JP2015030831A - Photo-erasable aqueous ink composition and marking pen - Google Patents
Photo-erasable aqueous ink composition and marking pen Download PDFInfo
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Images
Abstract
Description
本発明は、光消去性水性インキ組成物及びマーキングペンに関する。 The present invention relates to a photo-erasable water-based ink composition and a marking pen.
従来より、色材としてｐＨ指示薬を含む筆記具用インキ組成物を用いることにより、得られた筆記線が一定時間経過後に消色することが知られている（例えば、特許文献１〜３参照）。 Conventionally, by using an ink composition for a writing instrument containing a pH indicator as a coloring material, it is known that the obtained writing line is decolored after a certain period of time (see, for example, Patent Documents 1 to 3).
一方、光触媒用酸化チタン微粒子と水性染料とを併用したインキ組成物又は色材として紅麹色素を含むインキ組成物を用いることにより、光を照射した筆記線が消色することが知られている（例えば、特許文献４〜５参照）。 On the other hand, it is known that a writing line irradiated with light is decolored by using an ink composition containing titanium oxide fine particles for photocatalyst and an aqueous dye in combination or an ink composition containing a red pigment as a coloring material. (For example, refer to Patent Documents 4 to 5).
しかしながら、例えば、特許文献１〜３に開示されているインキ組成物は強塩基性であり、インキ組成物が皮膚に付着した場合、皮膚を侵すおそれがあった。 However, for example, the ink compositions disclosed in Patent Documents 1 to 3 are strongly basic, and when the ink composition adheres to the skin, there is a risk of damaging the skin.
また、特許文献４に開示されているインキ組成物では、消色に紫外線が必要でありＬＥＤ照射下では消色しない、及び、インキ消色後に酸化チタンによる白色が残る、などの問題があった。 In addition, the ink composition disclosed in Patent Document 4 has problems such as that ultraviolet light is required for color erasing and that the color is not erased under LED irradiation, and that white color remains due to titanium oxide after color erasing. .
さらに、特許文献５に開示されるインキ組成物において、色材として、例えば、モナスコルブリン又はアンカフラビンを用いた場合、消色に紫外線が必要でありＬＥＤ照射下では十分に消色しない、及び、太陽光への曝露なしに消色するには５時間以上必要となることがある、などの問題があった。 Furthermore, in the ink composition disclosed in Patent Document 5, when, for example, Monascorbulin or Ankaflavin is used as a colorant, ultraviolet light is required for decolorization, and the color is not sufficiently decolored under LED irradiation. In addition, there are problems such that it may take 5 hours or more to discolor without exposure to sunlight.
本発明は、上記課題に鑑みてなされたものであり、人体への安全性に優れ、紫外線を含む太陽光等に曝露した場合だけでなく、可視光線のみを照射した場合でも、短時間で消色する筆記線を得ることができる、光消去性水性インキ組成物、及びそれを用いたマーキングペンを提供することを目的とする。 The present invention has been made in view of the above problems, and is excellent in safety to the human body, and not only when exposed to sunlight including ultraviolet rays but also when irradiated only with visible light, can be quickly turned off. An object of the present invention is to provide a photo-erasable water-based ink composition capable of obtaining colored writing lines, and a marking pen using the same.
上記目的を達成するために、本発明は、モナスカスイエロー及び水溶性界面活性剤を含有し、上記水溶性界面活性剤の含有量は、光消去性水性インキ組成物の全量を基準として、３質量％以上である、光消去性水性インキを提供する。 In order to achieve the above object, the present invention contains Monascus yellow and a water-soluble surfactant, and the content of the water-soluble surfactant is 3 mass based on the total amount of the photo-erasable water-based ink composition. %, The photo-erasable water-based ink is provided.
本発明の光消去性水性インキ組成物は人体への安全性に優れ、上記光消去性水性インキ組成物によれば、紫外線を含む太陽光等に曝露した場合だけでなく、可視光線のみを照射した場合でも、短時間で消色する筆記線を得ることができる。 The photo-erasable water-based ink composition of the present invention is excellent in safety to the human body, and according to the above-mentioned photo-erasable water-based ink composition, not only when exposed to sunlight including ultraviolet rays, but only with visible light. Even in this case, it is possible to obtain a writing line that can be erased in a short time.
上記水溶性界面活性剤の２０℃における水への溶解度が３ｇ／１００ｇ−Ｈ２Ｏ以上であることが好ましい。 It is preferable that the solubility of the water-soluble surfactant in water at 20 ° C. is 3 g / 100 g-H 2 O or more.
本発明はまた、繊維芯又はプラスチック芯からなるペン先と、インキ収容部とを備え、上記光消去性水性インキ組成物が上記インキ収容部に収容されている、マーキングペンを提供する。 The present invention also provides a marking pen comprising a pen tip made of a fiber core or a plastic core and an ink storage portion, wherein the photo-erasable water-based ink composition is stored in the ink storage portion.
本発明によれば、人体への安全性に優れ、紫外線を含む太陽光等に曝露した場合だけでなく、可視光線のみを照射した場合でも、短時間で消色する筆記線を得ることができる光消去性水性インキ組成物、及びそれを用いたマーキングペンを提供することができる。 According to the present invention, it is excellent in safety to the human body, and it is possible to obtain a writing line that can be discolored in a short time not only when exposed to sunlight including ultraviolet rays but also when irradiated with only visible light. A photo-erasable water-based ink composition and a marking pen using the same can be provided.
