復するものと推察される。
Since the wax used in the present invention is a copolymer wax of ethylene and acrylic acid or ethylene and methacrylic acid, it has a carboxylic acid group, and is stable in water without adding a dispersant such as an emulsifier. Can be dispersed.
Regarding the cap-off performance, it is presumed that the wax precipitates at the pen tip to form a film to suppress ink evaporation, and the film is destroyed by impact during writing to recover the ink discharge.
前記ワックスとしては、BASF社製、商品名:poligen WE3、同WE4、三井化学(株)製、商品名:ケミパールS−100が使用できる。 As said wax, BASF Corporation make, brand name: POLIGEN WE3, the same WE4, the Mitsui Chemicals Co., Ltd. make, brand name: Chemipearl S-100 can be used.
前記ワックスエマルジョンの平均粒子径は0.1μm以下であることが好ましく、インキ中で安定的に存在すると共に、良好な垂れ下がり防止性能を付与できる。
平均粒子径が0.1μmを越えると、インキ中で分離する虞があり、所期の性能を満足させ難くなる。
なお、前記ワックスエマルジョンの平均粒子径は、好ましくは0.01〜0.1μm、より好ましくは0.02〜0.05μmである。
前記ワックスはインキ組成物全量に対して0.1〜5.0重量%、好ましくは0.5〜3.0重量%の範囲で配合される。0.1重量%未満では垂れ下がり防止効果が得られ難く、5.0重量%を越えるとインキの粘度が上昇して泣き出しやボテの原因になったり、追従性を妨げることがある。更には耐ドライアップ性を悪化させてしまうこともある。
The wax emulsion preferably has an average particle size of 0.1 μm or less, can stably exist in the ink, and can impart good sag prevention performance.
If the average particle diameter exceeds 0.1 μm, there is a risk of separation in the ink, making it difficult to satisfy the desired performance.
The average particle size of the wax emulsion is preferably 0.01 to 0.1 μm, more preferably 0.02 to 0.05 μm.
The wax is blended in the range of 0.1 to 5.0% by weight, preferably 0.5 to 3.0% by weight, based on the total amount of the ink composition. If the amount is less than 0.1% by weight, it is difficult to obtain a drooping prevention effect. If the amount exceeds 5.0% by weight, the viscosity of the ink increases, which may cause crying or blurring, and hinder followability. Furthermore, the dry-up resistance may be deteriorated.
前記着色剤は、水性媒体に溶解もしくは分散可能な染料及び顔料が全て使用可能であり、その具体例を以下に例示する。
酸性染料としては、
ニューコクシン(C.I.16255)、
タートラジン(C.I.19140)、
アシッドブルーブラック10B(C.I.20470)、
ギニアグリーン(C.I.42085)、
ブリリアントブルーFCF(C.I.42090)、
アシッドバイオレット6BN(C.I.43525)、
ソルブルブルー(C.I.42755)、
ナフタレングリーン(C.I.44025)、
エオシン(C.I.45380)、
フロキシン(C.I.45410)、
エリスロシン(C.I.45430)、
ニグロシン(C.I.50420)、
アシッドフラビン(C.I.56205)等が用いられる。
As the colorant, all dyes and pigments that can be dissolved or dispersed in an aqueous medium can be used, and specific examples thereof are exemplified below.
As an acid dye,
New coccin (CI. 16255),
Tartrazine (C.I. 19140),
Acid Blue Black 10B (C.I. 20470),
Guinea Green (C.I.42085),
Brilliant blue FCF (C.I.42090),
Acid Violet 6BN (C.I. 43525),
Soluble Blue (C.I. 42755),
Naphthalene green (C.I. 44025),
Eosin (C.I. 45380),
Phloxin (C.I. 45410),
Erythrosine (C.I. 45430),
Nigrosine (C.I. 50420),
Acid flavin (C.I. 56205) or the like is used.
塩基性染料としては、
クリソイジン(C.I.11270)、
メチルバイオレットFN(C.I.42535)、
クリスタルバイオレット(C.I.42555)、
マラカイトグリーン(C.I.42000)、
ビクトリアブルーFB(C.I.44045)、
ローダミンB(C.I.45170)、
アクリジンオレンジNS(C.I.46005)、
メチレンブルーB(C.I.52015)等が用いられる。
As basic dye,
Chrysoidine (C.I. 11270),
Methyl violet FN (C.I. 42535),
Crystal violet (C.I. 42555),
Malachite green (C.I. 42000),
Victoria Blue FB (C.I. 44045),
Rhodamine B (C.I. 45170),
Acridine orange NS (C.I. 46005),
Methylene blue B (C.I. 52015) or the like is used.
直接染料としては、
コンゴーレッド(C.I.22120)、
ダイレクトスカイブルー5B(C.I.24400)、
バイオレットBB(C.I.27905)、
ダイレクトディープブラックEX(C.I.30235)、
カヤラスブラックGコンク(C.I.35225)、
ダイレクトファストブラックG(C.I.35255)、
フタロシアニンブルー(C.I.74180)等が用いられる。
前記着色剤として染料を用いた場合、キャップを要しないノック式のボールペンに適用する系ではドライアップが顕著であり、耐ドライアップ性能は重要な要件となる。
As a direct dye,
Congo Red (C.I. 22120),
Direct Sky Blue 5B (C.I. 24400),
Violet BB (C.I. 27905),
Direct deep black EX (CI 30235),
Caillas Black G Conch (C.I. 35225),
Direct Fast Black G (C.I. 35255),
Phthalocyanine blue (C.I. 74180) or the like is used.
