JP2007332249A - Water-erasable solid drawing material - Google Patents
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Abstract
Description
本発明は、クレヨン、ホワイトボード用マーカー、建材用マーカー等に用いることができる水消去性固形描画材に関する。さらに詳しくは、水を含んだ布等で払拭することにより非吸収面に描画した筆跡が容易に除去され、また色が水で消えるので、払拭後の布等が着色して汚染されることがない水消去性固形描画材に関する。 The present invention relates to a water-erasable solid drawing material that can be used for crayons, whiteboard markers, building material markers, and the like. More specifically, by wiping with a cloth containing water, the handwriting drawn on the non-absorbing surface is easily removed, and the color disappears with water, so that the cloth after wiping may be colored and contaminated. There is no water erasable solid drawing material.
従来から、幼児用玩具の落書き用クレヨンやプラスチックボード用の筆記具などの用途に向けて、水拭きのみで簡単に拭い去れる固形描画材が提供されており、これらの描画材では筆跡の水拭き除去性を付与するために組成中に水溶性の原料を含んでいる。具体的には、例えばポリエチレングリコールと非イオン性界面活性剤を使用したもの（特許文献１）、ポリエチレングリコール誘導体を使用したもの（特許文献２）、特定のヒドロキシル価を有するワックス及び特定のHLB値を有する界面活性剤を使用したもの（特許文献３）等が知られている。しかしこれらの描画材は色材として顔料を使用しているために、筆跡乃至塗膜除去後の面に顔料が着色した部分が残ってしまい、水拭きでは完全に筆跡を消去することが難しい。また拭き取られた筆跡乃至塗膜の組成物は、顔料を含んだまま払拭布に移動するので、使用の度に払拭布は着色し汚れてしまう。従って払拭布は使い捨てとするか、もしくは洗濯を念入りに行う必要があるので、需要者にとっては使用後の処理が煩雑であり、かつ不経済的である。これらのことから、このような水消去性描画材においては、水拭きによる除去性が優れているのみではなく、払拭後の布の着色が水で消去可能となれば、非常に有利であると考えられる。 Traditionally, solid drawing materials that can be easily wiped off with just a wipe are provided for applications such as graffiti crayons for toys for infants and writing tools for plastic boards. In order to provide removability, a water-soluble raw material is included in the composition. Specifically, for example, one using polyethylene glycol and a nonionic surfactant (Patent Document 1), one using a polyethylene glycol derivative (Patent Document 2), a wax having a specific hydroxyl number, and a specific HLB value The thing using the surfactant which has (patent document 3) etc. is known. However, since these drawing materials use a pigment as a coloring material, a portion where the pigment is colored remains on the surface after the handwriting or coating film is removed, and it is difficult to completely erase the handwriting by wiping with water. Moreover, since the wiped handwriting or the composition of the coating film moves to the wiping cloth while containing the pigment, the wiping cloth becomes colored and dirty every time it is used. Accordingly, since the wiping cloth needs to be disposable or carefully washed, it is complicated and uneconomical for the consumer after use. Therefore, in such a water erasable drawing material, not only is the removability by water wiping excellent, but if the coloring of the cloth after wiping becomes erasable with water, it is very advantageous. Conceivable.
