JP2008001852A - Writing instrument - Google Patents

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JP2008001852A
JP2008001852A JP2006174978A JP2006174978A JP2008001852A JP 2008001852 A JP2008001852 A JP 2008001852A JP 2006174978 A JP2006174978 A JP 2006174978A JP 2006174978 A JP2006174978 A JP 2006174978A JP 2008001852 A JP2008001852 A JP 2008001852A
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ink
dispersion
pigment
writing instrument
colorant
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Kazuo Sakai
和夫 坂井
Tsutomu Ueda
勉 上田
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Fuji Pigment Co Ltd
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Fuji Pigment Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a writing instrument using a pigment dispersing ink based on an organic solvent, durable for a long time without cap, imparting a preferable writing in deep color. <P>SOLUTION: The invention relates to the writing instrument and ink for the same comprising a dispersing medium which is an isoparaffin, a coloring agent such as fine powder of carbon or organic pigment, and a polymer dispersant which is conventionally known as a dispwesant and soluble in the dispersing medium, wherein a dispersion aid such as (a) N, N-dialkylaminoethylacrylate and (b) N-(1'-sulfoxy-3'-methyl-5'-chloro)-3-hydroxy-2-naphthalenecarboxamide (abbreviated as naphthol AS-F), or N-(3'-sulfoxy)-3-hydroxy-2-naphthalenecarboxamide (abbreviated as naphthol AS-PS) are jointly used. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は有機溶剤系顔料分散インクを用いてなる筆記具に関するものである。   The present invention relates to a writing instrument using an organic solvent-based pigment-dispersed ink.

フェルトあるいは繊維束を芯とする筆記具類は、マーカーや筆ペンと呼ばれて日常生活に定着している。これらは水性あるいは油性媒体に、着色剤として染料を溶解するかあるいは顔料を微細分散したインクが用いられている。着色剤の耐水性や耐光性から顔料の使用が望ましいが、顔料ではインク中の微細分散粒子の安定性に問題がある。すなわち、顔料粒子が経時的に凝集沈殿してインクの流動性が低下し、目詰まりやかすれなどとなって筆記具として重要な機能が失われるのである。この傾向は水性媒体の場合に起こり易い。また、油性媒体ではインクの流動性は良いものの、顔料の分散安定性の問題に加えて、キャップを外した状態(キャップオフ)では油性媒体が蒸発して目詰まりやかすれなどの現象が加速する。従来、油性媒体としてケトン系、エステル系、アルコール系あるいはグリコールエーテル系等の溶剤が、単独または混合物として用いられ実用化されてきてし、改善の提案も枚挙に暇がないほどである。しかしながら、油性媒体使用で分散安定性の改善がなされた場合でも、キャップオフ時に外気に接するインクが固化して流動性を失い筆記具としての用をなさなくなるのである。グリコールエーテル系の高沸点溶剤の併用で改善がみられるものの、多用すると筆記後のインクの乾燥速度が遅くなって、そのための実用上の困難が新たに発生するのである。
特開昭49−50935号公報
Writing instruments with felt or fiber bundles as the core are called markers and brush pens, and have become established in daily life. These are inks in which a dye is dissolved as a colorant or a pigment is finely dispersed in an aqueous or oily medium. The use of a pigment is desirable because of the water resistance and light resistance of the colorant, but the pigment has a problem in the stability of finely dispersed particles in the ink. That is, pigment particles aggregate and precipitate over time, resulting in a decrease in ink fluidity, resulting in clogging and fading, and the loss of important functions as a writing instrument. This tendency is likely to occur with aqueous media. In addition, although the fluidity of the ink is good in the oily medium, in addition to the problem of the dispersion stability of the pigment, the oily medium evaporates and the phenomenon such as clogging and fading accelerates when the cap is removed (cap off). . Conventionally, ketone-based, ester-based, alcohol-based or glycol ether-based solvents as oily media have been put into practical use alone or as a mixture, and proposals for improvement are not enough. However, even when the dispersion stability is improved by using an oily medium, the ink that comes into contact with the outside air at the time of cap-off solidifies and loses fluidity, so that it cannot be used as a writing instrument. Although improvement can be seen when a glycol ether-based high-boiling solvent is used in combination, if it is used frequently, the drying speed of the ink after writing will be slowed down, and new practical difficulties will arise.
Japanese Patent Laid-Open No. 49-50935

前項に述べたように、顔料を着色剤とする筆記具用インクには難点があるので、筆記具として使いづらいというのが現状である。主たる難点は顔料の分散安定性とキャップオフ時間にあり、これらをともに改善する必要がある。  As described in the previous section, since there is a difficulty in ink for writing instruments using pigment as a colorant, it is currently difficult to use as a writing instrument. The main problems are the dispersion stability of the pigment and the cap-off time, and both of them need to be improved.

