JPWO2007063892A1 - Aqueous decolorizable ink composition for writing instruments - Google Patents
Aqueous decolorizable ink composition for writing instruments Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
本発明は、従来の筆記具用水性消色性インキ組成物における問題を解決するためになされたものであって、その筆跡を消去用インキ組成物でなぞったときに消色し、又は変色する速度が速く、作業性にすぐれる筆記具用水性消色性インキ組成物を提供することを目的とする。本発明によれば、水と、還元剤によって消色する塩基性染料と、ジ（長鎖アルキル）ジ（低級アルキル）アンモニウムハライドから選ばれる少なくとも1種からなる消色助剤を含有することを特徴とする筆記具用水性消色性インキ組成物が提供される。還元剤としては、特に、亜硫酸ナトリウム又は亜硫酸カリウムが好ましく用いられる。The present invention has been made in order to solve the problems in conventional water-based decoloring ink compositions for writing instruments, and is a rate of decoloring or discoloring when the handwriting is traced with an erasing ink composition. An object of the present invention is to provide a water-based decolorizable ink composition for a writing instrument that is fast and excellent in workability. According to the present invention, it contains water, a basic dye that can be decolored by a reducing agent, and a decoloring aid consisting of at least one selected from di (long-chain alkyl) di (lower alkyl) ammonium halides. A water-based decolorizable ink composition for a writing instrument is provided. As the reducing agent, sodium sulfite or potassium sulfite is particularly preferably used.
Description
本発明は筆記具用水性消色性インキ組成物に関する。詳しくは、本発明は、その筆跡を消去用インキ組成物でなぞることによって、消色し、又は変色させることができる筆記具用水性消色性インキ組成物であって、その消色又は変色の速度が早く、また、筆跡を消色する場合には、極めてよく消色することができる筆記具用水性消色性インキ組成物に関する。
The present invention relates to an aqueous decolorizable ink composition for writing instruments. Specifically, the present invention is a water-based decolorizable ink composition for a writing instrument that can be decolored or discolored by tracing its handwriting with an erasing ink composition, and the speed of decoloring or discoloration. The present invention relates to a water-based decolorizable ink composition for a writing instrument that can be erased very well when the handwriting is erased quickly.
従来、還元剤として、例えば、亜硫酸塩を含む消去用インキ組成物にて、その筆跡をなぞることによって消色することができる筆記具用水性インキ組成物として、例えば、特開昭５４−９２４２３号公報に記載されているように、塩基性染料を着色剤として含むものが知られている。同様に、その筆跡をなぞることによって、筆跡の色調を変化させることができる筆記具用水性インキ組成物として、例えば、特公昭６２−２８８３４号公報に記載されているように、酸化剤又は還元剤からなる脱色剤にて消去可能な着色剤と消去し難い着色剤とを配合してなるものが知られている。
しかしながら、上述したような従来から知られている筆記具用水性消色性インキ組成物は、その筆跡を消去用インキ組成物でなぞったときに消色し、又は変色する速度が遅く、いわば、作業性に劣るものであった。本発明は、そのような従来の筆記具用水性消色性インキ組成物における問題を解決するためになされたものであって、その筆跡を消去用インキ組成物でなぞったときに消色し、又は変色する速度が速く、作業性にすぐれる筆記具用水性消色性インキ組成物を提供することを目的とする。
However, conventionally known water-repellent ink compositions for writing instruments as described above have a slow rate of decoloring or discoloring when the handwriting is traced with an erasing ink composition, so to speak, work It was inferior in nature. The present invention has been made in order to solve the problems in such a conventional water-based decolorable ink composition for writing instruments, and is erased when the handwriting is traced with an erasing ink composition, or An object of the present invention is to provide a water-based decolorizable ink composition for a writing instrument that has a fast discoloration rate and excellent workability.
本発明によれば、水と、還元剤によって消色する塩基性染料と、
一般式（Ｉ）According to the present invention, water, a basic dye that is decolorized by a reducing agent,
Formula (I)
（式中、Ｒ１ は炭素原子数１０〜１８の長鎖アルキル基を示し、Ｒ2 はそれぞれ独立にメチル基又はエチル基を示す。）
で表される長鎖アルキルトリ（低級アルキル）アンモニウムハライド及び
一般式（II）
(In the formula, R 1 represents a long-chain alkyl group having 10 to 18 carbon atoms, and R 2 independently represents a methyl group or an ethyl group.)