一方、着色が水で消える描画材としては洋裁用チャコが知られている。チャコに用いる描画材としては、例えば、色材が顔料ではなく、界面活性剤の呈色剤を界面活性剤と発色反応させたものである描画材がある（特許文献４）。この描画材の筆跡は、界面活性剤を水で除去することで完全に消色できるが、その発色は青色のみであるため、本発明で検討するクレヨンや一般的な筆記具等、様々な色が要求される用途の描画材には不向きである。同様にチャコ用描画材として、ロイコ染料をサリチル酸亜鉛で発色させて色材とした水消去性固形描画材も知られている（特許文献５）。この描画材には、カルナバワックス、晒モンタンワックス、オーリキユリーワックス、キャンデリラワックス、酸化マイクロワックス、サゾールワックス、ヘキストワックス等の油溶性ワックスと非イオン性界面活性剤が含まれており、筆跡を水で濡らすと、サリチル酸亜鉛が水で溶解し、油溶性ワックスに残留するロイコ染料から外れることで消色するものである。しかし、この描画材の筆跡は水拭きしても油溶性ワックス成分が残留し、筆跡乃至塗膜の組成物は完全には除去されないため、水消去性のクレヨンや筆記具に用いることはできない。 On the other hand, chaco for dressmaking is known as a drawing material in which coloring disappears with water. As a drawing material used for the chaco, for example, there is a drawing material in which a coloring material is not a pigment, but a coloring agent of a surfactant is reacted with a surfactant (Patent Document 4). The handwriting of this drawing material can be completely erased by removing the surfactant with water, but since the color development is only blue, there are various colors such as crayons and general writing instruments studied in the present invention. It is not suitable for drawing materials for the required applications. Similarly, a water erasable solid drawing material in which a leuco dye is colored with zinc salicylate as a coloring material is also known as a drawing material for chaco (Patent Document 5). This drawing material contains oil-soluble wax and nonionic surfactant such as carnauba wax, bleached montan wax, auxiliary wax, candelilla wax, oxidized microwax, sazol wax, Hoechst wax, When the handwriting is wetted with water, the zinc salicylate dissolves in water and decolorizes by detaching from the leuco dye remaining in the oil-soluble wax. However, since the oil-soluble wax component remains even if the handwriting of this drawing material is wiped with water and the composition of the handwriting or the coating film is not completely removed, it cannot be used for a water erasable crayon or a writing instrument.
本発明の課題は、多様な色合いが得られ、また筆記直後の発色が鮮明でありながら、水拭きすることで簡単に筆跡を除去することができ、かつ払拭後の布やスポンジ等に着色した汚れも水で消色できる水溶性の固形描画材を提供することである。 The problem of the present invention is that various shades are obtained, and the color immediately after writing is clear, but the handwriting can be easily removed by wiping with water, and the cloth or sponge after wiping is colored. It is an object to provide a water-soluble solid drawing material that can be stained with water.
上記課題を解決するため鋭意検討した結果、本発明では、ロイコ染料、水溶性顕色剤及び水溶性ワックスを含む水消去性固形描画材を採用した。前記水溶性ワックスとしては、数平均分子量１５００〜２００００のポリエチレングリコールであることが好ましく、また前記水溶性ワックスは、固形描画材全量に対して３０〜９４重量％含まれることが好ましい。更に本発明の水消去性固形描画材は、カチオン系界面活性剤を含むことが好ましく、前記カチオン系界面活性剤は第４級アンモニウム塩であることが好ましい。また前記カチオン系界面活性剤は固形描画材全量に対して０．１〜２０重量％含まれることが好ましい。更に本発明の水消去性固形描画材は、体質顔料を、前記水溶性ワックス（Ａ）に対する当該体質顔料（Ｂ）の重量比（Ｂ／Ａ）が０．０５〜２．５となるように含むことが好ましく、この場合の水溶性ワックスは、数平均分子量１５００〜２００００のポリエチレングリコールであることが好ましい。 As a result of intensive studies to solve the above problems, the present invention employs a water-erasable solid drawing material containing a leuco dye, a water-soluble developer and a water-soluble wax. The water-soluble wax is preferably polyethylene glycol having a number average molecular weight of 1500 to 20000, and the water-soluble wax is preferably contained in an amount of 30 to 94% by weight based on the total amount of the solid drawing material. Furthermore, the water-erasable solid drawing material of the present invention preferably contains a cationic surfactant, and the cationic surfactant is preferably a quaternary ammonium salt. Moreover, it is preferable that 0.1-20 weight% of said cationic surfactant is contained with respect to the solid drawing material whole quantity. Further, in the water-erasable solid drawing material of the present invention, the extender pigment is adjusted such that the weight ratio (B / A) of the extender pigment (B) to the water-soluble wax (A) is 0.05 to 2.5. The water-soluble wax in this case is preferably polyethylene glycol having a number average molecular weight of 1500 to 20000.