顔料の安定で微細な分散を可能にする分散助剤を見出すこと、油性媒体を選択することのふたつの観点から検討し、両者を矛盾なく組み合わせて前記問題点を同時に改善する手段の可否を追求した結果本発明に到達した。 すなわち、本発明では従来公知の筆記具において、(1)着色剤としてカーボンブラックや有機顔料の群から選ばれた微細粒子状顔料、(2)分散媒体としてイソパラフィン、(3)分散剤として従来公知で該媒体に溶解性の高分子分散剤、および(4)分散助剤として(a)N,N−ジアルキルアミノエチルアクリレートと(b)N−(1'−スルホキシ−3'−メチル−5'−クロロ)−3−ヒドロキシ−2−ナフタレンカルボキサミド(略称:ナフトールAS−F)または/およびN−(3'−スルホキシ)−3−ヒドロキシ−2−ナフタレンカルボキサミド(略称:ナフトールAS−PS)である(a)と(b)の両者、さらに要すれば(5)インクの筆記対象物への密着剤として従来公知で該媒体に溶解性の石油系樹脂あるいは水添石油系樹脂の各者を構成要素として含有せしめたことを特徴とする溶剤系顔料分散インクを用ることで目的とする筆記具を実現することができた。   Finding a dispersion aid that enables stable and fine dispersion of pigments, and selecting oil-based media, and examining the possibility of simultaneously improving both of these problems by combining them consistently As a result, the present invention has been achieved. That is, in the presently known writing instrument in the present invention, (1) a fine particulate pigment selected from the group of carbon black and organic pigment as a colorant, (2) isoparaffin as a dispersion medium, (3) conventionally known as a dispersant. (4) (a) N, N-dialkylaminoethyl acrylate and (b) N- (1′-sulfoxy-3′-methyl-5′- Chloro) -3-hydroxy-2-naphthalenecarboxamide (abbreviation: naphthol AS-F) and / or N- (3′-sulfoxy) -3-hydroxy-2-naphthalenecarboxamide (abbreviation: naphthol AS-PS) ( Both a) and (b), and if necessary, (5) each component of a petroleum-based resin or hydrogenated petroleum-based resin that has been conventionally known as an adhesive for ink writing objects and is soluble in the medium Solvent characterized by containing as The pigment dispersion ink was able to realize a writing instrument of interest by Yeoul.

特定の分散助剤と分散媒体の組み合わせからなるインクを用いることで、乾燥固化が速く、キャップオフ時間が長く、濃色で順調な筆記性が長期に確保された筆記具が実現した。   By using an ink composed of a combination of a specific dispersion aid and a dispersion medium, a writing instrument that has a fast drying and solidification, a long cap-off time, a dark color and smooth writing performance has been realized.

本発明の筆記具で用いる溶剤系顔料分散インクにおいて、着色剤としての顔料はカーボンまたは有機顔料である。金属酸化物等の無機顔料は、本発明の分散系をもってしても微細で安定な分散液とするには不適当である。したがって本発明で実施可能な顔料はインクの着色剤として従来公知のカーボンブラックや各種の有機顔料である。カーボンブラックはその製法によって表面特性が異なるが、酸性カーボンやアルカリ性カーボン等の種類を問わず実施可能である。ただし、概して言えば酸性カーボンは分散剤と分散助剤の使用量が比較的に少なくても微細で安定な分散液とすることができるので好適である。有機顔料としては当業界で著明な顔料便覧に記載されている従来公知の顔料が実施可能である。このように多種多様の顔料で微細で安定な分散液が実現可能になったのは、ひとえに本発明の分散剤系、とくに分散助剤の選択によるものである。   In the solvent-based pigment-dispersed ink used in the writing instrument of the present invention, the pigment as the colorant is carbon or an organic pigment. Inorganic pigments such as metal oxides are unsuitable for obtaining a fine and stable dispersion even with the dispersion of the present invention. Therefore, the pigments that can be used in the present invention are conventionally known carbon black and various organic pigments as ink colorants. Although carbon black has different surface characteristics depending on its production method, it can be carried out regardless of the type of acidic carbon, alkaline carbon, or the like. However, generally speaking, acidic carbon is suitable because it can be made into a fine and stable dispersion even if the amount of dispersant and dispersion aid used is relatively small. As the organic pigment, conventionally known pigments described in the handbook of pigments notable in the art can be used. The reason why a fine and stable dispersion liquid can be realized with such a wide variety of pigments is solely due to the selection of the dispersant system of the present invention, particularly the dispersion aid.

本発明の筆記具で用いる溶剤系顔料分散インクにおいて、分散媒体は分岐構造の脂肪族飽和炭化水素であり、一般的にイソパラフィンと呼ばれる常温で液体の物質である。石油化学工業の精留品として市販されているので容易に入手可能である。イソパラフィンは分岐構造や分子量の異なる分子の混合物であり、蒸留温度範囲で特徴付けられる。インクの媒体としては蒸発温度が70℃以上350℃以下の留分が使用可能である。蒸発温度が70℃以下の留分が多いとインクとして低粘度で好ましいが揮発性が高過ぎてキャップオフ可能時間が短く不適当である。蒸発温度が高い、とりわけ300℃以上の留分が多いと上記の難点はないものの、インクの粘度が高くて流動性に劣り筆記速度にインクが追随しないとか、筆記後インクの基材への浸透あるいは乾燥固化の速度が遅いので不適当である。
このような観点から50%留出温度が100℃以上250℃以下の範囲内にある留分混合物が好ましい。本発明で好適な分散媒体として市場で入手可能な商品の例を挙げると、出光石油化学社製の「IPソルベント」やエクソンモービル社製の「アイソパー」があり、粘度や蒸発温度等の観点からIPソルベント1016、同1620や同2028、アイソパーE、同G、同H、同L、同M等である。通常の使用目的に供する筆記具用インクの媒体としてとくに好適な一例を示すと、常圧沸点が約90℃以上165℃以下の分留成分の混合物で、かつ、50%留出沸点が約115℃、90%留出沸点が約125℃のイソパラフィン、例えば前出のIPソルベント1016である。なお、当該分散媒体を使用することでインクが低臭性であることは望外の成果であった。
In the solvent-based pigment dispersion ink used in the writing instrument of the present invention, the dispersion medium is an aliphatic saturated hydrocarbon having a branched structure, and is a substance that is generally liquid at normal temperature called isoparaffin. Since it is marketed as a rectified product of the petrochemical industry, it can be easily obtained. Isoparaffins are a mixture of molecules with different branched structures and molecular weights and are characterized by a distillation temperature range. As an ink medium, a fraction having an evaporation temperature of 70 ° C. or higher and 350 ° C. or lower can be used. A large amount of a fraction having an evaporation temperature of 70 ° C. or less is preferable because it has a low viscosity as an ink. If the evaporation temperature is high, especially if there are many fractions of 300 ° C. or higher, the above-mentioned drawbacks are not present, but the ink viscosity is high and the fluidity is poor and the ink does not follow the writing speed, or the ink penetrates the base material after writing. Or it is unsuitable because the rate of drying and solidification is slow.
From such a viewpoint, a fraction mixture having a 50% distillation temperature in the range of 100 ° C. or more and 250 ° C. or less is preferable. Examples of commercially available products as suitable dispersion media in the present invention include “IP Solvent” manufactured by Idemitsu Petrochemical Co., Ltd. and “Isopar” manufactured by ExxonMobil Co., Ltd., from the viewpoint of viscosity, evaporation temperature, and the like. IP solvent 1016, 1620, 2028, Isopar E, G, H, L, M, etc. An example particularly suitable as a medium for ink for writing instruments used for ordinary purposes is a mixture of fractional distillation components having an atmospheric pressure boiling point of about 90 ° C. or more and 165 ° C. or less, and a 50% distillation boiling point of about 115 ° C. An isoparaffin having a 90% distillation boiling point of about 125 ° C., such as the IP solvent 1016 described above. It was an unexpected result that the ink has low odor by using the dispersion medium.