Long-chain alkyltri (lower alkyl) ammonium halides represented by the general formula (II)
（式中、Ｒ１ は炭素原子数１０〜１８の長鎖アルキル基を示し、Ｒ2 はそれぞれ独立にメチル基又はエチル基を示す。）
で表されるジ（長鎖アルキル）ジ（低級アルキル）アンモニウムハライドから選ばれる少なくとも1種からなる消色助剤を含有することを特徴とする筆記具用水性消色性インキ組成物が提供される。(In the formula, R 1 represents a long-chain alkyl group having 10 to 18 carbon atoms, and R 2 independently represents a methyl group or an ethyl group.)
An aqueous decolorizable ink composition for a writing instrument comprising a decoloring aid comprising at least one selected from di (long-chain alkyl) di (lower alkyl) ammonium halides represented by .
本発明においては、上記消色助剤は、好ましくは、長鎖アルキルトリメチルアンモニウムクロライド及びジ（長鎖アルキル）ジメチルアンモニウムクロライドから選ばれる少なくとも１つである。本発明による筆記具用水性消色性インキ組成物は、このような消色助剤を、通常、０．５〜１０重量％の範囲で含む。
本発明において、上記還元剤は、好ましくは、亜硫酸塩又はチオ硫酸塩であり、なかでも、亜硫酸ナトリウム及び亜硫酸カリウムから選ばれる少なくとも１つが好ましく用いられる。In the present invention, the decoloring aid is preferably at least one selected from long-chain alkyltrimethylammonium chloride and di (long-chain alkyl) dimethylammonium chloride. The aqueous decolorizable ink composition for a writing instrument according to the present invention usually contains such a decoloring aid in the range of 0.5 to 10% by weight.
In the present invention, the reducing agent is preferably a sulfite or a thiosulfate, and among them, at least one selected from sodium sulfite and potassium sulfite is preferably used.
更に、本発明によれば、上述したインキ組成物に還元剤によって消色しない着色剤を含有させてなる筆記具用水性変色性インキ組成物が提供される。
Furthermore, according to the present invention, there is provided an aqueous color-changing ink composition for a writing instrument, wherein the ink composition described above contains a colorant that is not decolored by a reducing agent.
本発明による筆記具用水性消色性インキ組成物は、水と、還元剤によって消色する塩基性染料と、
一般式（Ｉ）A water-based decolorizable ink composition for a writing instrument according to the present invention includes water, a basic dye that is decolorized by a reducing agent,
Formula (I)
（式中、Ｒ１ は炭素原子数１０〜１８の長鎖アルキル基を示し、Ｒ2 はそれぞれ独立にメチル基又はエチル基を示す。）
で表される長鎖アルキルトリ（低級アルキル）アンモニウムハライド及び
一般式（II）(In the formula, R 1 represents a long-chain alkyl group having 10 to 18 carbon atoms, and R 2 independently represents a methyl group or an ethyl group.)
Long-chain alkyltri (lower alkyl) ammonium halides represented by the general formula (II)
（式中、Ｒ１ は炭素原子数１０〜１８の長鎖アルキル基を示し、Ｒ2 はそれぞれ独立にメチル基又はエチル基を示す。）
で表されるジ（長鎖アルキル）ジ（低級アルキル）アンモニウムハライドから選ばれる少なくとも1種からなる消色助剤を含有する。(In the formula, R 1 represents a long-chain alkyl group having 10 to 18 carbon atoms, and R 2 independently represents a methyl group or an ethyl group.)
A decolorization aid comprising at least one selected from di (long-chain alkyl) di (lower alkyl) ammonium halides represented by the formula:
還元剤にて消色する塩基性染料のみを着色剤として含有する水性インキ組成物によって形成された筆跡は、そのような還元剤を含む消去用インキ組成物にてなぞることによって消色する。還元剤にて消色する塩基性染料と還元剤にて消色しない着色剤を共に含有するインキ組成物によって形成された筆跡は、そのような還元剤を含む消去用インキ組成物にてなぞることによって、筆跡を形成する着色剤のうち、上記還元剤にて消色する塩基性染料は消色するが、上記還元剤にて消色しない着色剤はそのまま残り、従って、筆跡は後者の着色剤に基づく色調を有する。かくして、還元剤にて消色しない着色剤として、還元剤にて消色する塩基性染料と色調の相違するものを用いてなるインキ組成物は、その筆跡を前記還元剤を含む消去用インキ組成物にてなぞることによって、当初の還元剤にて消色する塩基性染料と上記還元剤にて消色しない着色剤との混合色調から上記還元剤にて消色しない着色剤に基づく色調に変色させることができる。 The handwriting formed by the aqueous ink composition containing only the basic dye that is decolored by the reducing agent as the colorant is decolored by tracing with the erasing ink composition containing such a reducing agent. The handwriting formed by an ink composition containing both a basic dye that erases with a reducing agent and a colorant that does not erase with a reducing agent should be traced with an erasing ink composition containing such a reducing agent. Therefore, among the colorants that form handwriting, the basic dye that is decolored by the reducing agent is decolored, but the colorant that is not decolored by the reducing agent remains as it is, and therefore the handwriting is the latter colorant. It has a color tone based on. Thus, as a colorant that does not lose color with a reducing agent, an ink composition that uses a basic dye that has a color tone different from that with a reducing agent is used as an erasing ink composition containing the reducing agent. By tracing with a product, the color tone is changed from a mixed color tone of a basic dye that is decolored with the original reducing agent and a colorant that is not decolored with the reducing agent to a color tone based on the colorant that is not decolorized with the reducing agent. Can be made.