また本発明は、前記水消去性固形描画材からなるクレヨンであり、前記水消去性固形描画材からなるホワイトボード用固形マーカーであり、前記水消去性固形描画材からなる建材用固形マーカーである。更に前記水消去性固形描画材からなる筆記具と、非吸収面を有する被筆記物を含む玩具セットである。 Further, the present invention is a crayon made of the water erasable solid drawing material, a whiteboard solid marker made of the water erasable solid drawing material, and a building material solid marker made of the water erasable solid drawing material. . Furthermore, it is a toy set including a writing instrument made of the water-erasable solid drawing material and a writing object having a non-absorbing surface.
本発明の固形描画材は、ロイコ染料、水溶性顕色剤及び水溶性ワックスを含み、特に
水溶性ワックスとして数平均分子量１５００〜２００００のポリエチレングリコールを
含む固形描画材である。したがって、上記水溶性ワックスは常温で固体であるが、水拭きのみで速やかに溶解して除去できる筆跡乃至塗膜を形成するものである。また、上記水溶性ワックスを、固形描画材全量に対して３０〜９４重量％含有することで、油溶性ワックスや樹脂を用いた場合と同程度の成形性を担保することができた。
The solid drawing material of the present invention is a solid drawing material containing a leuco dye, a water-soluble developer and a water-soluble wax, and particularly containing polyethylene glycol having a number average molecular weight of 1500 to 20000 as the water-soluble wax. Therefore, although the water-soluble wax is solid at room temperature, it forms a handwriting or a coating film that can be quickly dissolved and removed only by wiping with water. Further, by containing the water-soluble wax in an amount of 30 to 94% by weight based on the total amount of the solid drawing material, it was possible to ensure the same moldability as when oil-soluble wax or resin was used.
また、色材は無色のロイコ染料を水溶性の顕色剤により発色させたものであり、筆跡乃至塗膜中の当該顕色剤が水に溶解して消色するものである。本発明の水溶性のワックスを用いた固形描画材は、油溶性のワックスを用いた場合とは異なり、ロイコ染料が顕色剤と伴に拭き取られるが、払拭の際にロイコ染料及び顕色剤が減感剤であるカチオン系界面活性剤と接触して発色が阻害されることで、その水消色性は完全なものとなった。 The coloring material is obtained by coloring a colorless leuco dye with a water-soluble developer, and the developer in the handwriting or the coating film is dissolved in water and decolored. The solid drawing material using the water-soluble wax of the present invention is different from the case of using an oil-soluble wax, the leuco dye is wiped off together with the developer. When the agent comes into contact with a cationic surfactant that is a desensitizer and the color development is inhibited, the water decoloring property becomes perfect.
更に、体質顔料を一定量添加することで、水溶性ワックスを３０重量％以上含んでいることにより生じるべたつきを防ぎ、かつ筆跡乃至塗膜の隠蔽性を向上させて色材の濃度を高く見せる効果を得た。 Furthermore, the addition of a certain amount of extender pigment prevents the stickiness caused by containing 30% by weight or more of a water-soluble wax, and also improves the concealability of handwriting or paint film, thereby increasing the colorant concentration. Got.
本発明で用いられるロイコ染料としては、トリフェニルメタン系、フルオラン系、スピロピラン系、インドリルフタリド系、ローダミンラクタム系、ロイコオーラミン系などを例示することができ、特に限定されるものではない。
上記ロイコ染料は、水消去性固形描画材組成物全量に対して０．１〜５重量％含ませることができ、好ましい含有量は０．５〜３重量％である。上記ロイコ染料が組成物全量に対して５重量％を超えると製造時に溶解することが困難であり、０．１重量％未満では発色濃度が薄く、筆記直後の筆跡の初期発色性が乏しい結果となる。
Examples of the leuco dye used in the present invention include triphenylmethane series, fluorane series, spiropyran series, indolylphthalide series, rhodamine lactam series, and leucoolamine series, and are not particularly limited. .