本発明の筆記具で用いる溶剤系顔料分散インクにおいて、分散剤は従来公知の分散剤で前記分散媒体に溶解性の重合体であって、従来公知の湿式分散技術で分散液調製して調製直後には一時的に本発明で使用する顔料の微細分散が可能な重合体である。より具体的には調製後1時間から12時間の静置で目視観察で顔料の凝集沈殿が認められない重合体である。すなわち、調製後1時間の静置で凝集沈殿の認められない分散重合体は後述の分散助剤を併用して長期の分散安定性が確保できるのである。反対に調製後1時間以内に凝集が認められる重合体では後述の分散助剤を併用しても長期の分散安定性が確保できず、また使用量を本発明の好適範囲を越えて過大にすると長期の安定性が確保できてもそのための別の難点が発現して不適当である。かかる分散剤重合体は当該技術分野の技術者は実験により容易に選択することができる。本発明で使用可能な分散剤重合体の例として、ルーブリゾール社製ソルスパース11200、ビックケミー社製デスパピック101やISP社製アンタロンV−216等を挙げることができる。   In the solvent-based pigment-dispersed ink used in the writing instrument of the present invention, the dispersant is a conventionally known dispersant and a polymer that is soluble in the dispersion medium. Is a polymer capable of temporarily finely dispersing the pigment used in the present invention. More specifically, it is a polymer in which agglomeration and precipitation of pigments are not observed by visual observation after standing for 1 to 12 hours after preparation. That is, a dispersion polymer in which aggregation and precipitation are not observed after standing for 1 hour after preparation can be used in combination with a dispersion aid described later to ensure long-term dispersion stability. On the other hand, in a polymer in which aggregation is observed within 1 hour after preparation, long-term dispersion stability cannot be ensured even when used in combination with a dispersion aid described below, and if the amount used exceeds the preferred range of the present invention. Even if long-term stability can be ensured, it is inappropriate because of the emergence of other difficulties. Such a dispersant polymer can be easily selected by an engineer in the art by experiment. Examples of the dispersant polymer that can be used in the present invention include Solsperse 11200 manufactured by Lubrizol, Desperpic 101 manufactured by Big Chemie, Antalon V-216 manufactured by ISP, and the like.

本発明の筆記具で用いる溶剤系顔料分散インクにおいて、もっとも重要な役割を担う分散助剤は、(a)N,N−ジアルキルアミノエチルアクリレートと、(b)N−(1'−スルホキシ−3'−メチル−5'−クロロ)−3−ヒドロキシ−2−ナフタレンカルボキサミド(略称:ナフトールAS−F)またはN−(3'−スルホキシ)−3−ヒドロキシ−2−ナフタレンカルボキサミド(略称:ナフトールAS−PS)である(a)と(b)の両者の併用である。本発明の分散助剤を前記分散剤重合体と比較的少量併用することで顔料の長期微細安定な溶剤系顔料分散インクが実現する。因みに分散剤重合体を用いることなくこの分散助剤ナフトールAS−FやナフトールAS−PSのみ、あるいはナフトールAS−FとナフトールAS−PSの両者併用のみでは、目的に適う溶剤系顔料分散インクは実現しない。   In the solvent-based pigment dispersion ink used in the writing instrument of the present invention, the dispersion assistant that plays the most important role is (a) N, N-dialkylaminoethyl acrylate, and (b) N- (1′-sulfoxy-3 ′). -Methyl-5'-chloro) -3-hydroxy-2-naphthalenecarboxamide (abbreviation: naphthol AS-F) or N- (3'-sulfoxy) -3-hydroxy-2-naphthalenecarboxamide (abbreviation: naphthol AS-PS) ) Is a combination of both (a) and (b). By using a relatively small amount of the dispersion aid of the present invention together with the dispersant polymer, a solvent-based pigment dispersion ink having a long-term fine stability of the pigment is realized. By the way, without using a dispersant polymer, a solvent-based pigment dispersion ink suitable for the purpose can be realized by using only the dispersion aid naphthol AS-F or naphthol AS-PS, or by using both naphthol AS-F and naphthol AS-PS alone. do not do.

なお、本発明における分散助剤の一方であるN,N−ジアルキルアミノエチルアクリレートの窒素の置換基であるアルキル基は炭素数8以下の直鎖または分岐状のアルキルである。顔料を分散する能力からメチル基、エチル基、プロピル基の場合が最適である。置換基の炭素数が大きくなると分散の安定性が低下する傾向があるので好ましくない。   In addition, the alkyl group which is a nitrogen substituent of N, N-dialkylaminoethyl acrylate which is one of the dispersion aids in the present invention is a linear or branched alkyl having 8 or less carbon atoms. In view of the ability to disperse the pigment, the methyl group, ethyl group, and propyl group are optimal. An increase in the number of carbon atoms in the substituent is not preferred because the dispersion stability tends to decrease.

