JP2006298990A - Aqueous ink composition for reversibly thermochromic writing utensil and writing utensil containing the same - Google Patents
Aqueous ink composition for reversibly thermochromic writing utensil and writing utensil containing the same Download PDFInfo
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- JP2006298990A JP2006298990A JP2005119222A JP2005119222A JP2006298990A JP 2006298990 A JP2006298990 A JP 2006298990A JP 2005119222 A JP2005119222 A JP 2005119222A JP 2005119222 A JP2005119222 A JP 2005119222A JP 2006298990 A JP2006298990 A JP 2006298990A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/305—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers with reversible electron-donor electron-acceptor compositions
Abstract
Description
本発明は可逆熱変色性筆記具用水性インキ組成物及びそれを収容した筆記具に関する。 The present invention relates to a water-based ink composition for a reversible thermochromic writing instrument and a writing instrument containing the same.
従来より、温度変化により色調が変化する筆跡を形成できる可逆熱変色性筆記具用水性インキと、それを収容した筆記具が開示されている（例えば、特許文献１参照）。
前記筆記具は、可逆熱変色性マイクロカプセル顔料の凝集、沈降を抑制し、筆記不能や筆跡の淡色化を防止できる筆記具であって、収容されるインキは高分子凝集剤の添加によりマイクロカプセル顔料粒子間のゆるい橋かけ作用を生じさせ、ゆるい凝集状態を示すため、繊維集束体からなるインキ吸蔵体及びマーキングペン体の毛管間隙でマイクロカプセル顔料の分離が発生し難く、前述の問題を抑制できるものである。
The writing instrument is a writing instrument that suppresses aggregation and sedimentation of reversible thermochromic microcapsule pigments and prevents inability to write and lightening of handwriting, and the ink contained therein is microcapsule pigment particles by adding a polymer flocculant. The microcapsule pigment is hardly separated in the capillary gap between the ink occlusion body and the marking pen body made of a fiber bundling body because it causes a loose bridging action between them and shows a loose aggregation state. It is.
しかしながら、前記可逆熱変色性筆記具用水性インキは高分子凝集剤の添加のみにより完全に筆記不能や筆跡の淡色化を防止できるものではなく、これはマイクロカプセル顔料の発色時と消色時の比重が異なることが要因であることを本発明者は見出して本発明を完成させた。 However, the water-based ink for reversible thermochromic writing instruments cannot completely prevent writing or lightening of the handwriting only by adding a polymer flocculant. This is because the specific gravity at the time of coloring and decoloring of microcapsule pigments is not possible. The present inventor found that the difference was a factor, and completed the present invention.
本発明は、前記した従来の可逆熱変色性筆記具用水性インキ組成物及びそれを収容した筆記具の問題点を解消しようとするものであって、即ち、（イ）電子供与性呈色性有機化合物、（ロ）電子受容性化合物、（ハ）前記両者の呈色反応の生起温度を決める反応媒体からなる可逆熱変色性組成物を内包させた可逆熱変色性マイクロカプセル顔料と、水と水溶性有機溶剤と水溶性高分子凝集剤とを少なくとも含有するビヒクルとからなる水性インキ組成物において、前記可逆熱変色性マイクロカプセル顔料の消色時の比重（Ｘ）と発色時の比重（Ｙ）とビヒクルの比重（Ｚ）が下記式（１）及び（２）を満たす可逆熱変色性筆記具用水性インキ組成物を要件とする。
Ｘ−０．０２≦Ｚ＜Ｙ （１）
Ｘ＜Ｙ≦Ｘ＋０．０３ （２）
更には、前記前記可逆熱変色性マイクロカプセル顔料の消色時の比重（Ｘ）が１．０以上であること、前記水溶性有機溶剤の比重が１．１以上であること等を要件とする。
更には、前記可逆熱変色性筆記具用水性インキ組成物を収容してなる筆記具、軸筒内に繊維集束体からなるインキ吸蔵体を収容し、軸筒先端部にマーキングペンチップを固着し、前記インキ吸蔵体とマーキングペンチップは直接又は接続部材を介して連通してなり、前記インキ吸蔵体に前記可逆熱変色性水性インキ組成物を含浸してなる筆記具を要件とする。
The present invention is intended to solve the problems of the above-described conventional water-based ink composition for reversible thermochromic writing instruments and writing instruments containing the same, namely, (a) an electron-donating color-forming organic compound. (B) an electron-accepting compound, (c) a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition comprising a reaction medium that determines the temperature at which the color reaction of both occurs, water and water solubility In a water-based ink composition comprising an organic solvent and a vehicle containing at least a water-soluble polymer flocculant, specific gravity (X) at the time of decoloring and specific gravity (Y) at the time of color development of the reversible thermochromic microcapsule pigment A water-based ink composition for a reversible thermochromic writing instrument satisfying the following formulas (1) and (2) is required.
X−0.02 ≦ Z <Y (1)
X <Y ≦ X + 0.03 (2)
Furthermore, the specific gravity (X) at the time of decoloration of the reversible thermochromic microcapsule pigment is 1.0 or more, and the specific gravity of the water-soluble organic solvent is 1.1 or more. .
Further, a writing instrument containing the water-based ink composition for reversible thermochromic writing instrument, an ink occlusion body comprising a fiber bundle in the shaft cylinder, a marking pen tip fixed to the tip of the shaft cylinder, The ink occlusion body and the marking pen tip communicate with each other directly or through a connecting member, and a writing instrument formed by impregnating the ink occlusion body with the reversible thermochromic aqueous ink composition is a requirement.
本発明は、経時によって筆記時のインキ流出性を損なうことがなく、よって、筆跡がかすれたり、淡色化することのない良好な筆記性能を示す可逆熱変色性筆記具用水性インキ組成物及びそれを収容した筆記具を提供する。 The present invention provides a water-based ink composition for a reversible thermochromic writing instrument that does not impair ink outflow properties during writing over time, and thus exhibits good writing performance without fading or fading. Provide housed writing instruments.
前記可逆熱変色性マイクロカプセル顔料は、従来より公知の（イ）電子供与性呈色性有機化合物、（ロ）電子受容性化合物、及び（ハ）前記両者の呈色反応の生起温度を決める反応媒体の必須三成分を少なくとも含む可逆熱変色性組成物をマイクロカプセル中に内包させたものが有効であり、発色状態からの加熱により消色する加熱消色型のマイクロカプセル顔料としては特公昭５１−４４７０６号公報、特公昭５１−４４７０７号公報、特公平１−２９３９８号公報等に記載のものが利用できる。
前記マイクロカプセル顔料は所定の温度（変色点）を境としてその前後で変色し、完全消色温度以上の温度域で消色状態、完全発色温度以下の温度域で発色状態を呈し、前記両状態のうち常温域では特定の一方の状態しか存在しない。即ち、もう一方の状態は、その状態が発現するのに要した熱又は冷熱が適用されている間は維持されるが、前記熱又は冷熱の適用がなくなれば常温域で呈する状態に戻る、ヒステリシス幅が比較的小さい特性（ΔＨＡ＝１〜７℃）を有する（図１参照）。
The reversible thermochromic microcapsule pigment is a conventionally known (a) electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction that determines the temperature at which the color reaction of both occurs. A reversible thermochromic composition containing at least the essential three components of the medium is effectively encapsulated in a microcapsule. -44706 gazette, Japanese Examined Patent Publication No. 51-44707 gazette, Japanese Patent Publication No. 1-29398 gazette, etc. can be used.
The microcapsule pigment discolors before and after a predetermined temperature (discoloration point), exhibits a decolored state in a temperature range above the complete decolorization temperature, and exhibits a color development state in a temperature range below the complete color development temperature. Of these, only one specific state exists at room temperature. That is, the other state is maintained while the heat or cold necessary to develop the state is applied, but when the heat or cold is not applied, the state returns to the state exhibited in the normal temperature range. The width is relatively small (ΔH A = 1-7 ° C.) (see FIG. 1).