When a dye is used as the colorant, dry-up is significant in a system applied to a knock-type ballpoint pen that does not require a cap, and the dry-up resistance is an important requirement.
前記顔料としては、カーボンブラック、群青などの無機顔料や銅フタロシアニンブルー、ベンジジンイエロー等の有機顔料の他、予め界面活性剤や樹脂を用いて微細に安定的に水媒体中に分散された水分散顔料製品等が用いられ、例えば、C.I.Pigment Blue 15:3B〔品名:Sandye Super Blue GLL、顔料分24%、山陽色素株式会社製〕、
C.I. Pigment Red 146〔品名:Sandye Super Pink FBL、顔料分21.5%、山陽色素株式会社製〕、
C.I.Pigment Yellow 81〔品名:TC Yellow FG、顔料分約30%、大日精化工業株式会社製〕、
C.I.Pigment Red 220/166〔品名:TC Red FG、顔料分約35%、大日精化工業株式会社製〕等を挙げることができる。
また、水溶性樹脂を用いた水分散顔料としては、
C.I.Pigment Black 7〔商品名:WA color Black A25 、顔料分15%、大日精化工業(株)製〕、
C.I.Pigment Green 7〔商品名:WA−S color Green、顔料分8%、大日精化工業(株)製〕、
C.I.Pigment Violet 23〔商品名:マイクロピグモ WMVT−5、顔料分20%、オリエント化学工業(株)製〕、
C.I.Pigment Yellow 83〔商品名:エマコールNSイエロー4618、顔料分30%、山陽色素(株)製〕が挙げられる。
Examples of the pigment include inorganic pigments such as carbon black and ultramarine, and organic pigments such as copper phthalocyanine blue and benzidine yellow, as well as water dispersion finely and stably dispersed in an aqueous medium in advance using a surfactant or resin. Pigment products and the like are used. I. Pigment Blue 15: 3B [Product name: Sandy Super Blue GLL, pigment content 24%, manufactured by Sanyo Dye Co., Ltd.]
C. I. Pigment Red 146 [Product name: Sandye Super Pink FBL, pigment content 21.5%, manufactured by Sanyo Dye Co., Ltd.]
C. I. Pigment Yellow 81 [Product name: TC Yellow FG, pigment content about 30%, manufactured by Dainichi Seika Kogyo Co., Ltd.]
C. I. Pigment Red 220/166 [Product name: TC Red FG, pigment content of about 35%, manufactured by Dainichi Seika Kogyo Co., Ltd.].
In addition, as a water-dispersed pigment using a water-soluble resin,
C. I. Pigment Black 7 (trade name: WA color Black A25, pigment content 15%, manufactured by Dainichi Seika Kogyo Co., Ltd.),
C. I. Pigment Green 7 [trade name: WA-S color Green, pigment content 8%, manufactured by Dainichi Seika Kogyo Co., Ltd.]
C. I. Pigment Violet 23 [trade name: Micropigmo WMVT-5, pigment content 20%, manufactured by Orient Chemical Co., Ltd.]
C. I. Pigment Yellow 83 [trade name: Emacol NS Yellow 4618, pigment content 30%, manufactured by Sanyo Color Co., Ltd.].
蛍光顔料としては、各種蛍光染料を樹脂マトリックス中に固溶体化した合成樹脂微細粒子状の蛍光顔料が使用できる。その他、金属光沢顔料、蓄光性顔料、二酸化チタン、シリカ、炭酸カルシウム等の白色顔料、可逆熱変色性組成物を内包したカプセル顔料、香料や香料を内包したカプセル顔料等を例示できる。
前記金属光沢顔料としては、アルミニウムや真鍮等の金属粉、芯物質として天然雲母、合成雲母、ガラス片、アルミナ、透明性フィルム片の表面を酸化チタン等の金属酸化物で被覆したパール顔料、金属蒸着膜の片面又は両面に透明又は着色透明フィルムを設けた金属光沢フィルム片を細かく裁断したもの、透明性樹脂層を複数積層した虹彩性フィルムを細かく裁断したものを例示できる。
なお、前記アルミニウムや真鍮等の金属粉を用いる場合、前記金属粉の表面を透明性樹脂や着色透明性樹脂で被覆したものが好適に用いられ、インキ組成物中での安定性に優れる。
As fluorescent pigments, synthetic resin fine particle fluorescent pigments in which various fluorescent dyes are formed into a solid solution in a resin matrix can be used. Other examples include metallic luster pigments, phosphorescent pigments, white pigments such as titanium dioxide, silica, and calcium carbonate, capsule pigments encapsulating a reversible thermochromic composition, capsule pigments encapsulating perfume and perfume.
Examples of the metallic luster pigment include metal powders such as aluminum and brass, natural mica, synthetic mica, glass pieces, alumina, and pearl pigments in which the surface of a transparent film piece is coated with a metal oxide such as titanium oxide, metal Examples thereof include those obtained by finely cutting a metallic glossy film piece provided with a transparent or colored transparent film on one side or both sides of the deposited film, and those obtained by finely cutting an iris film in which a plurality of transparent resin layers are laminated.
In addition, when using metal powders, such as said aluminum and brass, what coat | covered the surface of the said metal powder with transparent resin or colored transparent resin is used suitably, and it is excellent in stability in an ink composition.
また、着色剤として顔料を用いた場合、必要に応じて顔料分散剤を添加できる。
前記顔料分散剤としてはアニオン、ノニオン等の界面活性剤、ポリアクリル酸、スチレンアクリル酸等のアニオン性高分子、PVP、PVA等の非イオン性高分子等が用いられる。
Further, when a pigment is used as the colorant, a pigment dispersant can be added as necessary.