本発明においてインクの固体成分の筆記面への密着性をとくに高めるために、インク中に密着剤として石油系樹脂あるいは水添石油系樹脂を添加しておくことが可能である。これら樹脂は分散媒体に溶解性であり、しかも顔料の分散とその安定性を阻害しないことを条件に選定したものである。この使用により、筆記蔵が擦過や水濡れにより損傷することから保護されるのである。本発明で好適に使用される密着剤としては以下の物質が例示できる。水添脂環族炭化水素樹脂、例えば、エクソンモービル社製エスコレッツ5300や同変性品、脂肪族・芳香族炭化水素樹脂、例えば、日本ゼオン社製クイントンD−200等が好適に使用可能である。筆記像に永続性を求めない場合は、当然のことながら密着剤添加の必要性はない。   In the present invention, in order to particularly improve the adhesion of the solid component of the ink to the writing surface, it is possible to add a petroleum resin or a hydrogenated petroleum resin as an adhesion agent in the ink. These resins are selected on the condition that they are soluble in the dispersion medium and do not inhibit the dispersion and stability of the pigment. This use protects the writing warehouse from being damaged by rubbing and wetting. The following substances can be exemplified as the adhesive suitably used in the present invention. A hydrogenated alicyclic hydrocarbon resin, for example, Escorez 5300 manufactured by ExxonMobil, or a modified product thereof, and an aliphatic / aromatic hydrocarbon resin such as Quinton D-200 manufactured by Nippon Zeon Co., Ltd. can be suitably used. When permanentness is not required for the written image, it is needless to say that there is no need to add an adhesive.

本発明の筆記具で用いるインクにおける顔料の分散は、前項に述べた分散剤と分散助剤を溶解して含有する分散媒体と顔料を湿式分散することで達成される。効率よく分散するために濃厚分散液を調製し、これを分散媒体で希釈して所望濃度のインクとすることも可能である。湿式分散は当業界で従来公知の分散技術を適用して実施可能である。筆記目的に応じた性能に調製されたインクは筆記具に収蔵されて筆記具が完成する。   Dispersion of the pigment in the ink used in the writing instrument of the present invention is achieved by wet-dispersing the dispersion medium and the pigment containing the dispersant and dispersion aid described in the previous section. In order to disperse efficiently, a concentrated dispersion can be prepared and diluted with a dispersion medium to obtain an ink having a desired concentration. Wet dispersion can be carried out by applying dispersion techniques conventionally known in the art. Ink prepared for performance according to the purpose of writing is stored in the writing instrument to complete the writing instrument.

インクの組成配合は筆記目的によっておのずから異なるが、通常の使用目的においては以下の配合が好ましい。すなわち、本発明の筆記具で用いるインクにおいて、インク全量中着色剤(1)の含有量が3.0wt%以上20.0wt%以下、高分子分散剤(3)が前記着色剤の0.5重量倍以上1.0重量倍以下、分散助剤(4)の一方である分散助剤(a)N,N−ジアルキルアミノエチルアクリレートが前記着色剤の0.10重量倍以上0.80重量倍以下、他方の分散助剤(b)のナフトールAS−Fまたは/およびナフトールAS−PSが前記着色剤の0.01重量倍以上0.50重量倍以下、所望により含有する密着剤(5)が前記着色剤の0.02重量倍以上5.0重量倍以下である各範囲から選ばれた値であり、残余がイソパラフィンである組成比率からなる溶剤系顔料分散インクが好適である。上記の範囲をいくらか逸脱しても本発明は実施可能であるが、インクとしての性能が低いか過剰品質となるので好ましくない。   The composition of the ink is naturally different depending on the purpose of writing, but the following composition is preferred for normal use. That is, in the ink used in the writing instrument of the present invention, the content of the colorant (1) in the total amount of the ink is 3.0 wt% or more and 20.0 wt% or less, and the polymer dispersant (3) is 0.5 to 1.0 times the weight of the colorant. The dispersion aid (a) N, N-dialkylaminoethyl acrylate, which is one of the dispersion aids (4), is 0.10 to 0.80 times the colorant, and the other dispersion aid (b). Each of naphthol AS-F and / or naphthol AS-PS is 0.01 to 0.50 times by weight of the colorant, and the adhesive (5) optionally contained is 0.02 to 5.0 times by weight of the colorant. A solvent-based pigment-dispersed ink having a composition ratio in which the value is selected from the range and the balance is isoparaffin is preferable. Although the present invention can be carried out even if it deviates from the above range, it is not preferable because the performance as an ink is low or excessive.

本発明の筆記具で用いるインクにおいて、保管中あるいは使用中にインクに含まれるN,N−ジアルキルアミノエチルアクリレートの変質が心配される場合には、従来公知の酸化防止剤から当該インクに可溶性の酸化防止剤を選んで、その少量を追加配合することが可能である。その例としては、2,6-ジブチル-4-メチルフェノールが挙げられる。   In the ink used in the writing instrument of the present invention, when there is a concern about the deterioration of the N, N-dialkylaminoethyl acrylate contained in the ink during storage or use, a conventional oxidation inhibitor soluble in the ink is oxidized. It is possible to select an inhibitor and add a small amount thereof. An example is 2,6-dibutyl-4-methylphenol.