また、特公平４−１７１５４号公報、特開平７−１７９７７７号公報、特開平７−３３９９７号公報、特開平８−３９９３６号公報等に記載されている大きなヒステリシス特性（ΔＨＢ＝８〜５０℃）を示す、即ち、温度変化による着色濃度の変化をプロットした曲線の形状が、温度を変色温度域より低温側から上昇させていく場合と逆に変色温度域より高温側から下降させていく場合とで大きく異なる経路を辿って変色し、完全発色温度（ｔ１）以下の低温域での発色状態、又は完全消色温度（ｔ４）以上の高温域での消色状態が、特定温度域〔ｔ２〜ｔ３の間の温度域（実質的二相保持温度域）〕で色彩を記憶保持できる可逆熱変色性組成物をマイクロカプセル中に内包させた加熱消色型のマイクロカプセル顔料も適用できる（図２参照）。
なお、色彩を記憶保持できる加熱消色型のマイクロカプセル顔料としては、本出願人が先に出願した（ハ）成分として一般式（１）で示されるエステル化合物を用いたものが色濃度−温度曲線に関して広いヒステリシス幅（ΔＨＢ＝４０〜７０℃）を示して変色するため、好適である。
前記変色前後の両状態のうち常温域で特定の一方の状態のみ存在させるためには、ヒステリシス幅が４０〜７０℃、好ましくは５０〜７０℃、更に好ましくは６０〜７０℃であり、完全消色温度（ｔ４）が４５℃以上、好ましくは５０℃以上であり、且つ、発色開始温度（ｔ２）が０℃以下、好ましくは−５℃以下である。
式中のＲは炭素数４以上のアルキル基又はアルケニル基を示すが、好ましくは炭素数６〜２０のアルキル基、更に好ましくは炭素数８〜１８のアルキル基である。
前記化合物として具体的には、ブタン酸−４−ベンジルオキシフェニルエチル、ペンタン酸−４−ベンジルオキシフェニルエチル、ヘキサン酸−４−ベンジルオキシフェニルエチル、ヘプタン酸−４−ベンジルオキシフェニルエチル、オクタン酸−４−ベンジルオキシフェニルエチル、ノナン酸−４−ベンジルオキシフェニルエチル、デカン酸−４−ベンジルオキシフェニルエチル、ウンデカン酸−４−ベンジルオキシフェニルエチル、ドデカン酸−４−ベンジルオキシフェニルエチル、トリデカン酸−４−ベンジルオキシフェニルエチル、テトラデカン酸−４−ベンジルオキシフェニルエチル、ペンタデカン酸−４−ベンジルオキシフェニルエチル、ヘキサデカン酸−４−ベンジルオキシフェニルエチル、ヘプタデカン酸−４−ベンジルオキシフェニルエチル、オクタデカン酸−４−ベンジルオキシフェニルエチル、ノナデカン酸−４−ベンジルオキシフェニルエチル、エイコサン酸−４−ベンジルオキシフェニルエチル、トリコサン酸−４−ベンジルオキシフェニルエチル、テトラコサン酸−４−ベンジルオキシフェニルエチル、ペンタコサン酸−４−ベンジルオキシフェニルエチル、ヘキサコサン酸−４−ベンジルオキシフェニルエチル、ヘプタコサン酸−４−ベンジルオキシフェニルエチル、オクタコサン酸−４−ベンジルオキシフェニルエチル、ノナコサン酸−４−ベンジルオキシフェニルエチル、トリアコンタン酸−４−ベンジルオキシフェニルエチル、ヘントリアコンタン酸−４−ベンジルオキシフェニルエチルを例示できる。
In addition, large hysteresis characteristics (ΔH B = 8 to 50 ° C.) described in JP- B -4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ), That is, when the shape of the curve plotting the change in the color density due to the temperature change is lowering the temperature from the lower temperature side than the color changing temperature range, as opposed to increasing the temperature from the lower temperature side. In the specific temperature range, the color changes in a low temperature range below the complete color development temperature (t 1 ) or the color erase state in the high temperature range above the complete color erase temperature (t 4 ). There is also a heat decolorable microcapsule pigment in which a reversible thermochromic composition capable of storing and retaining colors in a temperature range between t 2 and t 3 (substantially two-phase holding temperature range) is encapsulated in microcapsules. Applicable (Figure Reference).
In addition, as the heat decoloring type microcapsule pigment capable of storing and retaining the color, the one using the ester compound represented by the general formula (1) as the component (c) previously filed by the present applicant is color density-temperature. This is suitable because the curve changes with a wide hysteresis width (ΔH B = 40 to 70 ° C.).
In order to allow only one of the states before and after the color change to exist in the normal temperature range, the hysteresis width is 40 to 70 ° C., preferably 50 to 70 ° C., more preferably 60 to 70 ° C. The color temperature (t 4 ) is 45 ° C. or higher, preferably 50 ° C. or higher, and the color development start temperature (t 2 ) is 0 ° C. or lower, preferably −5 ° C. or lower.
R in the formula represents an alkyl group or alkenyl group having 4 or more carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 8 to 18 carbon atoms.
Specific examples of the compound include butanoic acid-4-benzyloxyphenylethyl, pentanoic acid-4-benzyloxyphenylethyl, hexanoic acid-4-benzyloxyphenylethyl, heptanoic acid-4-benzyloxyphenylethyl, and octanoic acid. -4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, dodecanoic acid-4-benzyloxyphenylethyl, tridecanoic acid -4-benzyloxyphenylethyl, tetradecanoic acid-4-benzyloxyphenylethyl, pentadecanoic acid-4-benzyloxyphenylethyl, hexadecanoic acid-4-benzyloxyphenylethyl, heptadecanoic acid-4-benzylo Cyphenylethyl, octadecanoic acid-4-benzyloxyphenylethyl, nonadecanoic acid-4-benzyloxyphenylethyl, eicosanoic acid-4-benzyloxyphenylethyl, tricosanoic acid-4-benzyloxyphenylethyl, tetracosanoic acid-4-benzyl Oxyphenylethyl, pentacosanoic acid-4-benzyloxyphenylethyl, hexacosanoic acid-4-benzyloxyphenylethyl, heptacosanoic acid-4-benzyloxyphenylethyl, octacosanoic acid-4-benzyloxyphenylethyl, nonacosanoic acid-4-benzyl Examples thereof include oxyphenyl ethyl, triacontanoic acid-4-benzyloxyphenylethyl, and hentriacontanoic acid-4-benzyloxyphenylethyl.
更に、電子受容性化合物として炭素数３乃至１８の直鎖又は側鎖アルキル基を有する特定のアルコキシフェノール化合物を用いたり（特開平１１−１２９６２３号公報、特開平１１−５９７３号公報）、特定のヒドロキシ安息香酸エステルを用いたり（特開２００１−１０５７３２号公報）、没食子酸エステル等を用いた（特公昭５１−４４７０６号公報、特開２００３−２５３１４９号公報）加熱発色型のマイクロカプセル顔料を適用することもできる（図３参照）。
ここで、前記可逆熱変色性マイクロカプセル顔料中、或いはインキ中に非熱変色性の染料、顔料等の着色剤を配合して、有色（１）から有色（２）への互変的色変化を呈する構成となすこともできる。
Further, as the electron-accepting compound, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms may be used (Japanese Patent Laid-Open Nos. 11-129623 and 11-5973), Application of heating color developing type microcapsule pigment using hydroxybenzoic acid ester (Japanese Patent Laid-Open No. 2001-105732) or gallic acid ester (Japanese Patent Publication No. 51-44706, Japanese Patent Laid-Open No. 2003-253149) (See FIG. 3).
Here, the reversible thermochromic microcapsule pigment or the ink is blended with a colorant such as a non-thermochromic dye or pigment to change the color from color (1) to color (2). It can also be set as the structure which exhibits.
前記マイクロカプセル顔料は、円形断面の形態であっても非円形断面の形態であってもよい。
マイクロカプセル顔料の平均粒子径は０．５〜５．０μｍ、好ましくは０．５〜３μｍ、更に好ましくは１〜３μｍである。
平均粒子径が５．０μｍを越えるとインキ流出性が低下したり、筆記面に対する固着性が低下し易くなる。一方、平均粒子径が０．５μｍ未満では高濃度の発色性を示し難くなる。
また、可逆熱変色性組成物の壁膜に対する比率が大きくなると、壁膜の厚みが肉薄となり過ぎ、圧力や熱に対する耐性の低下を起こし、逆に、壁膜の可逆熱変色性組成物に対する比率が大きくなると発色時の色濃度及び鮮明性の低下を免れず、よって、可逆熱変色性組成物／壁膜＝６／１〜１／１（重量比）が好適である。
The microcapsule pigment may have a circular cross section or a non-circular cross section.
The average particle size of the microcapsule pigment is 0.5 to 5.0 μm, preferably 0.5 to 3 μm, more preferably 1 to 3 μm.
When the average particle diameter exceeds 5.0 μm, the ink outflow property is lowered and the fixing property to the writing surface is liable to be lowered. On the other hand, when the average particle size is less than 0.5 μm, it is difficult to exhibit high density color development.
In addition, when the ratio of the reversible thermochromic composition to the wall film increases, the wall film becomes too thin, causing a decrease in resistance to pressure and heat, and conversely, the ratio of the wall film to the reversible thermochromic composition. When the value is increased, a decrease in color density and sharpness during color development is unavoidable, and therefore, reversible thermochromic composition / wall film = 6/1 to 1/1 (weight ratio) is preferable.