本発明において、消去用インキ組成物にて「筆跡をなぞる」とは、本発明によるインキ組成物による筆跡部分を消去用インキ組成物にて正確に蔽うことに加えて、筆跡を含むより広い領域を蔽うことを意味する。例えば、文字列を消去用インキ組成物にて帯状に蔽うことは、本発明において、本発明によるインキ組成物にて形成した筆跡を消去用インキ組成物にてなぞることの代表例である。 In the present invention, “tracing the handwriting” with the erasing ink composition means that the handwriting portion of the ink composition according to the present invention is accurately covered with the erasing ink composition, and a wider area including the handwriting. It means to cover. For example, covering a character string in a strip shape with an erasing ink composition is a typical example of tracing the handwriting formed with the ink composition according to the present invention with the erasing ink composition in the present invention.
本発明において、還元剤にて消色する塩基性染料としては、そのような性質を有するものであればいずれでも用いることができるが、好ましい具体例として、例えば、Ｃ．Ｉ．Ｂａｓｉｃ Ｙｅｌｌｏｗ １４、同Ｏｒａｎｇｅ ２２、同Ｒｅｄ １３、１４、４６、同 Ｖｉｏｌｅｔ ３、７、１５、同Ｇｒｅｅｎ １、４、同 Ｂｌｕｅ ３、９、４１、５４、７５、１２９等を挙げることができる。これらの塩基性染料は、単独で、又は二種以上を組み合わせて用いることができる。 In the present invention, any basic dye that can be decolored with a reducing agent can be used as long as it has such properties. Preferred specific examples include C.I. I. Basic Yellow 14, Orange 22, Red 13, 14, 46, Violet 3, 7, 15, Green 1, 4, Blue 3, 9, 41, 54, 75, 129, and the like. These basic dyes can be used alone or in combination of two or more.
本発明によるインキ組成物は、このような還元剤にて消色する塩基性染料を、通常、０．１〜２０重量％の範囲で含有し、好ましくは、０．５〜１５重量％の範囲で含有する。還元剤にて消色する塩基性染料の含有量が０．１重量％よりも少ないときは、得られる筆跡が薄すぎて、実用的ではなく、他方、含有量が２０重量％を超えるときは、用いる塩基性染料の一部が溶媒である水に溶解できず、溶け残りが生じたり、また、得られるインキ組成物の粘度が高すぎて、例えば、マーキングペンに充填したとき、インキ組成物がペン先から円滑に流出し難く、筆記に支障を生じる等の不都合が生じる。
他方、本発明において、還元剤にて消色しない着色剤としては、還元剤で消色しない塩基性染料や顔料が好ましく用いられる。還元剤にて消色しない着色剤としては、例えば、Ｃ．Ｉ．Ｂａｓｉｃ Ｙｅｌｌｏｗ ２８、４０、６７、７３、同Ｒｅｄ １２、同Ｖｉｏｌｅｔ １０、１１、同Ｂｌｕｅ ７等を挙げることができる。The ink composition according to the present invention contains a basic dye that can be decolored with such a reducing agent, usually in the range of 0.1 to 20% by weight, preferably in the range of 0.5 to 15% by weight. Contains. When the content of the basic dye to be decolored with a reducing agent is less than 0.1% by weight, the handwriting obtained is too thin and impractical, whereas when the content exceeds 20% by weight In addition, when a part of the basic dye used cannot be dissolved in water as a solvent and undissolved, or the viscosity of the resulting ink composition is too high, for example, when filled in a marking pen, the ink composition Is difficult to flow out of the nib smoothly, resulting in problems such as hindering writing.