The leuco dye can be contained in an amount of 0.1 to 5% by weight based on the total amount of the water-erasable solid drawing material composition, and the preferred content is 0.5 to 3% by weight. If the leuco dye exceeds 5% by weight with respect to the total amount of the composition, it is difficult to dissolve at the time of manufacture, and if it is less than 0.1% by weight, the color density is thin and the initial color developability of the handwriting immediately after writing is poor. Become.
本発明で用いられる水溶性顕色剤としては、ｐ−トルエンスルホン酸、スルホサリチル酸、ナフタレンスルホン酸、サリチル酸亜鉛、マロン酸やリンゴ酸等のカルボン酸類などを例示することができ、特に限定されるものではない。
上記水溶性顕色剤は、水消去性固形描画材組成物全量に対して０．２〜２０重量％含ませることができ、好ましい含有量は０．５〜１０重量％である。上記水溶性の顕色剤が組成物全量に対して２０重量％を超えると水消去性が悪くなり、０．２重量％未満では発色濃度が薄く、筆記直後の筆跡の初期発色性が乏しい結果となる。
Examples of the water-soluble developer used in the present invention include p-toluenesulfonic acid, sulfosalicylic acid, naphthalenesulfonic acid, zinc salicylate, carboxylic acids such as malonic acid and malic acid, and the like. It is not a thing.
The water-soluble developer can be contained in an amount of 0.2 to 20% by weight with respect to the total amount of the water-erasable solid drawing material composition, and the preferred content is 0.5 to 10% by weight. When the water-soluble developer exceeds 20% by weight with respect to the total amount of the composition, the water erasability deteriorates. When the water-soluble developer is less than 0.2% by weight, the color density is low and the initial color developability of the handwriting immediately after writing is poor. It becomes.
本発明で用いられる水溶性ワックスとしては、ポリエチレングリコールが好ましい。本発明では、ポリエチレングリコールにはその誘導体も含まれる。その他、ポリオキシエチレンポリオキシプロピレンブロックコポリマー、ポリテトラメチレンエーテルグリコールなどを例示することができる。
また、ポリエチレングリコール数平均分子量は、本発明で求められるワックス状の性質を有するためには少なくとも１５００が好ましく、より好ましくは２０００以上、最適には５０００以上である。また数平均分子量の上限値は、好ましくは２００００、より好ましくは１５０００、さらに好ましくは１００００、最適には６０００であることが望ましい。
上記水溶性ワックスは、水消去性固形描画材組成物全量に対して３０重量％が好ましく、より好ましくは４０重量％、最適には５０重量％である。またその含有量の上限値も好ましくは９４重量％、より好ましくは９０重量％、最適には８０重量％である。上記水溶性ワックスがインキ組成物全量に対して９４重量％を超えると固形描画材が硬くなり、また手に持ったときのベタツキが発生する。反対に３０重量％未満では固形描画材の成形性が悪くなってしまう。
The water-soluble wax used in the present invention is preferably polyethylene glycol. In the present invention, polyethylene glycol includes derivatives thereof. Other examples include polyoxyethylene polyoxypropylene block copolymer, polytetramethylene ether glycol and the like.
The polyethylene glycol number average molecular weight is preferably at least 1500, more preferably 2000 or more, and most preferably 5000 or more in order to have the wax-like properties required in the present invention. The upper limit of the number average molecular weight is preferably 20000, more preferably 15000, still more preferably 10,000, and most preferably 6000.
The water-soluble wax is preferably 30% by weight, more preferably 40% by weight, and most preferably 50% by weight, based on the total amount of the water-erasable solid drawing material composition. The upper limit of the content is preferably 94% by weight, more preferably 90% by weight, and most preferably 80% by weight. When the water-soluble wax exceeds 94% by weight with respect to the total amount of the ink composition, the solid drawing material becomes hard and stickiness occurs when it is held in the hand. On the other hand, if it is less than 30% by weight, the moldability of the solid drawing material is deteriorated.