本発明の筆記具で用いるインクにおいて、気泡が発生して使用に困難をきたす場合があれば、少量の消泡剤を追加配合して前記困難を回避することができる。ビックケミー社製のBYK−088はその好適例である。本発明のインク組成物の使用に当たって、インクが使用に適した流動性を持つように粘性を調整するには、前記密着剤を所定量配合することでも、あるいは媒体のイソバラフインの留分組成を変更すれことでも可能である。また、本発明のインク組成物における媒体の蒸発速度を調整するには、用いるイソバラフインの留分組成を変更すれば良いので、例えば、市販のイソパラフィンのことなる銘柄を混合することで容易に目的を達成することが可能である。これらの変更は筆記具インクの使用目的を損なわない範囲で実施可能である。また、筆記具用インクでしばしば認められる防腐剤や界面活性剤の併用は、本発明のインク組成物では使用原料の特性からその必要性はない。   In the ink used in the writing instrument of the present invention, if there are cases where bubbles are generated and the use is difficult, a small amount of an antifoaming agent can be added to avoid the difficulty. BYK-088 manufactured by Big Chemie is a suitable example. In using the ink composition of the present invention, in order to adjust the viscosity so that the ink has fluidity suitable for use, the predetermined amount of the above-mentioned adhesion agent is blended or the fractional composition of isobaraffine in the medium is changed. You can also do anything. Further, in order to adjust the evaporation rate of the medium in the ink composition of the present invention, it is only necessary to change the fraction composition of isobaraffine used. For example, the purpose can be easily achieved by mixing brands different from commercially available isoparaffins. It is possible to achieve. These changes can be made within a range that does not impair the intended use of the writing instrument ink. Further, the combined use of preservatives and surfactants often observed in writing instrument inks is not necessary in the ink composition of the present invention because of the characteristics of the raw materials used.

以下に実施例を挙げて本発明実施の態様例を具体的に示す。なお、実施例や比較例における部は重量部である。   Examples of embodiments of the present invention will be specifically described below with reference to examples. In addition, the part in an Example and a comparative example is a weight part.

実施例1
分散助剤(a)N,N−ジメチルアミノエチルアクリレート(興人製)に併用分散助剤(b)ナフトールAS−Fを溶解した液を調製した。この液をイソバラフイン(出光石油化学製:IPソルベント1016)で希釈し、分散助剤(a)0.030部、分散助剤(b)0.118部およびイソパラフィン37.5部からなる分散助剤液とした。これに、高分子分散剤ソルスパース−11200(ルーグノゾル社製:純分40.0wt%)1.852部、カーボンブラック(デグサ社製:スペシャルブラック5)6.0部、密着剤用石油樹脂(日本ゼオン社製:クイントンD−200)4.5部を混合し、ビーズミルで分散させた。えられた濃厚分散液をイソパラフィン(IPソルベント1620)50.0部で希釈し、筆記具用溶剤系顔料分散インクがえられた。粘度は1.9(mPa)、顔料の平均粒径は120(nm)であった。インクの一部を2個のガラス容器に移して密栓し、一方は50℃の恒温室に10日間、他方は室温で2ケ月間静置した。いずれの場合も、インク調製直後同様に顔料の凝集や沈殿は認められなかった。このインクは調製直後と前記放置後にマーカーのインク溜に注入して筆記試験にに供したところ、紙やブラスチックフィルム等の基材表面に順調に濃色の筆記ができた。インクの乾燥速度は大で数秒後には固化していた。また、1時間のキャップオフ後の筆記も同様に順調であった。
Example 1
Dispersion aid (a) N, N-dimethylaminoethyl acrylate (manufactured by Kojin) was used together with a dispersion aid (b) naphthol AS-F dissolved in liquid. This solution was diluted with Isobaraphine (Idemitsu Petrochemicals: IP Solvent 1016) to obtain a dispersion aid liquid consisting of 0.030 parts of dispersion aid (a), 0.118 parts of dispersion aid (b) and 37.5 parts of isoparaffin. To this, 1.852 parts of a polymer dispersant Solsperse-11200 (manufactured by Lugnosol: 40.0 wt% pure), 6.0 parts of carbon black (manufactured by Degussa: Special Black 5), petroleum resin for adhesion agent (manufactured by Nippon Zeon: Quinton) D-200) 4.5 parts were mixed and dispersed with a bead mill. The obtained concentrated dispersion was diluted with 50.0 parts of isoparaffin (IP solvent 1620) to obtain a solvent-based pigment dispersion ink for writing instruments. The viscosity was 1.9 (mPa), and the average particle size of the pigment was 120 (nm). A portion of the ink was transferred to two glass containers and sealed, and one was left in a thermostatic chamber at 50 ° C. for 10 days and the other was left at room temperature for 2 months. In either case, as in the case immediately after the ink preparation, the aggregation and precipitation of the pigment was not observed. This ink was poured into the ink reservoir of the marker immediately after preparation and after being left standing, and subjected to a writing test. As a result, dark writing was smoothly performed on the surface of a substrate such as paper or plastic film. The drying speed of the ink was high and solidified after a few seconds. The writing after 1 hour of cap-off was also successful.

比較例1
実施例1における分散助剤(a)および/または分散助剤(b)を用いることなく実施例1の操作を行ったところ、えられたインクは顔料の分散に不安があり、室温放置試験で調製翌日から顔料の凝集・沈殿が明瞭に認められるようになった。それに対応して筆記試験でインクの出が悪くなった。なお、参考のためアルコール/グリコールエーテル媒体でのインクの調製を試みたが、分散助剤の有無に拘わらず分散の安定性が不十分、乾燥固化に十数秒の時間がかかり、キャップオフ20分で筆跡がかすれるようになった。
Comparative Example 1
When the operation of Example 1 was carried out without using the dispersion aid (a) and / or the dispersion aid (b) in Example 1, the obtained ink had anxiety about the dispersion of the pigment, and the room temperature standing test was conducted. From the day after the preparation, pigment aggregation and precipitation were clearly recognized. Correspondingly, the ink output deteriorated in the written test. For reference, preparation of an ink in an alcohol / glycol ether medium was attempted, but the dispersion stability was insufficient regardless of the presence or absence of a dispersion aid, and it took 10 seconds to dry and solidify. The handwriting was faded.