On the other hand, in the present invention, a basic dye or pigment that is not decolored with a reducing agent is preferably used as the colorant that is not decolored with a reducing agent. Examples of the colorant that does not fade with the reducing agent include C.I. I. Examples include Basic Yellow 28, 40, 67, 73, Red 12, Violet 10, 11, Blue 7.
ある塩基性染料が本発明において用いる還元剤にて消色するかどうかは、簡単な試験によって決定することができる。具体的には、亜硫酸ナトリウム１０％水溶液と染料２％水溶液をそれぞれ作製しておき、当該染料２％水溶液の一滴を前記亜硫酸ナトリウム１０％水溶液に点滴し、消色するか否かを判断する。 Whether a certain basic dye is decolored by the reducing agent used in the present invention can be determined by a simple test. Specifically, a 10% aqueous solution of sodium sulfite and a 2% aqueous solution of dye are prepared, and one drop of the 2% aqueous solution of the dye is instilled into the 10% aqueous solution of sodium sulfite to determine whether or not the color is to be erased.
本発明において、還元剤にて消色しない着色剤として用いる顔料については、特に、限定されるものではないが、例えば、モノアゾ顔料、ジスアゾ顔料、縮合アゾ顔料、キレートアゾ顔料のほか、フタロシアニン系、アントラキノン系、ペリレン系、ペリノン系、インジゴ系、チオインジゴ系、キナクリドン系、ジオキサジン系、イソインドリノン系、キノフタロン系等の多環式顔料、金属錯体顔料、染付けレーキ顔料、無機顔料等を挙げることができる。これらの顔料も、単独で、又は二種以上を組み合わせて用いることができる。また、これらの顔料は、インキ組成物の製造において、ポリビニルアルコール等の水溶性樹脂で水中に分散させた水性顔料分散体として用いることが好ましい。 In the present invention, the pigment used as a colorant not decolored by the reducing agent is not particularly limited. For example, in addition to monoazo pigments, disazo pigments, condensed azo pigments, chelate azo pigments, phthalocyanine-based, anthraquinones , Perylene, perinone, indigo, thioindigo, quinacridone, dioxazine, isoindolinone, quinophthalone, and other polycyclic pigments, metal complex pigments, dyed lake pigments, and inorganic pigments . These pigments can also be used alone or in combination of two or more. These pigments are preferably used as an aqueous pigment dispersion dispersed in water with a water-soluble resin such as polyvinyl alcohol in the production of an ink composition.
前述したように、着色剤として還元剤で消色する塩基性染料と還元剤で消色しない着色剤を併用して得られるインキ組成物にて筆記した後、その筆跡を還元剤を含む消去用インキ組成物にてなぞることによって、還元剤で消色する塩基性染料は消色し、還元剤で消色しない着色剤が筆跡に残る。従って、還元剤で消色しない着色剤として、還元剤で消色する塩基性染料とは異なる色調のものを用いてなるインキ組成物にて筆記し、その筆跡を還元剤を含む消去用インキ組成物にてなぞることによって、筆跡の色調を変化させることができる。 As described above, after writing with an ink composition obtained by using a basic dye that decolorizes with a reducing agent as a colorant and a colorant that does not decolorize with a reducing agent, the handwriting is for erasing containing the reducing agent. By tracing with the ink composition, the basic dye that is decolored with the reducing agent is decolored, and the colorant that is not decolorized with the reducing agent remains in the handwriting. Therefore, as a colorant that does not fade with a reducing agent, write with an ink composition that uses a color tone different from that of a basic dye that erases with a reducing agent, and the erasing ink composition containing the reducing agent with a handwriting The color of the handwriting can be changed by tracing with an object.
本発明において、還元剤で消色しない着色剤を用いる場合には、インキ組成物において、通常、０．１〜２０重量％の範囲で用いられ、好ましくは、０．５〜１５重量％の範囲で用いられる。前述したと同様に、還元剤で消色しない着色剤の含有量が０．１重量％よりも少ないときは、還元剤で消色する塩基性染料が消色した後に、還元剤で消色しない着色剤に基づく筆跡が残るが、この筆跡は、薄すぎて、実用的でない。他方、還元剤で消色しない着色剤の含有量が２０重量％を超えるときは、塩基性染料であっても、溶媒である水に溶解できず、溶け残りが生じたり、また、用いる着色剤が塩基性染料、顔料を問わず、得られるインキ組成物の粘度が高くなりすぎて、前述したように、筆記に支障を生じる等の不都合が生じる。 In the present invention, when a colorant that does not fade with a reducing agent is used, it is usually used in the range of 0.1 to 20% by weight, preferably in the range of 0.5 to 15% by weight, in the ink composition. Used in As described above, when the content of the colorant not decolored by the reducing agent is less than 0.1% by weight, the basic dye decolored by the reducing agent is decolored and is not decolored by the reducing agent. A handwriting based on the colorant remains, but this handwriting is too thin to be practical. On the other hand, when the content of the colorant not decolored by the reducing agent exceeds 20% by weight, even a basic dye cannot be dissolved in water as a solvent, resulting in undissolved or a colorant used. However, regardless of basic dyes and pigments, the viscosity of the resulting ink composition becomes too high, resulting in problems such as hindering writing as described above.