Examples of the pigment dispersant include surfactants such as anions and nonions, anionic polymers such as polyacrylic acid and styreneacrylic acid, and nonionic polymers such as PVP and PVA.
前記水溶性有機溶剤としては、例えば、エタノール、プロパノール、ブタノール、グリセリン、ソルビトール、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、エチレングリコール、ジエチレングリコール、チオジエチレングリコール、ヘキシレングリコール、1,3−ブタンジオール、ネオプレングリコール、ポリ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、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エチルエーテル、エチレングリコールモノブチルエーテル、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エチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、スルフォラン、2−ピロリドン、N−メチル−2−ピロリドン等が挙げられる。
前記水溶性有機溶剤は1種又は2種以上を併用することもできる。
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, hexylene glycol, 1,3-butanediol, and neoprene. Glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoether Ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N- methyl-2-pyrrolidone.
The water-soluble organic solvent can be used alone or in combination of two or more.
上記成分以外に、耐乾燥性を妨げない範疇でアルキッド樹脂、アクリル樹脂、スチレンマレイン酸共重合物、セルローズ誘導体、ポリビニルピロリドン、ポリビニルアルコール、デキストリン等の水溶性樹脂を1種又は2種以上添加したり、尿素、ノニオン系界面活性剤、ソルビット、マンニット、ショ糖、ぶどう糖、還元デンプン加水分解物、ピロリン酸ナトリウム等の湿潤剤を1種又は2種以上添加することもできる。
その他、必要に応じてpH調整剤、防錆剤、防腐剤或いは防黴剤、潤滑剤を添加することができる。
前記pH調整剤としては、炭酸ナトリウム、リン酸ナトリウム、水酸化ナトリウム、酢酸ソーダ等の無機塩類、トリエタノールアミンやジエタノールアミン等の水溶性のアミン化合物等の有機塩基性化合物等が挙げられる。
前記防錆剤としては、ベンゾトリアゾール及びその誘導体、トリルトリアゾール、ジシクロヘキシルアンモニウムナイトライト、ジイソプロピルアンモニウムナイトライト、チオ硫酸ナトリウム、エチレンジアミン四酢酸塩、サポニン、ジアルキルチオ尿素等が挙げられる。
前記防腐剤或いは防黴剤としては、石炭酸、1、2−ベンズイソチアゾリン−3−オンのナトリウム塩、安息香酸ナトリウム、デヒドロ酢酸ナトリウム、ソルビン酸カリウム、パラオキシ安息香酸プロピル、2,3,5,6−テトラクロロ−4−(メチルスルフォニル)ピリジン等が挙げられる。
前記潤滑剤としては、金属石鹸、ポリアルキレングリコール脂肪酸エステル、エチレンオキサイド付加型カチオン活性剤、リン酸エステル系活性剤、チオカルバミン酸塩、ジメチルジチオカルバミン酸塩等が挙げられる。
その他、溶剤の浸透性を向上させるフッ素系界面活性剤やノニオン、アニオン、カチオン系界面活性剤、ジメチルポリシロキサン等の消泡剤を添加することもできる。
In addition to the above components, one or more water-soluble resins such as alkyd resins, acrylic resins, styrene maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin are added in a category that does not impair drying resistance. Alternatively, one or more wetting agents such as urea, nonionic surfactant, sorbit, mannitol, sucrose, glucose, reduced starch hydrolyzate, sodium pyrophosphate and the like can be added.
In addition, a pH adjuster, a rust preventive, a preservative or a fungicide, and a lubricant can be added as necessary.
Examples of the pH adjusting agent include inorganic salts such as sodium carbonate, sodium phosphate, sodium hydroxide and sodium acetate, and organic basic compounds such as water-soluble amine compounds such as triethanolamine and diethanolamine.
Examples of the rust inhibitor include benzotriazole and derivatives thereof, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, sodium thiosulfate, ethylenediaminetetraacetate, saponin, and dialkylthiourea.
Examples of the preservative or antifungal agent include carboxylic acid, sodium salt of 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2, 3, 5, 6 -Tetrachloro-4- (methylsulfonyl) pyridine and the like.
Examples of the lubricant include metal soap, polyalkylene glycol fatty acid ester, ethylene oxide addition type cationic activator, phosphate ester activator, thiocarbamate, dimethyldithiocarbamate and the like.
In addition, an antifoaming agent such as a fluorine-based surfactant that improves the permeability of the solvent, a nonion, an anion, a cationic surfactant, or dimethylpolysiloxane may be added.
前記インキ組成物をインキ収容管内に直接充填し、且つ、インキ組成物後端面にインキ逆流防止体を配設するタイプのボールペンに用いる場合、インキ中に気体が混入していると、経時により気体が集まって気泡が発生し、筆記時のインキ出に悪影響を与えると共に、筆記先端部に気泡が存在すると筆記不能になる虞れがあるため、アスコルビン酸、アスコルビン酸誘導体、α−トコフェロール、カテキン、カテキン誘導体、合成ポリフェノール、コウジ酸、アルキルヒドロキシルアミン、オキシム誘導体、α−グルコシルルチン、ホスホン酸塩、ホスフィン酸塩、亜硫酸塩、スルホキシル酸塩、亜ジチオン酸塩、チオ硫酸塩、二酸化チオ尿素、ホルムアミジンスルフィン酸、グルタチオン等を添加して化学的に気泡を除去することが好ましい。 When the ink composition is directly filled into the ink containing tube and used in a ballpoint pen of the type in which an ink backflow preventer is provided on the rear end surface of the ink composition, if the gas is mixed in the ink, the gas As bubbles are gathered to generate ink, adversely affect the ink discharge at the time of writing, and there is a risk that writing will be impossible if bubbles exist at the tip of the writing, ascorbic acid, ascorbic acid derivative, α-tocopherol, catechin, Catechin derivatives, synthetic polyphenols, kojic acid, alkylhydroxylamine, oxime derivatives, α-glucosyl rutin, phosphonates, phosphinates, sulfites, sulfoxylate, dithionite, thiosulfate, thiourea dioxide, form It is preferable to chemically remove bubbles by adding amidinesulfinic acid, glutathione, etc. .