前記可逆熱変色性マイクロカプセル顔料は、インキ組成物全量に対し、２〜５０重量％、好ましくは５〜４０重量％、更に好ましくは１０〜３０重量％配合することができる。
２重量％未満では発色濃度が不十分であり、５０重量％を越えるとインキ流出性が低下し、筆記性能が阻害される。
The reversible thermochromic microcapsule pigment can be blended in an amount of 2 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight, based on the total amount of the ink composition.
If it is less than 2% by weight, the color density is insufficient, and if it exceeds 50% by weight, the ink outflow is reduced and the writing performance is hindered.
前記可逆熱変色性組成物のマイクロカプセル化は、界面重合法、界面重縮合法、ｉｎ Ｓｉｔｕ重合法、コアセルベート法等の公知の手段が適用できるが、本発明の前記した要件を満たす粒子径範囲の、非円形断面形状のマイクロカプセル顔料を得るためには、凝集、合一化が生じ難い界面重合法又は界面重縮合法の適用が効果的である。 For the microencapsulation of the reversible thermochromic composition, known means such as an interfacial polymerization method, an interfacial polycondensation method, an in situ polymerization method, and a coacervate method can be applied, but the particle size range satisfying the above-described requirements of the present invention. In order to obtain a microcapsule pigment having a non-circular cross-sectional shape, it is effective to apply an interfacial polymerization method or an interfacial polycondensation method that hardly causes aggregation or coalescence.
前記インキに用いられる溶剤としては、水と必要により水溶性有機溶剤が用いられる。
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、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−ピロリドン等が用いられる。
As a solvent used for the ink, water and, if necessary, a water-soluble organic solvent are used.
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and 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 monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2- Pyrrolidone, or the like is used.
前記インキ中に高分子凝集剤を添加することによって、前記凝集剤がマイクロカプセル顔料粒子間のゆるい橋かけ作用を生じさせ、ゆるい凝集状態を示す。このようなゆるい凝集状態を示すインキは繊維集束体からなるインキ吸蔵体（中綿）及び繊維の樹脂結束体からなるマーキングペン体の毛管状間隙においてマイクロカプセル顔料の分離が発生し難くなる。
前記水溶性高分子凝集剤としては非イオン性水溶性高分子化合物が用いられ、ポリビニルピロリドン、ポリエチレンオキサイド、水溶性多糖類等が挙げられる。
前記水溶性多糖類としてはトラガントガム、グアーガム、プルラン、サイクロデキストリン、非イオン性水溶性セルロース誘導体等が挙げられ、非イオン性水溶性セルロース誘導体の具体例としてはメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース等が挙げられる。
本発明の可逆熱変色性水性インキ組成物においては、マイクロカプセル顔料粒子間のゆるい橋架け作用を示す水溶性高分子であればすべて適用することができるが、なかでも水溶性セルロース誘導体が最も有効に作用する。
By adding a polymer flocculant in the ink, the flocculant causes a loose bridging action between the microcapsule pigment particles and exhibits a loose flocculent state. Ink showing such a loose agglomerated state is unlikely to cause separation of microcapsule pigments in the capillary space of an ink occlusion body (batting) made of a fiber bundling body and a marking pen body made of a resin bundle of fibers.
As the water-soluble polymer flocculant, a nonionic water-soluble polymer compound is used, and examples thereof include polyvinyl pyrrolidone, polyethylene oxide, and water-soluble polysaccharides.
Examples of the water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, cyclodextrin, nonionic water-soluble cellulose derivatives, etc. Specific examples of nonionic water-soluble cellulose derivatives include methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxy Examples include ethyl methyl cellulose and hydroxypropyl methyl cellulose.
In the reversible thermochromic water-based ink composition of the present invention, any water-soluble polymer exhibiting a loose bridging action between microcapsule pigment particles can be applied, but water-soluble cellulose derivatives are most effective. Act on.
その他、必要に応じてベンゾトリアゾール、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、サポニン等の防錆剤、石炭酸、１，２−ベンズチアゾリン−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）ピリジン等の防腐剤或いは防黴剤、尿素、ノニオン系界面活性剤、還元又は非還元デンプン加水分解物、トレハロース等の二糖類、オリゴ糖、ショ糖、サイクロデキストリン、ぶどう糖、デキストリン、ソルビット、マンニット、ピロリン酸ナトリム等の湿潤剤、消泡剤、分散剤、インキの浸透性を向上させるフッ素系界面活性剤やノニオン系の界面活性剤を使用してもよい。 In addition, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin and other rust preventives, carboxylic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, dehydro as necessary Preservatives or antifungal agents such as sodium acetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, urea, nonionic surfactants, reduced or non- Reduced starch hydrolyzate, disaccharides such as trehalose, oligosaccharides, sucrose, cyclodextrin, glucose, dextrin, sorbit, mannitol, sodium pyrophosphate and other wetting agents, antifoaming agents, dispersants, ink permeability Fluorosurfactant to improve It may be used anion type surfactant.
前記のようにして得られるインキ組成物は、ｐＨを３〜７に調整することが好ましい。
前述のようにインキ組成物を酸性域に調整することによって含有される可逆熱変色性マイクロカプセル顔料の低温域での凝集、沈降を抑制できる。
ｐＨが７を越えると、低温域、即ち、インキが凍結する温度域で放置した時のインキ流出性を損ない易く、また、ｐＨが３未満では、カプセル中に内包した可逆熱変色性組成物の発色性が強くなり、消色時に色残りが発生する不具合を生じ易くなる。
また、インキの粘度は２〜２０ｍＰａ・ｓ（２０℃）、好ましくは、２〜１０ｍＰａ・ｓであり、２０ｍＰａ・ｓを超えるとインキ流出性が低下して筆跡がかすれたり、途切れたりすることがある。
The ink composition obtained as described above is preferably adjusted to a pH of 3 to 7.
As described above, the reversible thermochromic microcapsule pigment contained by adjusting the ink composition to the acidic range can suppress aggregation and sedimentation in the low temperature range.
When the pH exceeds 7, it tends to impair the ink outflow when left in a low temperature range, that is, the temperature range where the ink freezes. When the pH is less than 3, the reversible thermochromic composition encapsulated in the capsule The color developability becomes strong, and it becomes easy to cause a problem that a color residue occurs at the time of decoloring.
Also, the viscosity of the ink is 2 to 20 mPa · s (20 ° C.), preferably 2 to 10 mPa · s. If it exceeds 20 mPa · s, the ink outflow may be reduced and the handwriting may be faded or interrupted. is there.
前記のようにして得られる可逆熱変色性筆記具用水性インキ組成物のマイクロカプセル顔料の消色時の比重（Ｘ）と発色時の比重（Ｙ）とビヒクルの比重（Ｚ）は、下記式（１）及び（２）を満たすことが必要になる。
Ｘ−０．０２≦Ｚ＜Ｙ （１）
Ｘ＜Ｙ≦Ｘ＋０．０３ （２）
前述のように可逆熱変色性組成物を内包したマイクロカプセル顔料は、可逆熱変色性組成物が発色状態と消色状態で比重が異なる。具体的は、発色状態の比重が消色状態の比重よりも大きくなる。
よって、ビヒクルの比重と発色状態のマイクロカプセル顔料、及び、消色状態のマイクロカプセル顔料の比重差が大きく異なると、筆記具に収容された状態でビヒクルと分離し易くなる。
本発明の可逆熱変色性筆記具用水性インキ組成物を収容した筆記具においては、収容した状態のマイクロカプセル顔料は発色状態、消色状態のいずれであってもよく、また、製造工程において筆記具自体を加温又は冷却してマイクロカプセル顔料を発色状態にしたり、消色状態にすることもあり、よって、前記式（１）及び（２）の比重を満たすことは重要な要件である。
従って、前記式（１）及び（２）の比重関係を満たすことにより、インキ中のマイクロカプセル顔料がインキ中で分離して筆跡が薄くなったり、かすれたりすることを防止できる。
なお、好適には式（１）はＸ−０．０１≦Ｚ＜Ｙであり、式（２）はＸ＜Ｙ≦Ｘ＋０．０２である。
特に、ヒステリシス幅の大きい可逆熱変色性組成物を内包したマイクロカプセル顔料には比重が概ね１を越えるため、適用する水溶性有機溶剤は１．１を超えるものが好適に用いられる。比重が１．１未満の水溶性有機溶剤ではカプセル顔料との比重差において式（１）及び式（２）を満たし難く、カプセル顔料の浮上、沈降を生じ易くなり、筆跡の濃淡を生じ易くなる。
The specific gravity (X) at the time of decoloration, the specific gravity at the time of color development (Y) and the specific gravity (Z) of the vehicle of the microcapsule pigment of the water-based ink composition for reversible thermochromic writing instruments obtained as described above are represented by the following formula ( It is necessary to satisfy 1) and (2).