本発明によれば、消色助剤として、前述したように、前記一般式（Ｉ）で表される長鎖アルキルトリ（低級アルキル）アンモニウムハライド及び前記一般式（II）で表されるジ（長鎖アルキル）ジ（低級アルキル）アンモニウムハライドから選ばれる少なくとも1種が用いられる。 According to the present invention, as described above, as the decoloring aid, as described above, the long-chain alkyltri (lower alkyl) ammonium halide represented by the general formula (I) and the di (II) represented by the general formula (II) At least one selected from long chain alkyl) di (lower alkyl) ammonium halides is used.
このような消色助剤において、上記長鎖アルキル基は、炭素原子数が１０〜１８の範囲にあり、例えば、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等を挙げることができる。上記低級アルキル基は、好ましくは、メチル基又はエチル基である。また、ハロゲン原子は、好ましくは、塩素又は臭素である。従って、本発明においては、前記一般式（Ｉ）で表される消色助剤として、例えば、ラウリルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウムブロミド、セチルジメチルエチルアンモニウムブロミド、ステアリルジメチルエチルアンモニウムブロミド、ステアリルトリメチルアンモニウムクロライド等を挙げることができる。また、前記一般式（II）で表される消色助剤として、例えば、ジセチルジメチルアンモニウムクロライド、ジデシルジメチルアンモニウムクロライド等を挙げることができる。なかでも、本発明によれば、ラウリルトリメチルアンモニウムクロライド又はステアリルトリメチルクロライドが好ましく用いられる。 In such a decoloring aid, the long-chain alkyl group has 10 to 18 carbon atoms, and examples thereof include a decyl group, dodecyl group, tetradecyl group, hexadecyl group, and octadecyl group. . The lower alkyl group is preferably a methyl group or an ethyl group. The halogen atom is preferably chlorine or bromine. Accordingly, in the present invention, as the decoloring aid represented by the general formula (I), for example, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyldimethylethylammonium bromide, stearyldimethylethylammonium Examples thereof include bromide and stearyltrimethylammonium chloride. Examples of the decoloring aid represented by the general formula (II) include dicetyldimethylammonium chloride and didecyldimethylammonium chloride. Among them, according to the present invention, lauryl trimethyl ammonium chloride or stearyl trimethyl chloride is preferably used.
本発明において、これらの消色助剤は、インキ組成物に基づいて、通常、０．１〜１０重量％の範囲で用いられる。インキ組成物における消色助剤の配合量が０．１重量％よりもすくないときは、還元剤による塩基性染料の消色を助ける効果が殆どなく、他方、１０重量％を超えるときは、紙に筆記したとき、筆跡が滲んだり、裏抜けが起きたりする。また、例えば、マーキングペンに充填した場合等にインキが洩れる原因となる。 In the present invention, these decoloring aids are usually used in the range of 0.1 to 10% by weight based on the ink composition. When the blending amount of the decoloring aid in the ink composition is less than 0.1% by weight, there is almost no effect of assisting the decoloring of the basic dye by the reducing agent, while when it exceeds 10% by weight, the paper When writing on the handwriting, the handwriting may be blurred or show through. In addition, for example, when the marking pen is filled, the ink leaks.