実施例2
実施例1における顔料のカーボンブラックを有機マゼンタ色顔料(大日精化社製:CFR−32H)に代えて実施例1の方法を繰り返し、目的とする溶剤系顔料分散インクをえた。粘度は3.2(mPa)、顔料の平均粒径は110(nm)であった。インクの一部をガラス容器に移して密栓し、50℃の恒温室に10日間、他方は2ケ月間放置した。いずれの場合も、分散液調製直後同様に顔料の凝集や沈殿は認められなかった。この溶剤系顔料インクは調製直後と前記放置後にマーカーのインク溜に注入して筆記試験にに供したところ、紙やブラスチックフィルム等の基材表面に順調に濃色の筆記ができた。インクの乾燥速度は大で数秒後には固化していた。また、1時間のキャップオフ後の筆記も同様に順調であった。
Example 2
The method of Example 1 was repeated by replacing the carbon black of the pigment in Example 1 with an organic magenta color pigment (manufactured by Dainichi Seika Co., Ltd .: CFR-32H) to obtain a target solvent-based pigment dispersion ink. The viscosity was 3.2 (mPa), and the average particle size of the pigment was 110 (nm). A part of the ink was transferred to a glass container and sealed, and left in a thermostatic chamber at 50 ° C. for 10 days and the other for 2 months. In any case, the aggregation and precipitation of the pigment were not observed as in the case immediately after preparation of the dispersion. When this solvent-based pigment ink was poured into the ink reservoir of the marker immediately after preparation and after the standing, it was used for the writing test. As a result, dark writing was smoothly performed on the surface of the substrate such as paper or plastic film. The drying speed of the ink was high and solidified after a few seconds. The writing after 1 hour of cap-off was also successful.

比較例2 実施例2における分散助剤(a)および/または分散助剤(b)を用いることなく実施例2の操作を行ったところ、えられた溶剤系顔料分散インク組成物は顔料の分散に不安があり、室温放置試験で調製3日後から顔料の凝集・沈殿が明瞭に認められるようになった。放置後のインクをマーカーに収蔵して筆記試験に供したところ、インクの乾燥固化速度は満足すべきものであったが、筆跡にかすれが生じて満足な筆記はできなかった。   Comparative Example 2 When the operation of Example 2 was performed without using the dispersion aid (a) and / or the dispersion aid (b) in Example 2, the obtained solvent-based pigment dispersion ink composition was a pigment dispersion. In the room temperature standing test, pigment aggregation and precipitation were clearly observed after 3 days of preparation. When the ink after storage was stored in a marker and subjected to a writing test, the drying and solidifying speed of the ink was satisfactory, but the writing was blurred, and satisfactory writing was not possible.

実施例3
顔料を有機黄色顔料(バイエル社製:イエローピクメントE4GN)、に代えて実施例1の方法を繰り返し、溶剤系顔料分散インクをえた。粘度は3.3(mPa)、顔料の平均粒径は130(nm)であった。インクの一部をガラス容器に移して密栓し、50℃の高温室に11日間、他方は2ケ月間放置した。いずれの場合も、分散液調製直後同様に顔料の凝集や沈殿は認められなかった。この溶剤系顔料分散インクは調製直後と前記放置後にマーカーのインク溜に注入して筆記試験にに供したところ、紙や木板等の基材表面に順調に濃色の筆記ができた。インクの乾燥速度は大で数秒後には固化していた。また、1時間のキャップオフ後の筆記も同様に順調であった。
Example 3
The method of Example 1 was repeated instead of the organic yellow pigment (manufactured by Bayer: Yellow Pigment E4GN) to obtain a solvent-based pigment-dispersed ink. The viscosity was 3.3 (mPa), and the average particle size of the pigment was 130 (nm). A portion of the ink was transferred to a glass container and sealed, and left in a high temperature chamber at 50 ° C. for 11 days and the other for 2 months. In any case, the aggregation and precipitation of the pigment were not observed as in the case immediately after preparation of the dispersion. When this solvent-based pigment-dispersed ink was poured into the ink reservoir of the marker immediately after preparation and after the standing, it was subjected to a writing test. As a result, dark writing was smoothly performed on the surface of a substrate such as paper or wood board. The drying speed of the ink was high and solidified after a few seconds. The writing after 1 hour of cap-off was also successful.

比較例3
実施例3における分散助剤(a)および/または分散助剤(b)を用いることなく実施例3の操作を行ったところ、えられた溶剤系顔料分散インクは顔料の分散に不安があり、50℃恒温静置試験2日目、室温静置試験で4日後から顔料の凝集・沈殿が明瞭に認められるようになり、それらのインクで筆記試験を行った結果は、インクの乾燥固化速度やキャップオフ時間はよいものの、肝心のインクの流動性が悪く筆跡にかすれが生じた。
Comparative Example 3
When the operation of Example 3 was carried out without using the dispersion aid (a) and / or the dispersion aid (b) in Example 3, the obtained solvent-based pigment dispersion ink had anxiety in pigment dispersion, On the second day of the 50 ° C. constant temperature test, pigment aggregation / precipitation was clearly recognized after 4 days in the room temperature static test. The results of the writing test with these inks showed that Although the cap-off time was good, the fluidity of the essential ink was poor and the handwriting was blurred.

実施例4
顔料を有機青色顔料(東洋インキ社製:リオノールブルー7400G)に代えて実施例1の方法を繰り返し、溶剤系顔料分散インクをえた。このインクで先行実施例同様に分散安定性試験や筆記試験に供したところ満足すべき結果を得た。
Example 4
The method of Example 1 was repeated by replacing the pigment with an organic blue pigment (Toyo Ink Co., Ltd .: Lionol Blue 7400G) to obtain a solvent-based pigment dispersion ink. When this ink was subjected to a dispersion stability test and a writing test as in the preceding examples, satisfactory results were obtained.