X−0.02 ≦ Z <Y (1)
X <Y ≦ X + 0.03 (2)
As described above, the microcapsule pigment encapsulating the reversible thermochromic composition has a specific gravity different between the reversible thermochromic composition in a colored state and a decolored state. Specifically, the specific gravity in the colored state is greater than the specific gravity in the decolored state.
Therefore, if the specific gravity difference between the specific gravity of the vehicle and the microcapsule pigment in the colored state and the microcapsule pigment in the decolored state are greatly different, it is easy to separate from the vehicle in the state of being accommodated in the writing instrument.
In the writing instrument that contains the water-based ink composition for reversible thermochromic writing instrument of the present invention, the microcapsule pigment in the accommodated state may be in a colored state or a decolored state. The microcapsule pigment may be colored or decolored by heating or cooling. Therefore, satisfying the specific gravity of the above formulas (1) and (2) is an important requirement.
Therefore, by satisfying the specific gravity relationship of the above formulas (1) and (2), it is possible to prevent the microcapsule pigment in the ink from separating in the ink and making the handwriting thin or faint.
Preferably, Formula (1) is X−0.01 ≦ Z <Y, and Formula (2) is X <Y ≦ X + 0.02.
In particular, a microcapsule pigment encapsulating a reversible thermochromic composition having a large hysteresis width has a specific gravity of more than 1, so that a water-soluble organic solvent to be applied is preferably used in excess of 1.1. A water-soluble organic solvent having a specific gravity of less than 1.1 is difficult to satisfy the formula (1) and formula (2) in the specific gravity difference from the capsule pigment, and the capsule pigment is likely to float and settle, and the density of the handwriting is likely to occur. .
前記インキ組成物は、チップを筆記先端部に装着したマーキングペンや筆ペン等の筆記具に収容して実用に供される。
マーキングペンに収容する場合、マーキングペン自体の構造、形状は特に限定されるものではないが、繊維チップ、フェルトチップ、プラスチックチップ等のマーキングペンチップを筆記先端部に装着し、軸筒内部に収容した繊維束からなるインキ吸蔵体にインキを含浸させ、筆記先端部にインキを供給する構造が好適である。
The ink composition is put to practical use by being housed in a writing instrument such as a marking pen or a brush pen having a tip attached to a writing tip.
When storing in a marking pen, the structure and shape of the marking pen itself are not particularly limited, but a marking pen tip such as a fiber tip, felt tip, plastic tip, etc. is attached to the writing tip and stored inside the shaft cylinder. A structure in which ink is impregnated into an ink occlusion body composed of a bundle of fibers and the ink is supplied to the writing tip is preferable.
インキを収容する軸筒は、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、ナイロン等の熱可塑性樹脂からなる透明性成形体が好適に用いられる。
前記軸筒の透明性とは着色透明、半透明、着色半透明を含み、インキ色を確認することができる。
なお、前記筆記具の形態は前述したものに限らず、相異なる形態のペン体を装着させたり、相異なる色調のインキを導出させるペン体を装着させたツインタイプの筆記具であってもよい。
For example, a transparent molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon is preferably used as the shaft cylinder that stores the ink.
The transparency of the shaft cylinder includes colored transparency, translucency, and colored translucency, and the ink color can be confirmed.
Note that the form of the writing instrument is not limited to that described above, and may be a twin-type writing instrument on which a pen body having a different form is mounted or a pen body on which different colors are derived is mounted.
前記インキ組成物を収容した筆記具より形成される筆跡は、指による擦過や加熱又は冷熱具の適用により変色させることができる。
前記加熱手段としては、抵抗発熱体を装備した通電加熱変色具、温水等を充填した加熱変色具、ヘアドライヤーの適用が挙げられるが、好ましくは、簡便な方法により変色可能な手段として擦過部材が用いられる。
前記擦過部材としては、弾性感に富み、擦過時に適度な摩擦を生じて摩擦熱を発生させることのできるエラストマー、プラスチック発泡体等の弾性体が好適であるが、プラスチック成形体、石材、木材、金属、布帛であってもよい。
なお、消しゴムを使用して筆跡を擦過することもできるが、擦過時に消しカスが発生するため、好ましくは前述のような擦過部材が用いられる。
前記擦過部材の材質としては、シリコーン樹脂やＳＥＢＳ樹脂（スチレンエチレンブタジエンスチレンブロック共重合体）が好適に用いられるが、シリコーン樹脂は擦過により消去した部分に樹脂が付着し易く、繰り返し筆記した際に筆跡がはじかれる傾向にあるため、ＳＥＢＳ樹脂がより好適に用いられる。
前記擦過部材は筆記具と別体の任意形状の部材であってもよいが、筆記具に固着させることにより、携帯性に優れる。
前記擦過部材を固着する箇所は、キャップ先端部（頂部）、或いは、軸筒先端部（筆記先端部を設けていない部分）が挙げられる。
更に、キャップの一部、或いは軸筒の一部に任意形象の小突部を設けて擦過部材とすることもできる。
冷却手段としては、ペルチエ素子を利用した冷熱変色具、冷水、氷片等の冷媒を充填した冷熱変色具、冷蔵庫や冷凍庫の適用が挙げられる。
The handwriting formed from the writing instrument containing the ink composition can be discolored by rubbing with a finger, heating, or application of a cooling / heating tool.
Examples of the heating means include a heating color changer equipped with a resistance heating element, a heating color changer filled with warm water, and a hair dryer. Preferably, a scraping member is used as a means capable of changing color by a simple method. Used.
As the rubbing member, an elastic body such as an elastomer or a plastic foam which is rich in elasticity and can generate frictional heat by rubbing at the time of rubbing is preferable, but a plastic molded body, stone material, wood, Metals and fabrics may be used.
Although it is possible to scrape the handwriting by using an eraser, it is preferable to use a rubbing member as described above because erase scraps are generated at the time of rubbing.
As the material of the rubbing member, silicone resin or SEBS resin (styrene ethylene butadiene styrene block copolymer) is preferably used. However, the silicone resin easily adheres to the portion erased by rubbing, and when repeatedly written. Since the handwriting tends to be repelled, SEBS resin is more preferably used.
The scraping member may be a member having an arbitrary shape that is separate from the writing instrument, but is excellent in portability by being fixed to the writing instrument.
Examples of the location where the rubbing member is fixed include a cap tip (top) or a shaft tube tip (portion where no writing tip is provided).
Furthermore, it is also possible to provide a small protrusion of any shape on a part of the cap or a part of the shaft tube to make a scraping member.
Examples of the cooling means include a cold / hot color changing tool using a Peltier element, a cold / hot color changing tool filled with a coolant such as cold water and ice pieces, a refrigerator and a freezer.
以下に本発明の実施例を示すが、本発明はこれに限定されるものではない。
実施例１
可逆熱変色性マイクロカプセル顔料の調製
（イ）成分として１，３−ジメチル−６−ジエチルアミノフルオラン２．５重量部、（ロ）成分として１，１−ビス（４′−ヒドロキシフェニル）ｎ−デカン４．０重量部、２，２−ビス（４′−ヒドロキシフェニル）ヘキサフルオロプロパン４．０重量部、（ハ）成分としてパルミチン酸４−メチルベンジル５０．０重量部からなる可逆熱変色性組成物を均一に加温溶解し、壁膜材料として芳香族多価イソシアネートプレポリマー３５．０重量部、助溶剤５０．０重量部を混合した溶液を、８％ポリビニルアルコール水溶液中で微小滴になるように乳化分散し、７０℃で約１時間攪拌を続けた後、水溶性脂肪族変性アミン２．５重量部を加え、更に６時間攪拌を続けて可逆熱変色性マイクロカプセル顔料懸濁液を得た。
前記懸濁液を遠心分離して可逆熱変色性マイクロカプセル顔料を単離した。
なお、前記マイクロカプセル顔料の消色時の比重は１．０４、発色時の比重は１．０５、平均粒子径２．５μｍ、完全消色温度は４２℃、完全発色温度は０℃であり、温度変化により橙色から無色に変色する。
Examples of the present invention are shown below, but the present invention is not limited thereto.
Example 1
Preparation of reversible thermochromic microcapsule pigment (a) 2.5 parts by weight of 1,3-dimethyl-6-diethylaminofluorane as component, (b) 1,1-bis (4'-hydroxyphenyl) n- Reversible thermochromic property comprising 4.0 parts by weight of decane, 4.0 parts by weight of 2,2-bis (4′-hydroxyphenyl) hexafluoropropane, and 50.0 parts by weight of 4-methylbenzyl palmitate as component (c). The composition is uniformly heated and dissolved, and a solution obtained by mixing 35.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 50.0 parts by weight of a co-solvent as a wall film material is formed into fine droplets in an 8% aqueous polyvinyl alcohol solution. The mixture was emulsified and dispersed, and stirred at 70 ° C. for about 1 hour. Then, 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and stirring was further continued for 6 hours to reversible thermochromic microcapsule. A pigment suspension was obtained.