本発明による筆記具用水性消色性インキ組成物は、上述した成分に加えて、必要に応じて、湿潤剤、ｐＨ調整剤、防腐防黴剤等を含んでいてもよい。上記湿潤剤は、得られるインキ組成物を、例えば、マーキングペンに用いた場合、ペン先の乾燥を抑制するために用いられる。湿潤剤としては、例えば、グリセリン、エチレングリコール、プロピレングリコール等の水溶性多価アルコールが好ましく用いられる。このような湿潤剤は、インキ組成物において、通常、１〜４０重量％の範囲で用いられる。湿潤剤のインキ組成物における割合が１重量％よりも少ないときは、ペン先の乾燥を抑制する効果が殆どなく、他方、４０重量％を超えるときは、この湿潤剤と水との混合物への塩基性染料の溶解性が低くなり、得られるインキ組成物の粘度が高くなるので、筆記性が悪くなるほか、筆跡の乾燥に過度に長時間を要する等の不具合が生じる。 The aqueous decolorizable ink composition for a writing instrument according to the present invention may contain a wetting agent, a pH adjuster, an antiseptic / antifungal agent, etc., if necessary, in addition to the components described above. The said wetting agent is used in order to suppress drying of a nib, when the obtained ink composition is used for a marking pen, for example. As the wetting agent, for example, water-soluble polyhydric alcohols such as glycerin, ethylene glycol, and propylene glycol are preferably used. Such a wetting agent is usually used in the range of 1 to 40% by weight in the ink composition. When the proportion of the humectant in the ink composition is less than 1% by weight, there is little effect of suppressing the drying of the nib, while when it exceeds 40% by weight, the mixture of the humectant with water is added. Since the solubility of the basic dye is lowered and the viscosity of the resulting ink composition is increased, the writing property is deteriorated, and problems such as an excessively long time for drying the handwriting occur.
本発明によるインキ組成物における残部を占める成分は、溶媒としての水である。インキ組成物におけるその割合は、特に限定されるものではないが、通常、５０〜９０重量％の範囲である。 The component occupying the balance in the ink composition according to the present invention is water as a solvent. The ratio in the ink composition is not particularly limited, but is usually in the range of 50 to 90% by weight.
本発明による上述したような筆記具用水性消色性インキ組成物による筆跡を消去するために用いる消去用インキ組成物は、還元剤のアルカリ性水溶液である。還元剤としては、扱いやすさの点から、亜硫酸塩又はチオ硫酸塩が好ましく用いられる。亜硫酸塩としては、例えば、亜硫酸ナトリウムや亜硫酸カリウムのような亜硫酸アルカリ金属塩、例えば、亜硫酸水素ナトリウムや亜硫酸水素カリウムのような亜硫酸水素アルカリ金属塩、更には、亜硫酸アンモニウム等を挙げることができる。一方、チオ硫酸塩としては、チオ硫酸ナトリウム、チオ硫酸カリウム、チオ硫酸アンモニウム等を挙げることができる。本発明においては、還元剤は、上記に限定されるものではなく、塩基性染料を還元し、消色するものであれば、いずれでも用いられるが、上述したなかでは、特に、亜硫酸ナトリウム及び亜硫酸カリウムから選ばれる少なくとも１つが好ましく用いられる。 The erasing ink composition used for erasing the handwriting by the aqueous decoloring ink composition for writing instruments as described above according to the present invention is an alkaline aqueous solution of a reducing agent. As the reducing agent, sulfite or thiosulfate is preferably used from the viewpoint of ease of handling. Examples of the sulfite include alkali metal sulfites such as sodium sulfite and potassium sulfite, alkali metal sulfites such as sodium hydrogen sulfite and potassium hydrogen sulfite, and ammonium sulfite. On the other hand, examples of the thiosulfate include sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate. In the present invention, the reducing agent is not limited to the above, and any reducing agent can be used as long as it reduces and discolors the basic dye. At least one selected from potassium is preferably used.
また、上記塩基としては、水溶性の無機塩基、有機塩基のいずれでも用いることができる。無機塩基としては、例えば、炭酸ナトリウムや炭酸水素ナトリウム等が好ましく、有機塩基としては、例えば、トリエタノールアミン等が好ましい。また、消去用インキ組成物も、必要に応じて、上述したような湿潤剤、ｐＨ調整剤、防腐防黴剤等を含有していてもよい。
In addition, as the base, either a water-soluble inorganic base or an organic base can be used. As the inorganic base, for example, sodium carbonate and sodium hydrogen carbonate are preferable, and as the organic base, for example, triethanolamine is preferable. The erasing ink composition may also contain a wetting agent, a pH adjuster, an antiseptic / antifungal agent, etc. as described above, if necessary.