本発明で用いられる体質顔料としては、特に限定されるものではないが、炭酸カルシウム、硫酸バリウム、炭酸マグネシウム、酸化チタン、カオリン、シリカなどを例示することができる。なかでも、炭酸カルシウム、硫酸バリウム、酸化チタン等、水分散性がよいものが好適に用いられる。
上記体質顔料は、前記水溶性ワックスに対する重量比が０．０５〜２．５であることが望ましい。また水消去性固形描画材組成物全量に対して５〜７０重量％含ませることができ、好ましい含有量は１０〜５０重量％である。上記体質顔料が組成物全量に対して７０重量％を超えると固形描画材が脆くなり、５重量％未満では固形描画材が硬くなり、また手に持ったときにベタツキが発生してしまう。
The extender pigment used in the present invention is not particularly limited, and examples thereof include calcium carbonate, barium sulfate, magnesium carbonate, titanium oxide, kaolin, and silica. Among them, those having good water dispersibility such as calcium carbonate, barium sulfate, titanium oxide and the like are preferably used.
The extender pigment preferably has a weight ratio to the water-soluble wax of 0.05 to 2.5. Moreover, 5 to 70 weight% can be included with respect to the water erasable solid drawing material composition whole quantity, and preferable content is 10 to 50 weight%. If the extender pigment exceeds 70% by weight based on the total amount of the composition, the solid drawing material becomes brittle. If it is less than 5% by weight, the solid drawing material becomes hard, and stickiness occurs when it is held in the hand.
本発明で用いられるカチオン系界面活性剤としては、減感剤としての性質を有するものが好ましく、塩化ラウリルトリメチルアンモニウム、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、塩化ヤシアルキルトリメチルアンモニウム、塩化牛脂アルキルトリメチルアンモニウム、塩化ベヘニルトリメチルアンモニウム、塩化ヘキサデシルトリメチルアンモニウム、塩化オクタデシルトリメチルアンモニウム、塩化ジオクチルジメチルアンモニウム、塩化アルキルベンジルジメチルアンモニウム、塩化ジステアリルジメチルアンモニウム、アルキルイミダゾリン４級塩、アルキルイソキノリニウム塩、塩化アルキルピリジニウム塩などの第４級アンモニウム塩を例示することができる。なかでも、塩化ベヘニルトリメチルアンモニウム、塩化ジステアリルジメチルアンモニウムが好適に用いられる。
上記カチオン系界面活性剤は、水消去性固形描画材組成物全量に対して０．１〜２０重量％含ませることができ、好ましい含有量は１〜１０重量％である。上記水溶性ワックスが組成物全量に対して２０重量％を超えると着色力が低下し、０．１重量％未満では消色効果が得られない。
As the cationic surfactant used in the present invention, those having a property as a desensitizer are preferable. Lauryltrimethylammonium chloride, alkyltrimethylammonium salt, dialkyldimethylammonium salt, coconut alkyltrimethylammonium chloride, tallow alkyltrimethyl chloride Ammonium, behenyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dioctyldimethylammonium chloride, alkylbenzyldimethylammonium chloride, distearyldimethylammonium chloride, alkylimidazoline quaternary salt, alkylisoquinolinium salt, alkyl chloride Quaternary ammonium salts such as pyridinium salts can be exemplified. Of these, behenyltrimethylammonium chloride and distearyldimethylammonium chloride are preferably used.
The cationic surfactant can be contained in an amount of 0.1 to 20% by weight with respect to the total amount of the water erasable solid drawing material composition, and the preferred content is 1 to 10% by weight. When the water-soluble wax exceeds 20% by weight with respect to the total amount of the composition, the coloring power decreases, and when it is less than 0.1% by weight, the decoloring effect cannot be obtained.
本発明の被筆記具の形態は特に限定されるものではなく、ボード状、絵本状、ボール状など様々な形態をとることができる。また、被筆記具に含まれる非吸収面としては、コート紙や、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、金属、ガラス等の素材からなるものが挙げられる。 The form of the writing instrument of the present invention is not particularly limited, and can take various forms such as a board shape, a picture book shape, and a ball shape. Moreover, as a non-absorbing surface contained in a writing instrument, what consists of raw materials, such as a coated paper, polyethylene, a polypropylene, a polyethylene terephthalate, a metal, glass, is mentioned.