The suspension was centrifuged to isolate a reversible thermochromic microcapsule pigment.
The specific gravity at the time of decoloration of the microcapsule pigment is 1.04, the specific gravity at the time of color development is 1.05, the average particle diameter is 2.5 μm, the complete color erasure temperature is 42 ° C., and the complete color development temperature is 0 ° C. The color changes from orange to colorless with temperature change.
可逆熱変色性筆記具用水性インキの調製
前記マイクロカプセル顔料２０．０重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．５重量部、グリセリン１８．０重量部、消泡剤０．０２重量部、防腐剤１．５重量部、水５９．８８重量部、１０％希釈リン酸溶液０．１重量部を加えて均一に攪拌を行い、インキのｐＨを５．５に調整して可逆熱変色性筆記具用水性インキを得た。
なお、前記インキのビヒクル比重は１．０４であった。
Preparation of water-based ink for reversible thermochromic writing instrument 20.0 parts by weight of the above microcapsule pigment, 0.5 parts by weight of hydroxyethyl cellulose [Union Carbide Japan Co., Ltd., trade name: Cellosize WP-09B], 18.0 parts by weight of glycerin Part, 0.02 part by weight of antifoaming agent, 1.5 part by weight of preservative, 59.88 parts by weight of water and 0.1 part by weight of 10% diluted phosphoric acid solution, and stirred uniformly to adjust the pH of the ink. The water-based ink for reversible thermochromic writing instruments was obtained by adjusting to 5.5.
The ink had a vehicle specific gravity of 1.04.
筆記具の作製
前記インキ（予め０℃以下に冷却してマイクロカプセル顔料を橙色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８７％）に２．０ｇ含浸させて軸筒内に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５３％）を取り付けてマーキングペンを得た。
前記マーキングペンには着脱自在のキャップを備えてなり、前記キャップには頂部に擦過部材としてＳＥＢＳ樹脂を装着してなる。
前記マーキングペンを用いて紙面に筆記して橙色の文字（筆跡）を形成した。
前記筆跡は、室温（２５℃）で橙色を呈しており、キャップに装着した擦過部材を用いて文字を擦過すると、該文字は消色して無色となり、この状態は、室温下では保持されており、０℃以下に冷却することにより、元の橙色に復色し、前記変色挙動は繰返し再現された。
Fabrication of a writing instrument The above-described ink (previously cooled to 0 ° C. or less and allowed to develop a microcapsule pigment in an orange color and then allowed to stand at room temperature), a fiber sizing ink occlusion body (porosity) coated with a polyester sliver with a synthetic resin film A marking pen was obtained by impregnating 2.0 g into a shaft cylinder and attaching a chisel type fiber pen body (porosity of about 53%) to the tip of the shaft cylinder.
The marking pen is provided with a detachable cap, and the cap is provided with a SEBS resin as a rubbing member on the top.
An orange character (handwriting) was formed by writing on the paper surface using the marking pen.
The handwriting has an orange color at room temperature (25 ° C.), and when characters are scraped with a scraping member attached to a cap, the characters are discolored and become colorless, and this state is maintained at room temperature. The original orange color was restored by cooling to 0 ° C. or lower, and the discoloration behavior was reproduced repeatedly.
実施例２
可逆熱変色性マイクロカプセル顔料の調製
（イ）成分として、２−（ジブチルアミノ）−８−（ジペンチルアミノ）−４−メチル−スピロ[５Ｈ−[1]ベンゾピラノ[２、３−ｇ]ピリミジン−５、１’（３’Ｈ）−イソベンゾフラン]−３−オン２．５重量部、（ロ）成分として１，１−ビス（４′−ヒドロキシフェニル）ｎ−デカン４．０重量部、２，２−ビス（４′−ヒドロキシフェニル）ヘキサフルオロプロパン４．０重量部、（ハ）成分としてパルミチン酸４−メチルベンジル５０．０重量部からなる可逆熱変色性組成物を均一に加温溶解し、壁膜材料として芳香族多価イソシアネートプレポリマー３５．０重量部、助溶剤５０．０重量部を混合した溶液を、８％ポリビニルアルコール水溶液中で微小滴になるように乳化分散し、７０℃で約１時間攪拌を続けた後、水溶性脂肪族変性アミン２．５重量部を加え、更に６時間攪拌を続けて可逆熱変色性マイクロカプセル顔料懸濁液を得た。
前記懸濁液を遠心分離して可逆熱変色性マイクロカプセル顔料を単離した。
なお、前記マイクロカプセル顔料の消色時の比重は１．０３、発色時の比重は１．０５、平均粒子径２．５μｍ、完全消色温度が４２℃、完全発色温度は−２℃であり、温度変化によりピンク色から無色に変色する。
Example 2
Preparation of reversible thermochromic microcapsule pigment (I) As component (2-), 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g] pyrimidine- 5, 2.5 parts by weight of 1 ′ (3′H) -isobenzofuran] -3-one, 4.0 parts by weight of 1,1-bis (4′-hydroxyphenyl) n-decane as component (2), 2 , 2-bis (4'-hydroxyphenyl) hexafluoropropane 4.0 parts by weight, and (c) a reversible thermochromic composition consisting of 5 parts by weight of 4-methylbenzyl palmitate as a component is uniformly heated and dissolved. Then, a solution prepared by mixing 35.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 50.0 parts by weight of a co-solvent as a wall film material is emulsified and dispersed in fine water droplets in an 8% aqueous polyvinyl alcohol solution. About ℃ After continued stirring time, added 2.5 parts by weight of a water-soluble aliphatic modified amine to give the reversible thermal discoloration microcapsule pigment suspension and stirring was further continued for 6 hours.
The suspension was centrifuged to isolate a reversible thermochromic microcapsule pigment.
The microcapsule pigment has a specific gravity at the time of decoloration of 1.03, a specific gravity at the time of color development of 1.05, an average particle diameter of 2.5 μm, a complete decolorization temperature of 42 ° C., and a complete color development temperature of −2 ° C. When the temperature changes, the color changes from pink to colorless.
可逆熱変色性筆記具用水性インキの調製
前記マイクロカプセル顔料２０．０重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．５重量部、グリセリン１５．０重量部、消泡剤０．０２重量部、防腐剤１．５重量部、水６２．８８重量部、１０％希釈リン酸溶液０．１重量部を加えて、均一に攪拌を行い、インキのｐＨを約５．５に調整した可逆熱変色性筆記具用水性インキを得た。
なお、前記インキのビヒクル比重は１．０３であった。
Preparation of water-based ink for reversible thermochromic writing instrument 20.0 parts by weight of the above microcapsule pigment, 0.5 parts by weight of hydroxyethylcellulose [Union Carbide Japan Co., Ltd., trade name: Cellosize WP-09B], 15.0 parts by weight of glycerin Part, 0.02 part by weight of antifoaming agent, 1.5 part by weight of preservative, 62.88 parts by weight of water, 0.1 part by weight of 10% diluted phosphoric acid solution, and stirred uniformly to make the pH of the ink Was obtained to obtain a water-based ink for a reversible thermochromic writing instrument, adjusted to about 5.5.
The ink had a vehicle specific gravity of 1.03.
筆記具の作製
前記インキ（予め−２℃以下に冷却してマイクロカプセル顔料をピンク色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８７％）に２．０ｇ含浸させて軸筒内に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５３％）を取り付けてマーキングペンを得た。
前記マーキングペンには着脱自在のキャップを備えてなり、前記キャップには頂部に擦過部材としてシリコーンゴムを装着してなる。
前記マーキングペンを用いて紙面に筆記してピンク色の文字（筆跡）を形成した。
前記筆跡は、室温（２５℃）でピンク色を呈しており、キャップに装着した擦過部材を用いて文字を擦過すると、該文字は消色して無色となり、この状態は、室温下では保持されており、−２℃以下に冷却することにより、元のピンク色に復色し、前記変色挙動は繰返し再現された。
Fabrication of writing instrument A fiber-gathering ink occlusion body in which the ink (previously cooled to −2 ° C. or lower and the microcapsule pigment is colored pink and left at room temperature) is coated with a polyester sliver with a synthetic resin film. 2.0 g of (porosity of about 87%) was impregnated and accommodated in the shaft tube, and a chisel type fiber pen body (porosity of about 53%) was attached to the tip of the shaft tube to obtain a marking pen.
The marking pen is provided with a detachable cap, and the cap is provided with silicone rubber as a scraping member on the top.
The marking pen was used to write on the paper to form pink characters (handwriting).