本発明のボールペン用水性インキ組成物には、所望により公知の剪断減粘性付与剤、例えば、水に可溶乃至分散性の、キサンタンガム、ウェランガム、構成単糖がグルコースとガラクトースの有機酸修飾ヘテロ多糖体であるサクシノグリカン(平均分子量約100乃至800万)、グアーガム、ローカストビーンガム及びその誘導体、ヒドロキシエチルセルロース、アルギン酸アルキルエステル類、メタクリル酸のアルキルエステルを主成分とする分子量10万〜15万の重合体、グルコマンナン、寒天やカラゲニン等の海藻より抽出されるゲル化能を有する増粘多糖類、ベンジリデンソルビトール及びベンジリデンキシリトール又はこれらの誘導体、架橋性アクリル酸重合体、無機質微粒子、ポリグリセリン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンヒマシ油、ポリオキシエチレンラノリン・ラノリンアルコール・ミツロウ誘導体、ポリオキシエチレンアルキルエーテル・ポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、脂肪酸アミド等のHLB値が8〜12のノニオン系界面活性剤、ジアルキル又はジアルケニルスルホコハク酸の塩類等を例示でき、単独或いは混合して使用することができる。
更に、N−アルキル−2−ピロリドンとアニオン系界面活性剤の混合物、ポリビニルアルコールとアクリル系樹脂の混合物を用いることもできる。
インキの剪断減粘性とは静止状態あるいは応力の低い時は高粘度で流動し難い性質を有し、応力が増大すると低粘度化して良流動性を示すレオロジー特性を言うものであり、チクソトロピー性あるいは擬似可塑性とも呼ばれる液性を意味している。よって、インキ組成物は筆記時の高剪断応力下においては三次元構造が一時的に破壊されインキの粘度が低下し、筆記先端部のインキは筆記に適した低粘度インキとなり、紙面に転移される。非筆記時にはインキの粘度が高くなり、インキの漏出を防止したり、インキの分離、逆流を防ぐことができる。又、インキ物性を経時的に安定に保つことができる。
The aqueous ink composition for ballpoint pens of the present invention contains a known shear thinning agent, for example, xanthan gum, welan gum, organic acid-modified heteropolysaccharide composed of glucose and galactose, which is soluble or dispersible in water. Succinoglycan (average molecular weight of about 100 to 8 million), guar gum, locust bean gum and derivatives thereof, hydroxyethyl cellulose, alginic acid alkyl esters, methacrylic acid alkyl ester as a main component and a molecular weight of 100,000 to 150,000 Polymer, glucomannan, thickening polysaccharide with gelling ability extracted from seaweed such as agar and carrageenin, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester , Polyoxye Lensorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid amide, etc. Nonionic surfactants having an HLB value of 8 to 12, salts of dialkyl or dialkenylsulfosuccinic acid and the like can be exemplified, and these can be used alone or in combination.
Furthermore, a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, a mixture of polyvinyl alcohol and an acrylic resin can also be used.
Ink shear thinning is a rheological property that has a high viscosity and is difficult to flow in a static state or when stress is low, and shows low fluidity and good fluidity when stress increases. It means liquidity called pseudo plasticity. Therefore, the ink composition is temporarily destroyed in the three-dimensional structure under high shear stress at the time of writing and the viscosity of the ink is lowered, and the ink at the tip of the writing becomes a low-viscosity ink suitable for writing and is transferred to the paper surface. The When not writing, the viscosity of the ink becomes high, and leakage of the ink can be prevented, and separation and backflow of the ink can be prevented. Also, the ink physical properties can be kept stable over time.
インキ収容管内に直接収容されるインキの粘性特性として、EM型回転粘度計の100rpmにおける測定粘度(20℃)が、3〜160mPa・sの範囲にあり、且つ剪断減粘性指数〔粘度計による剪断応力値(T)及び剪断速度(j)値の流動学的測定により導かれる、実験式(T=Kj n :但し、K及びnは計算された定数である)を適用して計算されるn値〕が、0.9〜0.99の範囲から選ばれる剪断減粘性水性インキ、B型回転粘度計の60rpmにおける測定粘度(20℃)が、1〜20mPa・sの範囲にあり、且つ、剪断減粘性指数が0.9〜0.99の範囲にある剪断減粘性水性インキ、或いは、B型回転粘度計の60rpmにおける測定粘度(20℃)が、1〜20mPa・sの範囲にある非剪断減粘性水性インキが好適である。 As viscosity characteristics of the ink directly stored in the ink storage tube, the measured viscosity (20 ° C.) at 100 rpm of the EM type rotational viscometer is in the range of 3 to 160 mPa · s, and the shear thinning index [shear by viscometer N calculated by applying an empirical formula (T = Kj n, where K and n are calculated constants), derived from rheological measurements of stress (T) and shear rate (j) values. Value] is a shear-thinning water-based ink selected from the range of 0.9 to 0.99, the measured viscosity at 20 rpm (20 ° C.) of a B-type rotational viscometer is in the range of 1 to 20 mPa · s, and A shear-thinning water-based ink having a shear-thinning index in the range of 0.9 to 0.99, or a measured viscosity at 20 rpm (20 ° C.) of a B-type rotational viscometer in the range of 1 to 20 mPa · s. Shear thinning water-based ink Is preferred.