比較例4
実施例4における分散助剤(a)および/または分散助剤(b)を用いることなく実施例4の操作を行ったところ、えられた溶剤系顔料分散インク組成物は顔料の分散に不安があり、50℃恒温静置試験2日目、室温静置試験で4日後から顔料の凝集・沈殿が明瞭に認められるようになり、筆記試験でも満足な結果はえられなかった。
Comparative Example 4
When the operation of Example 4 was performed without using the dispersion aid (a) and / or the dispersion aid (b) in Example 4, the obtained solvent-based pigment dispersion ink composition was uneasy about pigment dispersion. In addition, pigment aggregation and precipitation were clearly recognized after 4 days in the 50 ° C. constant temperature standing test on the second day and the room temperature standing test, and satisfactory results were not obtained even in the writing test.

実施例5
顔料を有機赤色顔料(冨士色素社製:フジファーストレッド1010)に代え、かつ、密着剤の石油樹脂を用いることなく実施例1と同様の方法で、顔料4.0部、分散助剤(a)N,N−ジメチルアミノエチルアクリレート0.200部、分散助剤(b)ナフトールAS−F0.050部、高分子分散剤ソルスパース1.750部、分散媒体イソパラフィン94.0部からなる溶剤系顔料分散インクをえた。粘度は3.0(mPa)、顔料の平均粒径は125(nm)であった。インクの一部をガラス容器に移して密栓し、50℃の高温室に14日間、他方は2ケ月間放置した。いずれの場合も、分散液調製直後同様に顔料の凝集や沈殿は認められなかった。これらのインクで先行実施例同様に分散安定性試験や筆記試験に供したところ満足すべき結果を得た。
Example 5
The pigment was replaced with an organic red pigment (manufactured by Fuji Color Co., Ltd .: Fuji First Red 1010), and 4.0 parts of pigment and dispersion aid (a) N were obtained in the same manner as in Example 1 without using a petroleum resin as an adhesive. , N-dimethylaminoethyl acrylate, 0.200 parts of dispersion aid (b) naphthol AS-F 0.050 parts, polymer dispersant Solsperse 1.750 parts, and dispersion medium isoparaffin 94.0 parts were obtained. The viscosity was 3.0 (mPa), and the average particle size of the pigment was 125 (nm). A part of the ink was transferred to a glass container and sealed, and left in a high temperature chamber at 50 ° C. for 14 days and the other for 2 months. In any case, the aggregation and precipitation of the pigment were not observed as in the case immediately after preparation of the dispersion. When these inks were subjected to a dispersion stability test and a writing test in the same manner as in the previous examples, satisfactory results were obtained.

比較例5
実施例5における分散助剤(a)および/または分散助剤(b)を用いることなく実施例5の操作を行ったところ、えられた溶剤系顔料分散インク組成物は顔料の分散に不安があり、50℃恒温静置試験2日目、室温静置試験で5日後から顔料の凝集・沈殿が明瞭に認められるようになり、筆記試験でも満足な結果はえられなかった。
Comparative Example 5
When the operation of Example 5 was carried out without using the dispersion aid (a) and / or the dispersion aid (b) in Example 5, the obtained solvent-based pigment dispersion ink composition was uneasy about pigment dispersion. Yes, pigment aggregation and precipitation were clearly recognized after 5 days in the room temperature standing test on the second day of the 50 ° C. constant temperature test, and satisfactory results were not obtained in the written test.

実施例6
分散助剤(a)N,N−ジメチルアミノエチルアクリレート0.20部、分散助剤(b)ナフトールAS−PS0.02部、高分子分散剤ソルスパース1.80部、密着剤用石油樹脂(クイントンD−200)7.0部、およびイソパラフィン(IPソルベント1620)90.08部からなる均一溶液に、カーボンブラック(デグサ社製:スペシャルブラック4)4.00部を混合した。混合液を長時間かけてビーズミルで分散し、目的とする溶剤系顔料分散インクをえた。粘度は2.4(mPa)、顔料の平均粒径は110(nm)であった。その一部を用いて50℃の静置10日間と室温静置2ヶ月の分散安定性試験に供した。いずれの場合も、分散液調製直後同様に顔料の凝集や沈殿は認められなかった。この溶剤系顔料分散インクは調製直後と前記放置後に先行実施例同様の分散安定性試験や筆記試験に供したところ満足すべき結果を得た。
Example 6
Dispersing aid (a) N, N-dimethylaminoethyl acrylate 0.20 parts, Dispersing aid (b) Naphthol AS-PS 0.02 parts, Polymer dispersant Solsperse 1.80 parts, Adhesive petroleum resin (Quinton D-200) Carbon black (Degussa Co., Ltd .: Special Black 4) 4.00 parts was mixed with a homogeneous solution consisting of 7.0 parts and isoparaffin (IP solvent 1620) 90.08 parts. The mixed liquid was dispersed with a bead mill over a long period of time to obtain a target solvent-based pigment dispersion ink. The viscosity was 2.4 (mPa), and the average particle size of the pigment was 110 (nm). A part of the sample was subjected to a dispersion stability test for 10 days at 50 ° C. and 2 months at room temperature. In any case, the aggregation and precipitation of the pigment were not observed as in the case immediately after preparation of the dispersion. The solvent-based pigment-dispersed ink was subjected to a dispersion stability test and a writing test similar to the preceding examples immediately after preparation and after the standing, and satisfactory results were obtained.

比較例6
実施例6における分散助剤(a)および/または分散助剤(b)を用いることなく実施例6の操作を行ったところ、えられた溶剤系顔料分散インクは顔料の分散に不安があり、50℃静置試験開始の翌日、室温静置試験3日後から顔料の凝集・沈殿が明瞭に認められるようになった。放置後のインクの筆記試験でも満足な結果はえられなかった。
Comparative Example 6
When the operation of Example 6 was performed without using the dispersion aid (a) and / or the dispersion aid (b) in Example 6, the obtained solvent-based pigment dispersion ink had anxiety in pigment dispersion, The day after the start of the 50 ° C. static test, and 3 days after the static test at room temperature, pigment aggregation and precipitation were clearly observed. Satisfactory results were not obtained in the ink writing test after being left.