The handwriting has a pink color at room temperature (25 ° C.), and when characters are scraped with a scraping member attached to a cap, the characters are discolored and become colorless, and this state is maintained at room temperature. By cooling to −2 ° C. or lower, the original pink color was restored, and the discoloration behavior was reproduced repeatedly.
実施例３
可逆熱変色性マイクロカプセル顔料の調製
（イ）成分として１，３−ジメチル−６−ジエチルアミノフルオラン２．５重量部、（ロ）成分として４、４′−（２−メチルプロピリデン）ビスフェノール４．０重量部、２，２−ビス（４′−ヒドロキシフェニル）ヘキサフルオロプロパン４．０重量部、（ハ）成分としてカプリン酸４−ベンジルオキシフェニルエチル５０．０重量部からなる可逆熱変色性組成物を均一に加温溶解し、壁膜材料として芳香族多価イソシアネートプレポリマー２５．０重量部、助溶剤５０．０重量部を混合した溶液を、８％ポリビニルアルコール水溶液中で微小滴になるように乳化分散し、７０℃で約１時間攪拌を続けた後、水溶性脂肪族変性アミン２．５重量部を加え、更に６時間攪拌を続けて可逆熱変色性マイクロカプセル顔料懸濁液を得た。
前記懸濁液を遠心分離して可逆熱変色性マイクロカプセル顔料を単離した。
なお、前記マイクロカプセル顔料の消色時の比重は１．０７、発色時の比重は１．０８、平均粒子径２．５μｍ、完全消色温度は６０℃、完全発色温度は−２０℃であり、温度変化により橙色から無色に変色する。
Example 3
Preparation of reversible thermochromic microcapsule pigment (a) 2.5 parts by weight of 1,3-dimethyl-6-diethylaminofluorane as component (4), 4 '-(2-methylpropylidene) bisphenol 4 as component (b) 1.0 part by weight, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 4.0 part by weight, and (c) 4-benzyloxyphenylethyl caprate as component (5) reversible thermochromic property The composition is uniformly heated and dissolved, and a solution prepared by mixing 25.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 50.0 parts by weight of a co-solvent as a wall film material is formed into fine droplets in an 8% aqueous polyvinyl alcohol solution. The mixture was emulsified and dispersed, and stirred at 70 ° C. for about 1 hour. Then, 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and stirring was further continued for 6 hours. A microcapsule pigment suspension was obtained.
The suspension was centrifuged to isolate a reversible thermochromic microcapsule pigment.
The microcapsule pigment has a specific gravity at the time of decoloration of 1.07, a specific gravity at the time of color development of 1.08, an average particle diameter of 2.5 μm, a complete decolorization temperature of 60 ° C., and a complete color development temperature of −20 ° C. When the temperature changes, the color changes from orange to colorless.
可逆熱変色性筆記具用水性インキの調製
前記マイクロカプセル顔料２０．０重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．５重量部、グリセリン２５．０重量部、消泡剤０．０２重量部、防腐剤１．５重量部、水５２．８８重量部、１０％希釈リン酸溶液０．１重量部を加えて、均一に攪拌を行い、インキのｐＨを約５．５に調整して可逆熱変色性筆記具用水性インキを得た。
なお、前記インキのビヒクル比重は１．０６であった。
Preparation of water-based ink for reversible thermochromic writing instrument 20.0 parts by weight of the above microcapsule pigment, 0.5 parts by weight of hydroxyethyl cellulose [Union Carbide Japan Co., Ltd., trade name: Cellosize WP-09B], 25.0 parts by weight of glycerin Part, 0.02 part by weight of antifoaming agent, 1.5 parts by weight of preservative, 52.88 parts by weight of water, 0.1 part by weight of 10% diluted phosphoric acid solution, and stirred uniformly to make the pH of the ink Was adjusted to about 5.5 to obtain a water-based ink for a reversible thermochromic writing instrument.
The ink had a vehicle specific gravity of 1.06.
筆記具の作製
前記インキ（予め−２０℃以下に冷却してマイクロカプセル顔料を橙色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８７％）に２．０ｇ含浸させて軸筒内に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５３％）を取り付けてマーキングペンを得た。
前記マーキングペンには着脱自在のキャップを備えてなり、前記キャップには頂部に擦過部材としてＳＥＢＳ樹脂を装着してなる。
前記マーキングペンを用いて紙面に筆記して橙色の文字（筆跡）を形成した。
前記筆跡は、室温（２５℃）で橙色を呈しており、キャップに装着した擦過部材を用いて文字を擦過すると、該文字は消色して無色となり、この状態は、室温下では保持されており、−２０℃以下に冷却することにより、元の橙色に復色し、前記変色挙動は繰返し再現された。
Fabrication of writing instrument A fiber-focused ink occlusion body in which the ink (previously cooled to −20 ° C. or lower and the microcapsule pigment is colored orange and left at room temperature) is coated with a polyester sliver with a synthetic resin film ( A marking pen was obtained by impregnating 2.0 g of the porosity (about 87%) into the shaft cylinder and mounting the chisel-type fiber pen (porosity about 53%) on the tip of the shaft cylinder.
The marking pen is provided with a detachable cap, and the cap is provided with a SEBS resin as a rubbing member on the top.
An orange character (handwriting) was formed by writing on the paper surface using the marking pen.
The handwriting has an orange color at room temperature (25 ° C.), and when characters are scraped with a scraping member attached to a cap, the characters are discolored and become colorless, and this state is maintained at room temperature. Then, by cooling to −20 ° C. or lower, the original orange color was restored, and the discoloration behavior was reproduced repeatedly.
実施例４
可逆熱変色性マイクロカプセル顔料の調製
（イ）成分として、２−（ジブチルアミノ）−８−（ジペンチルアミノ）−４−メチル−スピロ[５Ｈ−[1]ベンゾピラノ[２、３−ｇ]ピリミジン−５、１’（３’Ｈ）−イソベンゾフラン]−３−オン２．５重量部、（ロ）成分として４、４′−（２−メチルプロピリデン）ビスフェノール４．０重量部、２，２−ビス（４′−ヒドロキシフェニル）ヘキサフルオロプロパン４．０重量部、（ハ）成分としてカプリン酸４−ベンジルオキシフェニルエチル５０．０重量部からなる可逆熱変色性組成物を均一に加温溶解し、壁膜材料として芳香族多価イソシアネートプレポリマー２５．０重量部、助溶剤５０．０重量部を混合した溶液を、８％ポリビニルアルコール水溶液中で微小滴になるように乳化分散し、７０℃で約１時間攪拌を続けた後、水溶性脂肪族変性アミン２．５重量部を加え、更に６時間攪拌を続けて可逆熱変色性マイクロカプセル顔料懸濁液を得た。
前記懸濁液を遠心分離して可逆熱変色性マイクロカプセル顔料を単離した。
なお、前記マイクロカプセル顔料の消色時の比重は１．０７、発色時の比重は１．０８、粒子径２．５μｍ、完全消色温度は６０℃、完全発色温度は−１８℃であり、温度変化によりピンク色から無色に変色する。
Example 4
Preparation of reversible thermochromic microcapsule pigment (i) 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g] pyrimidine- 5, 1 ′ (3′H) -isobenzofuran] -3-one 2.5 parts by weight, (b) 4,4 ′-(2-methylpropylidene) bisphenol 4.0 parts by weight, 2,2 -A reversible thermochromic composition comprising 4.0 parts by weight of bis (4'-hydroxyphenyl) hexafluoropropane and 50.0 parts by weight of 4-benzyloxyphenylethyl caprate as component (c) is uniformly heated and dissolved. Then, a solution in which 25.0 parts by weight of aromatic polyisocyanate prepolymer and 50.0 parts by weight of a co-solvent are mixed as a wall film material is emulsified and dispersed to form fine droplets in an aqueous 8% polyvinyl alcohol solution. After stirring at 70 ° C. for about 1 hour, 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and stirring was further continued for 6 hours to obtain a reversible thermochromic microcapsule pigment suspension.
The suspension was centrifuged to isolate a reversible thermochromic microcapsule pigment.
The specific gravity at the time of decoloration of the microcapsule pigment is 1.07, the specific gravity at the time of color development is 1.08, the particle diameter is 2.5 μm, the complete color erasure temperature is 60 ° C., and the complete color development temperature is −18 ° C. It changes from pink to colorless due to temperature change.