なお、本発明の固形描画材は、水拭きによる除去性や水消去性を主としているが、水による消去等に限定されるものではなく、例えばアルコールなどの水溶性有機溶剤を用いて消去することもできる。 Although the solid drawing material of the present invention mainly has removability by water wiping and water erasability, it is not limited to water erasing and the like, for example, erasing using a water-soluble organic solvent such as alcohol. You can also.
＜描画材組成物＞
表１に示す組成により、以下の製造工程にて実施例１〜実施例１０の描画材組成物を得た。
<Drawing material composition>
With the compositions shown in Table 1, the drawing material compositions of Examples 1 to 10 were obtained in the following production steps.
＜実施例製造工程＞
（１）ポリエチレングリコール、ロイコ染料、顕色剤（サリチル酸亜鉛）を１２０℃で加熱攪拌し、溶液（Ａ）を得た。
（２）上記で得た溶液（Ａ）に体質顔料（炭酸カルシウム又は酸化チタン）を添加し、３本ロールミルにて均一な分散体（Ｂ）を得た。その後、各処方に応じて４級アンモニウム塩を添加し、緩やかに攪拌した。
（３）上記で得た分散体（Ｂ）を流し込み成形し、固形描画材（円柱状、直径１０ｍｍ、長さ４０ｍｍ）を得た。
<Example manufacturing process>
(1) Polyethylene glycol, leuco dye, and developer (zinc salicylate) were heated and stirred at 120 ° C. to obtain a solution (A).
(2) An extender pigment (calcium carbonate or titanium oxide) was added to the solution (A) obtained above, and a uniform dispersion (B) was obtained with a three-roll mill. Then, quaternary ammonium salt was added according to each prescription, and it stirred gently.
(3) The dispersion (B) obtained above was cast and molded to obtain a solid drawing material (columnar shape, diameter 10 mm, length 40 mm).
＜評価＞
実施例１〜実施例１０で得られた各固形描画材を用いて、ＰＥＴシートに筆記した際の描画性を評価した。その後、その筆跡の消色性及び消去性を以下に示す方法、基準にて評価した。結果を表１に示す。
<Evaluation>
Using each solid drawing material obtained in Example 1 to Example 10, the drawing property when writing on a PET sheet was evaluated. Then, the decoloring property and erasing property of the handwriting were evaluated by the following methods and standards. The results are shown in Table 1.
（筆跡の消去性）
ＰＥＴシートに筆記後、水を含ませた布で筆跡を消去する。
○：綺麗に消去できる
△：筆跡の一部が残る
×：消去されない
（筆跡の消色性）
ＰＥＴシートに筆記後、筆跡に水滴を滴下し、筆跡の消色を評価した。
○：消色する
△：若干色残りがある
×：消色されない
(Eraseability of handwriting)
After writing on the PET sheet, erase the handwriting with a cloth soaked in water.
○: Clearly erased △: Part of the handwriting remains ×: Not erased (erasability of handwriting)
After writing on the PET sheet, a water droplet was dropped on the handwriting to evaluate the decolorization of the handwriting.
○: Decolored △: Some color residue ×: Not decolored
本発明は、水又は水を含んだスポンジや布等で筆跡を消去することができるホワイトボード用又は描画シート用の描画材や、建材のマーキングペン用描画材などに用いることができる。 INDUSTRIAL APPLICABILITY The present invention can be used for drawing materials for white boards or drawing sheets that can erase handwriting with water or a sponge or cloth containing water, drawing materials for marking pens for building materials, and the like.