本発明による筆記具用水性消色性インキ組成物は、水と、還元剤によって消色する塩基性染料と、長鎖アルキルトリ（低級アルキル）アンモニウムハライド及び（長鎖アルキル）ジ（低級アルキル）アンモニウムハライドから選ばれる少なくとも1種からなる消色助剤を含有し、その筆跡を上記還元剤を含有する消去用インキ組成物でなぞることによって、速やかに消色して、作業性にすぐれるものである。また、着色剤として還元剤で消色する塩基性染料と共に、還元剤で消色せず、しかも、上記塩基性染料と異なる色調を有する着色剤を併用して得られるインキ組成物は、その筆跡を還元剤を含む消去用インキ組成物にてなぞることによって、速やかに変色する。 A water-based decolorizable ink composition for a writing instrument according to the present invention comprises water, a basic dye that is decolored by a reducing agent, a long-chain alkyltri (lower alkyl) ammonium halide, and a (long-chain alkyl) di (lower alkyl) ammonium. It contains at least one decoloring aid selected from halides, and by tracing the handwriting with an erasing ink composition containing the above reducing agent, it can be quickly decolored and has excellent workability. is there. In addition, an ink composition obtained by using, together with a basic dye decolored with a reducing agent as a colorant, a colorant that is not decolorized with a reducing agent and has a color tone different from that of the basic dye, Is quickly changed in color with an erasing ink composition containing a reducing agent.
実施例
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例によって何ら限定されるものではない。
実施例１〜５及び比較例１〜５
第１表に示す塩基性染料、消色助剤、湿潤剤及び防腐防黴剤をイオン交換水に加えた後、室温で２時間攪拌して、第１表に示す組成を有する筆記具用水性インキ組成物をそれぞれ調製した。このようにして得られたインキ組成物をそれぞれ、中綿に充填して、マーキングペンに組み立てた。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
Examples 1-5 and Comparative Examples 1-5
A basic dye, a decoloring aid, a wetting agent and an antiseptic / antifungal agent shown in Table 1 are added to ion-exchanged water, followed by stirring at room temperature for 2 hours, and a water-based ink for writing instruments having the composition shown in Table 1 Each composition was prepared. Each of the ink compositions thus obtained was filled into a batting and assembled into a marking pen.
また、トリエタノールアミン９重量部、エチレングリコール１０重量部、防腐防黴剤０．６重量部（０．３重量部の日本エンバイロケミカルズ（株）製防腐剤コートサイドＨと０．３重量部のアーチ・ケミカルズ・ジャパン社製プロクセルＸＬ２）をイオン交換水７０．４重量部に加え、室温で３０分間攪拌した後、これに還元剤である亜硫酸ナトリウム１０重量部を加え、更に、室温で１時間攪拌して、消去用水性インキ組成物を調製した。これも、同様に、中綿に充填して、消色用ペンに組み立てた。 Further, 9 parts by weight of triethanolamine, 10 parts by weight of ethylene glycol, 0.6 parts by weight of antiseptic / antifungal agent (0.3 parts by weight of preservative coated side H manufactured by Nippon Enviro Chemicals Co., Ltd. and 0.3 parts by weight) Arch Chemicals Japan Proxel XL2) was added to 70.4 parts by weight of ion-exchanged water and stirred at room temperature for 30 minutes, and then 10 parts by weight of sodium sulfite as a reducing agent was added thereto, and further at room temperature for 1 hour. By stirring, an erasing water-based ink composition was prepared. This was similarly filled in a batting and assembled into a decoloring pen.
上記マーキングペンをそれぞれ用いて、実施例１〜５及び比較例１〜５で得られた水性インキ組成物にて普通紙に線（筆跡）を描き、温度２０℃及び相対湿度６５％の環境条件下に１時間乾燥させた後、上記筆跡を上記消去用ペンでなぞって、以下のようにして、筆跡の消色又は変色の速度を調べた。 Using each of the marking pens, a line (handwriting) is drawn on plain paper with the aqueous ink compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 5, and the environmental conditions are a temperature of 20 ° C. and a relative humidity of 65%. After drying for 1 hour, the handwriting was traced with the erasing pen, and the speed of decoloring or discoloration of the handwriting was examined as follows.
消色性
実施例１〜３及び比較例１〜３で得られたインキ組成物による筆跡については、筆記してから２０秒後及び１時間後にＬ*ａ*ｂ*を測定し、併せて、筆跡を形成した普通紙のＬ*ａ*ｂ*も測定して、筆跡を消去した後の紙上の筆跡跡と当初の紙との色差ΔＥ*ａｂを下記計算式により算出した。
ΔＥ*ａｂ＝[(ΔＬ*)2 ＋ (Δａ*)2 ＋ (Δｂ*)2]1/2 … （１）
実施例４〜５及び比較例４〜５で得られたインキ組成物による筆跡については、筆記してから２０秒後及び１時間後の色調を目視で評価した。以上の結果を第１表に示す。For the handwriting by the ink compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3, L * a * b * was measured 20 seconds and 1 hour after writing, The L * a * b * of the plain paper on which the handwriting was formed was also measured, and the color difference ΔE * ab between the handwriting on the paper after erasing the handwriting and the original paper was calculated by the following formula.