可逆熱変色性筆記具用水性インキの調製
前記マイクロカプセル顔料２０．０重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．５重量部、グリセリン２０．０重量部、消泡剤０．０２重量部、防腐剤１．５重量部、水５７．８８重量部、１０％希釈リン酸溶液０．１重量部を加えて、均一に攪拌を行い、インキのｐＨを約５．５に調整した可逆熱変色性筆記具用水性インキを得た。
なお、前記インキのビヒクル比重は１．０５であった。
Preparation of water-based ink for reversible thermochromic writing instrument 20.0 parts by weight of the above microcapsule pigment, 0.5 parts by weight of hydroxyethylcellulose [Union Carbide Japan Co., Ltd., trade name: Cellosize WP-09B], 20.0 parts by weight of glycerin Part, 0.02 part by weight of antifoaming agent, 1.5 part by weight of preservative, 57.88 part by weight of water, 0.1 part by weight of 10% diluted phosphoric acid solution, and stirred uniformly to make the pH of the ink Was obtained to obtain a water-based ink for a reversible thermochromic writing instrument, adjusted to about 5.5.
The ink had a vehicle specific gravity of 1.05.
筆記具の作製
前記インキ（予め−１８℃以下に冷却してマイクロカプセル顔料を橙色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８７％）に２．０ｇ含浸させて軸筒内に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５３％）を取り付けてマーキングペンを得た。
前記マーキングペンには着脱自在のキャップを備えてなり、前記キャップには頂部に擦過部材としてシリコーンゴムを装着してなる。
前記マーキングペンを用いて紙面に筆記してピンク色の文字（筆跡）を形成した。
前記筆跡は、室温（２５℃）でピンク色を呈しており、キャップに装着した擦過部材を用いて文字を擦過すると、該文字は消色して無色となり、この状態は、室温下では保持されており、−１８℃以下に冷却することにより、元のピンク色に復色し、前記変色挙動は繰返し再現された。
Fabrication of writing instrument The above-mentioned ink (previously cooled to −18 ° C. or lower and the microcapsule pigment is colored orange and left at room temperature), a fiber sizing ink occlusion body in which a polyester sliver is coated with a synthetic resin film ( A marking pen was obtained by impregnating 2.0 g of the porosity (about 87%) into the shaft cylinder and mounting the chisel-type fiber pen (porosity about 53%) on the tip of the shaft cylinder.
The marking pen is provided with a detachable cap, and the cap is provided with silicone rubber as a scraping member on the top.
The marking pen was used to write on the paper to form pink characters (handwriting).
The handwriting has a pink color at room temperature (25 ° C.), and when characters are scraped with a scraping member attached to a cap, the characters are discolored and become colorless, and this state is maintained at room temperature. By cooling to −18 ° C. or lower, the original pink color was restored, and the discoloration behavior was reproduced repeatedly.
比較例１
可逆熱変色性筆記具用水性インキの調製
実施例１の可逆熱変色性マイクロカプセル顔料２０．０重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．５重量部、グリセリン５．０重量部、消泡剤０．０２重量部、防腐剤１．５重量部、水７２．８８重量部、１０％希釈リン酸溶液０．１重量部を加えて均一に攪拌を行い、インキのｐＨを約５．５に調整した可逆熱変色性インキを得た。
なお、前記インキのビヒクル比重は１．０１であった。
Comparative Example 1
Preparation of water-based ink for reversible thermochromic writing instrument 20.0 parts by weight of reversible thermochromic microcapsule pigment of Example 1, hydroxyethyl cellulose [manufactured by Union Carbide Japan Co., Ltd., trade name: Serosize WP-09B] 0.5 weight Part, glycerin 5.0 parts by weight, antifoaming agent 0.02 parts by weight, preservative 1.5 parts by weight, water 72.88 parts by weight, 10% diluted phosphoric acid solution 0.1 part by weight To obtain a reversible thermochromic ink in which the pH of the ink was adjusted to about 5.5.
The ink had a vehicle specific gravity of 1.01.
筆記具の作製
前記インキ（予め０℃以下に冷却してマイクロカプセル顔料を橙色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８７％）に２．０ｇ含浸させて軸筒内に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５３％）を取り付けてマーキングペンを得た。
Fabrication of a writing instrument The above-described ink (previously cooled to 0 ° C. or less and allowed to develop a microcapsule pigment in an orange color and then allowed to stand at room temperature), a fiber sizing ink occlusion body (porosity) coated with a polyester sliver with a synthetic resin film A marking pen was obtained by impregnating 2.0 g into a shaft cylinder and attaching a chisel type fiber pen body (porosity of about 53%) to the tip of the shaft cylinder.
比較例２
可逆熱変色性筆記具用水性インキの調製
実施例２の可逆熱変色性マイクロカプセル顔料２０．０重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．５重量部、グリセリン５．０重量部、消泡剤０．０２重量部、防腐剤１．５重量部、水７２．８８重量部、１０％希釈リン酸溶液０．１重量部を加えて均一に攪拌を行い、インキのｐＨを約５．５０に調整した可逆熱変色性インキを得た。
なお、前記インキのビヒクル比重は１．０１であった。
Comparative Example 2
Preparation of water-based ink for reversible thermochromic writing instrument 20.0 parts by weight of reversible thermochromic microcapsule pigment of Example 2, hydroxyethyl cellulose [manufactured by Union Carbide Japan Co., Ltd., trade name: Serosize WP-09B] 0.5 weight Part, glycerin 5.0 parts by weight, antifoaming agent 0.02 parts by weight, preservative 1.5 parts by weight, water 72.88 parts by weight, 10% diluted phosphoric acid solution 0.1 part by weight To obtain a reversible thermochromic ink in which the pH of the ink was adjusted to about 5.50.
The ink had a vehicle specific gravity of 1.01.
筆記具の作製
前記インキ（予め−２℃以下に冷却してマイクロカプセル顔料をピンク色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８７％）に２．０ｇ含浸させて軸筒内に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５３％）を取り付けてマーキングペンを得た。
Fabrication of writing instrument A fiber-gathering ink occlusion body in which the ink (previously cooled to −2 ° C. or lower and the microcapsule pigment is colored pink and left at room temperature) is coated with a polyester sliver with a synthetic resin film. 2.0 g of (porosity of about 87%) was impregnated and accommodated in the shaft tube, and a chisel type fiber pen body (porosity of about 53%) was attached to the tip of the shaft tube to obtain a marking pen.
比較例３
可逆熱変色性筆記具用水性インキの調製
実施例３の可逆熱変色性マイクロカプセル顔料２０．０重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．５重量部、グリセリン５．０重量部、消泡剤０．０２重量部、防腐剤１．５重量部、水７２．８８重量部、１０％希釈リン酸溶液０．１重量部を加えて均一に攪拌を行い、インキのｐＨを約５．５０に調整した可逆熱変色性インキを得た。
なお、前記インキのビヒクル比重は１．０１であった。
Comparative Example 3
Preparation of water-based ink for reversible thermochromic writing instrument 20.0 parts by weight of reversible thermochromic microcapsule pigment of Example 3, hydroxyethyl cellulose [manufactured by Union Carbide Japan Co., Ltd., trade name: Serosize WP-09B] 0.5 weight Part, glycerin 5.0 parts by weight, antifoaming agent 0.02 parts by weight, preservative 1.5 parts by weight, water 72.88 parts by weight, 10% diluted phosphoric acid solution 0.1 part by weight To obtain a reversible thermochromic ink in which the pH of the ink was adjusted to about 5.50.
The ink had a vehicle specific gravity of 1.01.
筆記具の作製
前記インキ（予め−２０℃以下に冷却してマイクロカプセル顔料を橙色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８７％）に２．０ｇ含浸させて軸筒内に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５３％）を取り付けてマーキングペンを得た。
Fabrication of writing instrument A fiber-focused ink occlusion body in which the ink (previously cooled to −20 ° C. or lower and the microcapsule pigment is colored orange and left at room temperature) is coated with a polyester sliver with a synthetic resin film ( A marking pen was obtained by impregnating 2.0 g of the porosity (about 87%) into the shaft cylinder and mounting the chisel-type fiber pen (porosity about 53%) on the tip of the shaft cylinder.
比較例４
可逆熱変色性筆記具用水性インキの調製
実施例４の可逆熱変色性マイクロカプセル顔料２０．０重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．５重量部、グリセリン５．０重量部、消泡剤０．０２重量部、防腐剤１．５重量部、水７２．８８重量部、１０％希釈リン酸溶液０．１重量部を加えて、均一に攪拌を行い、インキのｐＨを約５．５に調整した可逆熱変色性インキを得た。
なお、前記インキのビヒクル比重は１．０１であった。
Comparative Example 4
Preparation of water-based ink for reversible thermochromic writing instrument 20.0 parts by weight of reversible thermochromic microcapsule pigment of Example 4, hydroxyethyl cellulose [manufactured by Union Carbide Japan Co., Ltd., trade name: cello size WP-09B] 0.5 weight Part, glycerin 5.0 parts by weight, antifoaming agent 0.02 parts by weight, preservative 1.5 parts by weight, water 72.88 parts by weight, 10% diluted phosphoric acid solution 0.1 part by weight, uniformly Stirring was performed to obtain a reversible thermochromic ink in which the pH of the ink was adjusted to about 5.5.