Claims (11)
A toy set comprising a writing instrument comprising the water-erasable solid drawing material according to any one of claims 1 to 7 and a writing object having a non-absorbing surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006164943A JP5089088B2 (en) | 2006-06-14 | 2006-06-14 | Water erasable solid drawing material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006164943A JP5089088B2 (en) | 2006-06-14 | 2006-06-14 | Water erasable solid drawing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007332249A true JP2007332249A (en) | 2007-12-27 |
| JP5089088B2 JP5089088B2 (en) | 2012-12-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006164943A Expired - Fee Related JP5089088B2 (en) | 2006-06-14 | 2006-06-14 | Water erasable solid drawing material |
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| JP (1) | JP5089088B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558952A (en) * | 2012-01-06 | 2012-07-11 | 浙江大学 | Irreversible thermally induced decoloring printing ink and preparation method thereof |
| CN102604483A (en) * | 2012-01-15 | 2012-07-25 | 山西大学 | White board wax pencil capable of wiping up writing marks by water |
| CN103073956A (en) * | 2013-01-14 | 2013-05-01 | 山西大学 | Fadable coloured chalk for white board |
| JP2015052064A (en) * | 2013-09-09 | 2015-03-19 | 株式会社パイロットコーポレーション | Solid writing article, and solid writing article set containing the same |
| GB2566364A (en) * | 2017-09-08 | 2019-03-13 | Crayola Llc | Color development writing compositions and writing instruments |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5382507A (en) * | 1976-12-24 | 1978-07-21 | Naigai Ink Mfg Co Ltd | Water decoloring drawing material |
| JPS60147469A (en) * | 1983-12-19 | 1985-08-03 | モベイ・コーポレーシヨン | Polyethylene terephthalate composition |
| JPS6357683A (en) * | 1986-08-29 | 1988-03-12 | Bunchiyou:Kk | Production of crayon |
| JPS63242677A (en) * | 1987-03-31 | 1988-10-07 | Sony Corp | Reversible coloring and decoloring material |
| JPH06128523A (en) * | 1989-12-19 | 1994-05-10 | Union Carbide Chem & Plast Co Inc | Water-soluble crayon composition |
| JPH08332452A (en) * | 1995-06-07 | 1996-12-17 | Sakura Color Prod Corp | Painting method and crayon |
| JPH11116880A (en) * | 1997-10-09 | 1999-04-27 | Sakura Color Prod Corp | Color-changing crayon set and composition for color-changing crayon |
-
2006
- 2006-06-14 JP JP2006164943A patent/JP5089088B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5382507A (en) * | 1976-12-24 | 1978-07-21 | Naigai Ink Mfg Co Ltd | Water decoloring drawing material |
| JPS60147469A (en) * | 1983-12-19 | 1985-08-03 | モベイ・コーポレーシヨン | Polyethylene terephthalate composition |
| JPS6357683A (en) * | 1986-08-29 | 1988-03-12 | Bunchiyou:Kk | Production of crayon |
| JPS63242677A (en) * | 1987-03-31 | 1988-10-07 | Sony Corp | Reversible coloring and decoloring material |
| JPH06128523A (en) * | 1989-12-19 | 1994-05-10 | Union Carbide Chem & Plast Co Inc | Water-soluble crayon composition |
| JPH08332452A (en) * | 1995-06-07 | 1996-12-17 | Sakura Color Prod Corp | Painting method and crayon |
| JPH11116880A (en) * | 1997-10-09 | 1999-04-27 | Sakura Color Prod Corp | Color-changing crayon set and composition for color-changing crayon |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558952A (en) * | 2012-01-06 | 2012-07-11 | 浙江大学 | Irreversible thermally induced decoloring printing ink and preparation method thereof |
| CN102604483A (en) * | 2012-01-15 | 2012-07-25 | 山西大学 | White board wax pencil capable of wiping up writing marks by water |
| CN103073956A (en) * | 2013-01-14 | 2013-05-01 | 山西大学 | Fadable coloured chalk for white board |
| JP2015052064A (en) * | 2013-09-09 | 2015-03-19 | 株式会社パイロットコーポレーション | Solid writing article, and solid writing article set containing the same |
| GB2566364A (en) * | 2017-09-08 | 2019-03-13 | Crayola Llc | Color development writing compositions and writing instruments |
| US11192395B2 (en) | 2017-09-08 | 2021-12-07 | Crayola Llc | Color development writing compositions and writing instruments |
| GB2566364B (en) * | 2017-09-08 | 2022-02-23 | Crayola Llc | Writing compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5089088B2 (en) | 2012-12-05 |
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