Claims (3)

(1)着色剤としてカーボンブラックや有機顔料の群から選ばれた微細粒子状顔料、(2)分散媒体としてイソパラフィン、(3)分散剤として従来公知で該媒体に溶解性の高分子分散剤、および(4)分散助剤として(a)N,N−ジアルキルアミノエチルアクリレートと(b)N−(1'−スルホキシ−3'−メチル−5'−クロロ)−3−ヒドロキシ−2−ナフタレンカルボキサミドまたは/およびN−(3'−スルホキシ)−3−ヒドロキシ−2−ナフタレンカルボキサミドである(a)と(b)の両者、さらに要すれば(5)密着剤として従来公知で該媒体に溶解性の石油系樹脂あるいは水添石油系樹脂を構成要素として含有する溶剤系顔料分散インクを用いてなることを特徴とする筆記具。   (1) Fine particulate pigment selected from the group of carbon black and organic pigment as a colorant, (2) isoparaffin as a dispersion medium, (3) a polymer dispersant conventionally known as a dispersant and soluble in the medium, And (4) (a) N, N-dialkylaminoethyl acrylate and (b) N- (1′-sulfoxy-3′-methyl-5′-chloro) -3-hydroxy-2-naphthalenecarboxamide as a dispersion aid And / or N- (3′-sulfoxy) -3-hydroxy-2-naphthalenecarboxamide (a) and (b), and if necessary, (5) conventionally known as an adhesive and soluble in the medium A writing instrument comprising a solvent-based pigment-dispersed ink containing a petroleum resin or hydrogenated petroleum resin as a constituent element. 請求項1記載の筆記具において、インク全量中着色剤(1)の含有量が3.0wt%以上20.0wt%以下、高分子分散剤(3)が前記着色剤の0.5重量倍以上1.0重量倍以下、分散助剤(4)の一方である分散助剤(a)N,N−ジアルキルアミノエチルアクリレートが前記着色剤の0.10重量倍以上0.80重量倍以下、他方の分散助剤(b)N−(1'−スルホキシ−3'−メチル−5'−クロロ)−3−ヒドロキシ−2−ナフタレンカルボキサミドまたは/およびN−(3'−スルホキシ)−3−ヒドロキシ−2−ナフタレンカルボキサミドが前記着色剤の0.01重量倍以上0.50重量倍以下、所望により含有する密着剤(5)が前記着色剤の0.02重量倍以上5.0重量倍以下である各範囲から選ばれた値であり、残余がイソパラフィンである組成比率からなる溶剤系顔料分散インクを用いてなることを特徴とする請求項1に記載の筆記具。   The writing instrument according to claim 1, wherein the content of the colorant (1) in the total amount of the ink is 3.0 wt% or more and 20.0 wt% or less, and the polymer dispersant (3) is 0.5 wt% or more and 1.0 wt% or less of the colorant, The dispersion aid (a) N, N-dialkylaminoethyl acrylate, which is one of the dispersion aids (4), is 0.10 to 0.80 times the colorant, and the other dispersion aid (b) N- (1 '-Sulfoxy-3'-methyl-5'-chloro) -3-hydroxy-2-naphthalenecarboxamide or / and N- (3'-sulfoxy) -3-hydroxy-2-naphthalenecarboxamide is 0.01 weight of the colorant 2 to 0.50 times by weight, the adhesive (5) optionally contained is a value selected from each range from 0.02 to 5.0 times by weight of the colorant, and consists of a composition ratio in which the balance is isoparaffin The solvent-based pigment dispersion ink is used. Writing instrument. 請求項2記載の筆記具のインクにおいて、分散媒体であるイソパラフィンの常圧沸点が約90℃以上165℃以下の分留成分で、かつ、50%留出沸点が約115℃、90%留出沸点が約125℃であることを特徴とする、請求項2に記載の筆記具。
3. The ink of the writing instrument according to claim 2, wherein isoparaffin as a dispersion medium has a fractional distillation component having an atmospheric pressure boiling point of about 90 ° C. or more and 165 ° C. or less, a 50% distillation boiling point of about 115 ° C., and a 90% distillation boiling point. The writing instrument according to claim 2, wherein is approximately 125 ° C.
JP2006174978A 2006-06-26 2006-06-26 Writing instrument Pending JP2008001852A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008138126A (en) * 2006-12-04 2008-06-19 Sakura Color Prod Corp Black ink composition for oily marking pen
JP2008156421A (en) * 2006-12-21 2008-07-10 Zebra Pen Corp Oily ink for marking pen
JP2011042699A (en) * 2009-08-19 2011-03-03 Riso Kagaku Corp Nonaqueous pigment ink
CN102023662A (en) * 2010-11-25 2011-04-20 美的集团有限公司 Control circuit for heating device and heating device using same
JP2011080025A (en) * 2009-10-10 2011-04-21 Pilot Ink Co Ltd Reversible thermochromic oil ink composition for ballpoint pen and ballpoint pen incorporating the same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008138126A (en) * 2006-12-04 2008-06-19 Sakura Color Prod Corp Black ink composition for oily marking pen
JP2008156421A (en) * 2006-12-21 2008-07-10 Zebra Pen Corp Oily ink for marking pen
JP2011042699A (en) * 2009-08-19 2011-03-03 Riso Kagaku Corp Nonaqueous pigment ink
JP2011080025A (en) * 2009-10-10 2011-04-21 Pilot Ink Co Ltd Reversible thermochromic oil ink composition for ballpoint pen and ballpoint pen incorporating the same
CN102023662A (en) * 2010-11-25 2011-04-20 美的集团有限公司 Control circuit for heating device and heating device using same
CN102023662B (en) * 2010-11-25 2015-08-19 美的集团股份有限公司 A kind of control circuit of heating appliances and adopt the heating appliances of this control circuit

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