本発明のボールペン用水性インキ組成物を充填する筆記具自体の構造、形状は特に限定されるものではなく、従来より汎用のものが適用でき、例えば、軸筒内にインキ組成物を充填したインキ収容管を有し、該インキ収容管はボールを先端部に装着したボールペンチップに連通しており、さらにインキの端面には逆流防止用のインキ逆流防止体が密接しているボールペンや、ボールペンチップが外気に晒された状態で軸筒内に収納されており、ノック式、回転式、スライド式等の出没機構を有するボールペン等が例示できる。 The structure and shape of the writing instrument itself filled with the water-based ink composition for the ballpoint pen of the present invention is not particularly limited, and a conventional one can be applied, for example, ink storage in which the ink composition is filled in a shaft cylinder The ink storage tube communicates with a ballpoint pen tip with a ball attached to the tip, and a ballpoint pen with a backflow prevention body for preventing backflow is in close contact with the end surface of the ink. Examples thereof include a ballpoint pen that is housed in the shaft cylinder in a state exposed to the outside air and has a retracting mechanism such as a knock type, a rotary type, and a slide type.
前記ボールペンチップは、従来より汎用のチップ機構、例えば、金属を切削加工して内部にボール受け座とインキ導出部を形成したもの、金属製パイプの先端近傍の内面に複数の内方突出部を外面からの押圧変形により設け、前記内方突出部の相互間に、中心部から径方向外方に放射状に延びるインキ流出間隙を形成したもの等を適用でき、特に押圧変形によるチップは、ボール後端との接触面積が比較的小であり、低筆記圧でのスムーズな筆記感を与えることができる。
前記ボールペンチップに抱持されるボールは、超硬合金、ステンレス鋼、ルビー、セラミック等の外径0.3〜1.5mmのボールが有効であり、前記チップのボール抱持部の内径とボールとの径方向の可動距離は10〜50μm、ボールの軸方向の可動距離は10〜30μmの範囲であることが好ましい。
なお、前記ボールペンチップには、チップ内にボールの後端を前方に弾発する弾発部材を配して、非筆記時にはチップ先端の内縁にボールを押圧させて密接状態とし、筆記時には筆圧によりボールを後退させてインキを流出可能に構成することが好ましく、不使用時のインキ漏れを抑制できる。
前記弾発部材は、金属細線のスプリング、前記スプリングの一端にストレート部(ロッド部)を備えたもの、線状プラスチック加工体等を例示でき、15〜45gの弾発力により、押圧可能に構成して適用される。
The ballpoint pen tip is a conventional general-purpose tip mechanism, for example, a metal cutting machine formed with a ball receiving seat and an ink lead-out portion inside, and a plurality of inward protruding portions on the inner surface near the tip of a metal pipe. It can be applied by pressing deformation from the outer surface, and an ink outflow gap extending radially outward from the central portion can be applied between the inward protruding portions. The contact area with the edge is relatively small, and a smooth writing feeling can be given with a low writing pressure.
Balls held by the ballpoint pen tip are effectively balls having an outer diameter of 0.3 to 1.5 mm, such as cemented carbide, stainless steel, ruby, ceramic, and the like. The movable distance in the radial direction is preferably in the range of 10 to 50 μm, and the movable distance in the axial direction of the ball is preferably in the range of 10 to 30 μm.
The ballpoint pen tip is provided with a resilient member for projecting the rear end of the ball forward in the tip. When not writing, the ball is pressed against the inner edge of the tip of the tip to bring it into close contact, and when writing, it is It is preferable that the ball is retracted so that ink can flow out, and ink leakage when not in use can be suppressed.
Examples of the elastic member include a metal thin wire spring, a member provided with a straight portion (rod portion) at one end of the spring, and a linear plastic processed body. The elastic member can be pressed by an elastic force of 15 to 45 g. Applied.
前記ボールペンチップと直接、或いは、接続部材を介して連結されるインキ収容管は、汎用の筒状成形部材、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート等の熱可塑性樹脂による成形部材が適用され、インキの低蒸発性、生産性の面で好適に用いられる。
又、前記インキ収容管は、2.5〜10mmの内径を有するものが好適に用いられる。
更に、前記インキ収容管として透明、着色透明、或いは半透明の成形体を用いることにより、インキ色やインキ残量等を確認できる。
前記インキ収容管はレフィルの形態として軸筒内に収容したり、先端部にチップを装着した軸筒自体をインキ収容管として、前記軸筒内に直接インキを充填してもよい。
The ink storage tube connected to the ballpoint pen tip directly or via a connecting member is a general-purpose cylindrical molded member, for example, a molded member made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, etc. It is preferably used in terms of low evaporation and productivity.
Further, the ink containing tube having an inner diameter of 2.5 to 10 mm is preferably used.
Furthermore, by using a transparent, colored transparent, or translucent molded body as the ink containing tube, the ink color, the remaining amount of ink, and the like can be confirmed.
The ink storage tube may be accommodated in the shaft cylinder as a form of refill, or the shaft cylinder itself having a tip attached to the tip may be used as an ink storage tube, and ink may be directly filled into the shaft cylinder.