The ink had a vehicle specific gravity of 1.01.
筆記具の作製
前記インキ（予め−１８℃以下に冷却してマイクロカプセル顔料をピンク色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８７％）に２．０ｇ含浸させて軸筒内に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５３％）を取り付けてマーキングペンを得た。
Fabrication of a writing instrument A fiber-focused ink occlusion body in which the above-mentioned ink (previously cooled to -18 ° C or lower and the microcapsule pigment is colored pink and left at room temperature) is coated with a polyester sliver with a synthetic resin film. 2.0 g of (porosity of about 87%) was impregnated and accommodated in the shaft tube, and a chisel type fiber pen body (porosity of about 53%) was attached to the tip of the shaft tube to obtain a marking pen.
前記各実施例及び比較例で得た筆記具を用いて以下の試験を行った。
筆記試験
実施例１乃至４及び比較例１乃至４で作製した筆記具を５０℃の恒温槽中に横置き状態で入れて、３０日間放置した後、白色紙にそれぞれ筆記を行った（各１０行）。
なお、実施例１及び２、比較例１及び２で作製した筆記具は、恒温槽から取り出して放冷後に０℃の冷蔵庫に入れて５時間冷却し、室温下で１時間放置した後、白色紙に筆記を行った。
The following tests were carried out using the writing instruments obtained in the respective examples and comparative examples.
Writing test The writing tools produced in Examples 1 to 4 and Comparative Examples 1 to 4 were placed horizontally in a thermostatic bath at 50 ° C. and allowed to stand for 30 days, and then written on white paper (each 10 lines). ).
The writing instruments prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were taken out of the thermostatic bath, allowed to cool, then placed in a 0 ° C. refrigerator, cooled for 5 hours, allowed to stand at room temperature for 1 hour, and then white paper. Written on
試験結果を以下の表に示す。
なお、表中の記号に関する評価は以下の通りである。
○：初期の筆跡と比較してかすれや途切れがみられない。
×：初期の筆跡と比較してかすれや途切れがみられる。
In addition, the evaluation regarding the symbol in a table | surface is as follows.
○: No fading or discontinuity compared to the initial handwriting.
X: Blurred or discontinuous compared to the initial handwriting.
ｔ１ 加熱消色型の可逆熱変色性マイクロカプセル顔料の完全発色温度
ｔ２ 加熱消色型の可逆熱変色性マイクロカプセル顔料の発色開始温度
ｔ３ 加熱消色型の可逆熱変色性マイクロカプセル顔料の消色開始温度
ｔ４ 加熱消色型の可逆熱変色性マイクロカプセル顔料の完全消色温度
Ｔ１ 加熱発色型の可逆熱変色性マイクロカプセル顔料の完全消色温度
Ｔ２ 加熱発色型の可逆熱変色性マイクロカプセル顔料の消色開始温度
Ｔ３ 加熱発色型の可逆熱変色性マイクロカプセル顔料の発色開始温度
Ｔ４ 加熱発色型の可逆熱変色性マイクロカプセル顔料の完全発色温度
t 1 Complete color development temperature of reversible thermochromic microcapsule pigment with heat decoloring type t 2 Color development start temperature of reversible thermochromic microcapsule pigment with heat decoloration type t 3 Reversible thermochromic microcapsule pigment with heat decoloration type Decoloration start temperature of t 4 Complete decolorization temperature of reversible thermochromic microcapsule pigment of heat decoloring type T 1 Complete decoloration temperature of reversible thermochromic microcapsule pigment of 1 heating color developing type T 2 Reversible heat of color developing type of heat decoloring type Discoloration start temperature of the color-changing microcapsule pigment T 3 Color development start temperature of the reversible thermochromic microcapsule pigment of the 3 heating coloring type T 4 Color development temperature of the reversible thermochromic microcapsule pigment of the 4 heating coloring type
Claims (5)
Ｘ−０．０２≦Ｚ＜Ｙ （１）
Ｘ＜Ｙ≦Ｘ＋０．０３ （２） (B) Reversible heat encapsulating a reversible thermochromic composition comprising a reaction medium that determines the temperature at which the color reaction of both occurs (b) an electron-donating color-forming organic compound; In a water-based ink composition comprising a discolorable microcapsule pigment and a vehicle containing at least water, a water-soluble organic solvent, and a water-soluble polymer flocculant, the specific gravity at the time of decoloration of the reversible thermochromic microcapsule pigment ( A water-based ink composition for a reversible thermochromic writing instrument in which X), the specific gravity during color development (Y), and the specific gravity of a vehicle (Z) satisfy the following formulas (1) and (2).
X−0.02 ≦ Z <Y (1)
X <Y ≦ X + 0.03 (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2005119222A JP2006298990A (en) | 2005-04-18 | 2005-04-18 | Aqueous ink composition for reversibly thermochromic writing utensil and writing utensil containing the same |
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| JP2005119222A JP2006298990A (en) | 2005-04-18 | 2005-04-18 | Aqueous ink composition for reversibly thermochromic writing utensil and writing utensil containing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007224295A (en) * | 2006-01-30 | 2007-09-06 | Pilot Ink Co Ltd | Reversibly and thermally allochroic aqueous ink composition and direct liquid type writing utensil containing the same |
| JP2008291049A (en) * | 2007-05-22 | 2008-12-04 | Pilot Ink Co Ltd | Reversibly thermochromic aqueous ink composition and filling type writing instrument using the same |
| WO2011021610A1 (en) * | 2009-08-18 | 2011-02-24 | パイロットインキ株式会社 | Reversibly thermochromic aqueous ink composition, and writing instrument and writing instrument set each utilizing same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62140881A (en) * | 1985-12-14 | 1987-06-24 | Pilot Ink Co Ltd | Color-storing printed matter |
| JPS6454081A (en) * | 1987-08-25 | 1989-03-01 | Pilot Ink Co Ltd | Writing utensils containing reversibly thermochromic ink |
| JP2003206432A (en) * | 2001-11-12 | 2003-07-22 | Pilot Ink Co Ltd | Writing utensil color-changeable by frictional heat and set changing color with frictional heat by using the same |
| JP2004148744A (en) * | 2002-10-31 | 2004-05-27 | Pilot Ink Co Ltd | Friction body and writing utensil |
| JP2005001369A (en) * | 2003-05-16 | 2005-01-06 | Pilot Ink Co Ltd | Thermochromic color memorizing composition and thermochromic color memorizing microcapsule pigment containing the same |
| JP2005088308A (en) * | 2003-09-16 | 2005-04-07 | Pilot Ink Co Ltd | Writing utensil equipped with thermally discolored reversible appearing and disappearing function |
-
2005
- 2005-04-18 JP JP2005119222A patent/JP2006298990A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62140881A (en) * | 1985-12-14 | 1987-06-24 | Pilot Ink Co Ltd | Color-storing printed matter |
| JPS6454081A (en) * | 1987-08-25 | 1989-03-01 | Pilot Ink Co Ltd | Writing utensils containing reversibly thermochromic ink |
| JP2003206432A (en) * | 2001-11-12 | 2003-07-22 | Pilot Ink Co Ltd | Writing utensil color-changeable by frictional heat and set changing color with frictional heat by using the same |
| JP2004148744A (en) * | 2002-10-31 | 2004-05-27 | Pilot Ink Co Ltd | Friction body and writing utensil |
| JP2005001369A (en) * | 2003-05-16 | 2005-01-06 | Pilot Ink Co Ltd | Thermochromic color memorizing composition and thermochromic color memorizing microcapsule pigment containing the same |
| JP2005088308A (en) * | 2003-09-16 | 2005-04-07 | Pilot Ink Co Ltd | Writing utensil equipped with thermally discolored reversible appearing and disappearing function |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007224295A (en) * | 2006-01-30 | 2007-09-06 | Pilot Ink Co Ltd | Reversibly and thermally allochroic aqueous ink composition and direct liquid type writing utensil containing the same |
| JP2008291049A (en) * | 2007-05-22 | 2008-12-04 | Pilot Ink Co Ltd | Reversibly thermochromic aqueous ink composition and filling type writing instrument using the same |
| WO2011021610A1 (en) * | 2009-08-18 | 2011-02-24 | パイロットインキ株式会社 | Reversibly thermochromic aqueous ink composition, and writing instrument and writing instrument set each utilizing same |
| JP2011038048A (en) * | 2009-08-18 | 2011-02-24 | Pilot Ink Co Ltd | Reversible thermochromic aqueous ink composition, writing implement using the same and writing implement set |
| US8845799B2 (en) | 2009-08-18 | 2014-09-30 | The Pilot Ink Co., Ltd. | Reversibly thermochromic aqueous ink composition, and writing instrument and writing instrument set each utilizing same |
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