ΔE * ab = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ] 1/2 (1)
About the handwriting by the ink composition obtained in Examples 4-5 and Comparative Examples 4-5, the color tone 20 seconds after and 1 hour after writing was evaluated visually. The above results are shown in Table 1.
第１表から明らかなように、実施例１〜３で得られたインキ組成物による筆跡は、消去用ペンを用いて、消去用インキ組成物でなぞってから、２０秒後にかなりの程度に消色した。これに対して、比較例１〜３で得られたインキ組成物による筆跡は、それを消去用ペンを用いて、消去用インキ組成物でなぞってから、２０秒後にも、紙とのΔＥ*ａｂが大きく、筆跡が消色する速度が遅かった。
実施例４及び５で得られた水性インキ組成物による筆跡は、消去用インキでなぞってから、２０秒後にかなりの程度に変色したが、比較例４及び５で得られたインキ組成物による筆跡は、消去用インキでなぞってから、２０秒後にも、変色の速度が遅く、明確に変色しなかった。
As is apparent from Table 1, the handwritings of the ink compositions obtained in Examples 1 to 3 were erased to a considerable extent 20 seconds after tracing with the erasing ink composition using an erasing pen. Colored. On the other hand, the handwriting by the ink composition obtained in Comparative Examples 1 to 3 was traced with the erasing ink composition using the erasing pen, and ΔE * with the paper was 20 seconds later . The ab was large and the speed at which the handwriting was erased was slow.
Although the handwriting by the aqueous ink composition obtained in Examples 4 and 5 was traced to a considerable degree after 20 seconds after tracing with the erasing ink, the handwriting by the ink composition obtained in Comparative Examples 4 and 5 was used. After tracing with the erasing ink, even after 20 seconds, the speed of the color change was slow and the color did not change clearly.
Claims (8)
一般式（Ｉ）
（式中、Ｒ１ は炭素原子数１０〜１８の長鎖アルキル基を示し、Ｒ2 はそれぞれ独立にメチル基又はエチル基を示す。）
で表される長鎖アルキルトリ（低級アルキル）アンモニウムハライド及び
一般式（II）
（式中、Ｒ１ は炭素原子数１０〜１８の長鎖アルキル基を示し、Ｒ2 はそれぞれ独立にメチル基又はエチル基を示す。）
で表されるジ（長鎖アルキル）ジ（低級アルキル）アンモニウムハライドから選ばれる少なくとも1種からなる消色助剤を含有することを特徴とする筆記具用水性消色性インキ組成物。
Water, a basic dye that is decolorized by a reducing agent and sulfite,
Formula (I)
(In the formula, R 1 represents a long-chain alkyl group having 10 to 18 carbon atoms, and R 2 independently represents a methyl group or an ethyl group.)
Long-chain alkyltri (lower alkyl) ammonium halides represented by the general formula (II)
(In the formula, R 1 represents a long-chain alkyl group having 10 to 18 carbon atoms, and R 2 independently represents a methyl group or an ethyl group.)
An aqueous decolorizable ink composition for a writing instrument, comprising a decoloring aid comprising at least one selected from di (long-chain alkyl) di (lower alkyl) ammonium halides represented by:
The aqueous decolorizable ink composition for a writing instrument according to claim 1, wherein the long-chain alkyltri (lower alkyl) ammonium halide is a long-chain alkyltrimethylammonium chloride.
The aqueous decolorizable ink composition for a writing instrument according to claim 1, wherein the di (long chain alkyl) di (lower alkyl) ammonium halide is di (long chain alkyl) dimethylammonium chloride.
The aqueous decolorizable ink composition for a writing instrument according to claim 1, comprising a decoloring aid in the range of 0.5 to 10% by weight.
The aqueous decolorizable ink composition for a writing instrument according to claim 1, wherein the reducing agent is sulfite or thiosulfate.
The aqueous decolorizable ink composition for a writing instrument according to claim 5, wherein the sulfite is at least one selected from sodium sulfite and potassium sulfite.
An aqueous color-changing ink composition for a writing instrument, wherein the ink composition according to any one of claims 1 to 5 further containing a colorant that is not decolored by sulfite.
The aqueous discoloring ink composition for a writing instrument according to claim 7, wherein the reducing agent is sulfite or thiosulfate.
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| PCT/JP2006/323801 WO2007063892A1 (en) | 2005-12-01 | 2006-11-29 | Aqueous decolorable ink composition for use in writing instruments |
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