前記インキ収容管に収容したインキの後端にはインキ逆流防止体が充填される。
前記インキ逆流防止体は、ポリブテン、α−オレフィンオリゴマー、シリコーン油、精製鉱油等の従来より公知の不揮発性液体或いは難揮発性液体からなる基油に、シリカ、珪酸アルミニウム、膨潤性雲母、脂肪酸アマイド等の増粘剤を添加したものが適用される。
前記基油としては、ポリブテン又はシリコーン油が好適に用いられ、増粘剤としては脂肪酸アマイド又はシリカが好適に用いられる。
本発明に用いられるインキ逆流防止体は、インキ粘度がEM型回転粘度計の100rpmにおける測定粘度(20℃)が、3〜160mPa・sの範囲にあり、且つ剪断減粘性指数が、0.9〜0.99の範囲にある剪断減粘性水性インキ、B型回転粘度計の60rpmにおける測定粘度(20℃)が、1〜20mPa・sの範囲にあり、且つ剪断減粘性指数が、0.9〜0.99の範囲にある剪断減粘性水性インキ、或いは、B型回転粘度計の60rpmにおける測定粘度(20℃)が、1〜20mPa・sの範囲にある非剪断減粘性水性インキを用いる場合、粘弾性測定におけるtanδが1を越える点(ω)が20rad/s≦ω≦450rad/sの範囲にあることが好ましい。
これを詳しく説明すると、前記インキは静置状態での粘度が低く、剪断減粘指数を0.1〜0.6程度に調整した従来の剪断減粘性水性インキと比べて耐衝撃性に劣る。よって、インキ収容管後部からインキの漏れ出しを生じ易く、筆記不能になったり、商品価値を損なう虞がある。
よって、インキの後端に配置されるインキ逆流防止体に耐衝撃性を付与して前述した不具合を解消する必要がある。
前記粘弾性測定におけるtanδが1を越える点(ω)が20rad/s≦ω≦450rad/sの範囲にあるインキ逆流防止体は粘弾性を示し、弾性応答と粘性応答の中間的な性質を示す。
粘弾性測定は、レオメーターの振動法により測定し、tanδとは損失弾性率の値を貯蔵弾性率の値で割ったものであり、この値が低い(tanδ<1)と、弾性特性が高く、且つ、粘性特性が低くなる。一方、この値が高い(tanδ>1)と、弾性特性が低く、且つ、粘性特性が高くなる。
前述の粘弾性測定において、角周波数(rad/s)が20以上の領域は筆記具に落下等の衝撃を加えた状態に近い領域となる。
従って、20rad/sでtanδが1を越える粘弾性を示すインキ逆流防止体は、粘性応答の強さに依存して耐衝撃性を満足させることができる。
前記tanδが1を越える点は20rad/s以上であるが、450rad/sを越えると弾性応答が強くなってインキ追従性を損ないがちであり、インキ出に乏しくなる。
よって、インキ逆流防止体のtanδが1を越える点(ω)を20rad/s≦ω≦450rad/sの範囲に調整することにより、耐衝撃性と筆記性能を共に満足させることができる。
なお、インキ逆流防止体には、樹脂成形による固体栓を併用することもできる。
An ink backflow preventer is filled at the rear end of the ink stored in the ink storage tube.
The ink backflow preventer is a base oil composed of conventionally known non-volatile liquid or hardly volatile liquid such as polybutene, α-olefin oligomer, silicone oil, refined mineral oil, silica, aluminum silicate, swellable mica, fatty acid amide. What added the thickeners, such as, is applied.
Polybutene or silicone oil is preferably used as the base oil, and fatty acid amide or silica is preferably used as the thickener.
The ink backflow preventer used in the present invention has an ink viscosity measured at 100 rpm (20 ° C.) of an EM rotational viscometer in the range of 3 to 160 mPa · s, and a shear thinning index of 0.9. The measured viscosity at 20 rpm (20 ° C.) of a shear-thinning water-based ink in the range of ˜0.99 and a B-type rotational viscometer is in the range of 1 to 20 mPa · s, and the shear thinning index is 0.9 When using a shear-thinning water-based ink in the range of ~ 0.99 or a non-shear-thinning water-based ink having a viscosity measured at 60 rpm (20 ° C) of a B-type rotational viscometer in the range of 1 to 20 mPa · s The point (ω) where tan δ in viscoelasticity measurement exceeds 1 is preferably in the range of 20 rad / s ≦ ω ≦ 450 rad / s.
More specifically, the ink has a low viscosity in a stationary state, and is inferior in impact resistance as compared with a conventional shear thinning water-based ink having a shear thinning index adjusted to about 0.1 to 0.6. Therefore, ink is likely to leak out from the rear part of the ink containing tube, and writing may become impossible or the commercial value may be impaired.
Therefore, it is necessary to provide impact resistance to the ink backflow preventer disposed at the rear end of the ink to eliminate the above-described problems.
The ink backflow prevention body in which the point (ω) where tan δ in the viscoelasticity measurement exceeds 1 is in the range of 20 rad / s ≦ ω ≦ 450 rad / s exhibits viscoelasticity and exhibits an intermediate property between elastic response and viscous response. .
The viscoelasticity is measured by a rheometer vibration method. Tan δ is obtained by dividing the value of the loss elastic modulus by the value of the storage elastic modulus. When this value is low (tan δ <1), the elastic property is high. In addition, the viscosity characteristics are lowered. On the other hand, when this value is high (tan δ> 1), the elastic characteristics are low and the viscosity characteristics are high.
In the above-described viscoelasticity measurement, the region where the angular frequency (rad / s) is 20 or more is a region close to a state where an impact such as a drop is applied to the writing instrument.
Therefore, the ink backflow preventive body showing viscoelasticity with tan δ exceeding 1 at 20 rad / s can satisfy the impact resistance depending on the strength of the viscous response.
The point where tan δ exceeds 1 is 20 rad / s or more, but if it exceeds 450 rad / s, the elastic response becomes strong and the ink followability tends to be deteriorated, resulting in poor ink discharge.
Therefore, both the impact resistance and the writing performance can be satisfied by adjusting the point (ω) where tan δ of the ink backflow preventive body exceeds 1 to the range of 20 rad / s ≦ ω ≦ 450 rad / s.
The ink backflow preventer can be used in combination with a solid plug formed by resin molding.
以下に実施例を説明するが、本発明はこれらの実施例に限定されるものではない。以下の表に実施例及び比較例のボールペン用水性インキの組成と粘度を示す。
なお,表中の組成の数値は重量部を示す。
実施例1〜4、比較例1〜4、6〜9のインキ粘度は20℃でB型回転粘度計〔東京計器(株)製、BLアダプター使用〕を用いて、60rpmにて測定した。
実施例5、及び、比較例5のインキ粘度は20℃でEMD型回転粘度計〔東機産業(株)製、RE−80R、標準ロータ使用〕を用いて、60rpmにて測定した。
前記実施例2、4、及び、比較例2、4、9のインキの剪断減粘指数は0.97であり、実施例5、及び、比較例5のインキの剪断減粘指数は0.3であった。
Examples will be described below, but the present invention is not limited to these examples. The following table shows compositions and viscosities of water-based inks for ballpoint pens of Examples and Comparative Examples.
In addition, the numerical value of a composition in a table | surface shows a weight part.
The ink viscosities of Examples 1 to 4 and Comparative Examples 1 to 4 and 6 to 9 were measured at 60 ° C. using a B-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd., using BL adapter) at 20 ° C.
The ink viscosity of Example 5 and Comparative Example 5 was measured at 60 rpm using an EMD type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., RE-80R, using a standard rotor) at 20 ° C.
The shear thinning index of the inks of Examples 2 and 4 and Comparative Examples 2, 4, and 9 is 0.97, and the shear thinning index of the inks of Examples 5 and Comparative Example 5 is 0.3. Met.
表中の原料の内容について注番号に沿って説明する。
(1)オリエント化学工業(株)製、商品名:フィスコブラック886、有効成分15%
(2)アイゼン保土谷(株)製、C.I.45410、商品名:フロキシン
(3)住友化学工業(株)製、C.I.42655、商品名:アシッドブルーPG
(4)BASF社製、商品名:poligen WE3、エチレンアクリル酸コポリマーワックスエマルジョン、平均粒子径0.1μm以下、固形分25%
(5)BASF社製、商品名:poligen WE4、エチレンアクリル酸コポリマーワックスエマルジョン、平均粒子径0.1μm以下、固形分21%
(6)三井化学(株)製、商品名:ケミパールS−100、平均粒子径0.1μm以下、固形分27%
(7)三晶(株)製、商品名:レオザン
(8)1,2−ベンズチアゾリン−3−オン、アビシア(株)製、商品名:プロキセルXL−2
(9)リン酸エステル系界面活性剤、第一工業製薬(株)製、商品名:プライサーフAL
(10)エレメンティスジャパン社製、商品名:SLIP−AID 635E、カルナバワックスエマルジョン、粒子径0.1〜1μm、固形分35%
(11)ジョンソンポリマー社製、商品名:ジョンクリル780、平均粒子径0.1μm、固形分48%、最低造膜温度50℃以上
(12)クラリアントジャパン社製、商品名:モビニール972、平均粒子径0.1μm以上、固形分50%、最低造膜温度220℃
(13)日本エヌエスシー(株)製、商品名:カネビノールKD5、平均粒子径0.02μm、固形分35%、最低造膜温度65℃以上
The contents of the raw materials in the table will be described along the note numbers.
(1) Orient Chemical Industry Co., Ltd., trade name: FISCO BLACK 886, active ingredient 15%
(2) Eisen Hodogaya Co., Ltd., C.I. I. 45410, trade name: Phloxine (3) manufactured by Sumitomo Chemical Co., Ltd., C.I. I. 42655, Product Name: Acid Blue PG
(4) Product name: POLIGEN WE3, ethylene acrylic acid copolymer wax emulsion, average particle size of 0.1 μm or less, solid content 25%, manufactured by BASF
(5) Product name: POLIGEN WE4, ethylene acrylic acid copolymer wax emulsion, average particle size of 0.1 μm or less, solid content 21%, manufactured by BASF
(6) Made by Mitsui Chemicals, trade name: Chemipearl S-100, average particle size 0.1 μm or less, solid content 27%
(7) Sanki Co., Ltd., trade name: Leozan (8) 1,2-benzthiazolin-3-one, Avicia Co., Ltd., trade name: Proxel XL-2
(9) Phosphate ester surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prisurf AL
(10) Product name: SLIP-AID 635E, carnauba wax emulsion, particle size 0.1 to 1 μm, solid content 35%, manufactured by Elementis Japan
(11) Made by Johnson Polymer Co., Ltd., trade name: Jonkrill 780, average particle size 0.1 μm, solid content 48%, minimum film forming temperature 50 ° C. or higher (12) Made by Clariant Japan, trade name: Mobile 972, average particle Diameter 0.1μm or more, solid content 50%, minimum film-forming temperature 220 ° C
(13) Nippon NS Co., Ltd., trade name: Kanebinol KD5, average particle size 0.02 μm, solid content 35%, minimum film forming temperature 65 ° C. or higher
インキ逆流防止体の調製
基油としてポリブテン85部中に、増粘剤として脂肪酸アマイド15部を添加した後、3本ロールにて混練してインキ逆流防止体を得た。
なお、前記インキ逆流防止体は、20℃でレオメーター〔Paar Physica社製、DSR4000、2°のコーンプレート(直径25mm)使用〕を用いて測定した結果、100rad/sでtanδが1を越えるものであった。
Preparation of Ink Backflow Preventer Body In 85 parts of polybutene as a base oil, 15 parts of fatty acid amide as a thickener was added, and then kneaded with three rolls to obtain an ink backflow preventer body.
The ink backflow preventer was measured at 20 ° C. using a rheometer (Paar Physica, DSR4000, 2 ° cone plate (diameter 25 mm)). As a result, tan δ exceeded 1 at 100 rad / s. Met.
水性ボールペンの作製
前記各インキ組成物を直径0.5mmのボールを抱持するステンレススチール製チップがポリプロピレン製パイプ(内径3.8mm)の一端に嵌着されたボールペンレフィルに充填し、その後端に前記インキ逆流防止体を配設した後、前記ボールペンレフィルを軸筒に組み込み、水性ボールペンを作製した。
Preparation of water-based ballpoint pen Each ink composition was filled in a ballpoint pen refill fitted with one end of a polypropylene pipe (inner diameter: 3.8 mm) with a stainless steel chip holding a ball of 0.5 mm in diameter. After the ink backflow prevention body was disposed, the ballpoint pen refill was incorporated into a shaft tube to produce an aqueous ballpoint pen.
前記各水性ボールペンにより以下のテストを行った。
垂れ下がり試験
キャップを外した水性ボールペンを、ペン先(ボールペンチップ)非接触状態で下向き(倒立)に保持し、温度20℃、相対湿度90%の雰囲気下に20時間放置した後、ペン先の外観を目視で観察し、以下の基準で評価した。
キャップオフ試験
組み立て後、筆記可能であることを確認した水性ボールペンを、ペン先を露出した状態で室温(20℃)、湿度55〜75%RHの条件下に横置き、10日間放置後、JIS P3201筆記用紙Aに手書きで丸を一行に12個連続筆記し、何行目から正常に筆記できるかを調べ、以下の基準で評価した。
インキ安定性試験
各インキ組成物を室温(20℃)及び50℃で7日間放置した後、インキの状態を目視により観察した。
The following tests were performed with each of the water-based ballpoint pens.
Dripping test A water-based ballpoint pen with the cap removed is held downward (inverted) in a non-contact state with the pen tip (ballpoint pen tip) and left for 20 hours in an atmosphere at a temperature of 20 ° C. and a relative humidity of 90%. Were visually observed and evaluated according to the following criteria.
Cap-off test After assembly, the water-based ballpoint pen, which was confirmed to be writable, was placed horizontally under conditions of room temperature (20 ° C.) and humidity 55-75% RH with the pen tip exposed, and left for 10 days. P3201 writing paper A was handwritten and 12 circles were written continuously in one line, and from what line the writing was normally performed was examined and evaluated according to the following criteria.
Ink stability test Each ink composition was allowed to stand at room temperature (20 ° C) and 50 ° C for 7 days, and then the state of the ink was visually observed.
試験結果を以下の表に示す。
尚、テスト結果の評価の記号の内容は以下のとおり。
垂れ下がり試験
○:インキの漏れだし(垂れ下がり)が認められない。
△:チップ先端にインキの小滴が認められる。
×:チップ先端に、大きいインキ滴が認められる、或いはチップ先端から漏れたインキが落下している。
キャップオフ試験
○:即筆記可能
×:即筆記不可能(1行以内で筆記可能)
インキ安定性試験
○:異常なし。
×:エマルジョンが浮いたり、沈降している。
The contents of the test result evaluation symbols are as follows.
Sag test ○: No ink leakage (sag) was observed.
Δ: Ink droplets are observed at the tip of the chip.
X: Large ink droplets are observed at the tip of the chip, or ink leaking from the tip of the chip is falling.
Cap-off test ○: Can be written immediately ×: Cannot be written immediately (can be written within 1 line)
Ink stability test ○: No abnormality.
X: The emulsion floats or settles.
Claims (5)
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| JP4690662B2 (en) * | 2004-04-26 | 2011-06-01 | 株式会社パイロットコーポレーション | Water-based ballpoint pen |
| JP2007177023A (en) * | 2005-12-27 | 2007-07-12 | Pilot Ink Co Ltd | Water-based ink composition for ballpoint pen and ballpoint pen having the same therein |
| JP4971675B2 (en) * | 2006-04-28 | 2012-07-11 | パイロットインキ株式会社 | Intrusion ballpoint pen |
| JP6921901B2 (en) * | 2015-06-26 | 2021-08-18 | 株式会社パイロットコーポレーション | Aqueous ink composition for writing tools and writing tools using it |
| JP6559480B2 (en) * | 2015-06-26 | 2019-08-14 | 株式会社パイロットコーポレーション | Water-based ink composition for writing instrument and writing instrument using the same |
| JP6796958B2 (en) * | 2016-06-30 | 2020-12-09 | 株式会社パイロットコーポレーション | Aqueous ink composition for writing instruments and writing instruments using it |
| JP2021062634A (en) * | 2021-01-18 | 2021-04-22 | 株式会社パイロットコーポレーション | Aqueous ball point pen |
| JP7153152B1 (en) | 2021-03-31 | 2022-10-13 | 大日精化工業株式会社 | Resin composition and method for producing resin composition |
| TW202246419A (en) * | 2021-03-31 | 2022-12-01 | 日商大日精化工業股份有限公司 | Resin composition and production method for resin composition |
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