以下、必要に応じて図面を参照しながら、本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary.
（光消去性水性インキ組成物）
本実施形態の光消去性水性インキ組成物は、モナスカスイエロー及び水溶性界面活性剤を含有する。上記水溶性界面活性剤の含有量は、光消去性水性インキ組成物全量を基準として、３質量％以上である。
(Light erasable water-based ink composition)
The photoerasable water-based ink composition of this embodiment contains Monascus yellow and a water-soluble surfactant. The content of the water-soluble surfactant is 3% by mass or more based on the total amount of the photoerasable water-based ink composition.
モナスカスイエローは、紅麹菌の菌体または培養液を各種溶媒で中和することで得られる紅麹色素の１種である。モナスカスイエローは、上記培養液を塩酸酸性エタノールで抽出することにより得られる。色材としてモナスカスイエローを用いることで、紫外線を照射せず可視光線のみを照射した場合でも筆記線が消去しやすくなる。 Monascus yellow is a kind of red yeast pigment obtained by neutralizing bacterial cells or culture solution of red yeast. Monascus yellow can be obtained by extracting the culture solution with hydrochloric acid ethanol. By using Monascus yellow as the color material, the writing lines can be easily erased even when only visible light is irradiated without irradiating ultraviolet rays.
モナスカスイエローの含有量は、光消去性水性インキ組成物全量を基準として、１０〜５０質量％であることが好ましく、２０〜４０質量％であることがより好ましい。モナスカスイエローの含有量が１０質量％以上であることにより、筆記線の良好な視認性を得ることができる傾向がある。モナスカスイエローの含有量が５０質量％以下であることにより、筆記に用いた光消去性水性インキ組成物が筆記面の裏面まで浸透しにくい傾向がある。 The content of Monascus yellow is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, based on the total amount of the photoerasable aqueous ink composition. When the content of Monascus yellow is 10% by mass or more, there is a tendency that good visibility of the writing line can be obtained. When the content of Monascus yellow is 50% by mass or less, the photo-erasable water-based ink composition used for writing tends to hardly penetrate to the back surface of the writing surface.
水溶性界面活性剤は分子内に親水基と疎水基をもつ物質であり、親水基の形態により、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、及びノニオン性界面活性剤に大別される。また、水溶性界面活性剤は、疎水基の形態により、炭化水素系界面活性剤、シリコーン系界面活性剤、フッ素系界面活性剤に大別される。本実施形態の光消去性水性インキ組成物には上記いずれの形態の水溶性界面活性剤も用いることができる。光消去性水性インキ組成物がモナスカスイエローと水溶性界面活性剤の両方を含むことにより、可視光線照射時の筆記線の消去を促進し、筆記線を短時間で消去することが可能となる。これは、光消去性水性インキ組成物中のモナスカスイエローの周囲の環境が疎水性となることにより、色素の可視光退色を引き起こす一重項酸素が長寿命化することによるものと考えられる。 A water-soluble surfactant is a substance having a hydrophilic group and a hydrophobic group in the molecule. Depending on the form of the hydrophilic group, the surfactant is classified into an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Broadly divided. Water-soluble surfactants are roughly classified into hydrocarbon surfactants, silicone surfactants, and fluorine surfactants according to the form of hydrophobic groups. Any of the above water-soluble surfactants can be used in the photoerasable water-based ink composition of the present embodiment. When the light erasable water-based ink composition contains both Monascus yellow and a water-soluble surfactant, erasing of the writing line during irradiation with visible light is promoted, and the writing line can be erased in a short time. This is thought to be due to the fact that the singlet oxygen that causes visible light fading of the dye extends the life because the environment around Monascus yellow in the photoerasable aqueous ink composition becomes hydrophobic.
上記水溶性界面活性剤の２０℃における水への溶解度（水１００ｇに溶ける水溶性界面活性剤の質量（ｇ））は３ｇ／１００ｇ−Ｈ２Ｏ以上であることが好ましく、３ｇ／１００ｇ−Ｈ２Ｏ以上３０ｇ／１００ｇ−Ｈ２Ｏ以下であることがより好ましい。水溶性界面活性剤の上記溶解度が３ｇ／１００ｇ−Ｈ２Ｏ以上であることにより、光消去性水性インキ組成物の筆記性能及び光消去性能の経時安定性が良好となる傾向がある。また、水溶性界面活性剤の上記溶解度が３０ｇ／１００ｇ−Ｈ２Ｏ以下であることにより、モナスカスイエローの消色後、筆記線上に残る水溶性界面活性剤が目視で認識しにくく、一層明確な光消去が可能となる傾向がある。 The solubility of the water-soluble surfactant in water at 20 ° C. (mass (g) of the water-soluble surfactant soluble in 100 g of water) is preferably 3 g / 100 g-H 2 O or more, preferably 3 g / 100 g-H. More preferably, it is 2 O or more and 30 g / 100 g-H 2 O or less. When the solubility of the water-soluble surfactant is 3 g / 100 g-H 2 O or more, the writing performance of the photo-erasable aqueous ink composition and the temporal stability of the photo-erasability tend to be good. In addition, when the solubility of the water-soluble surfactant is 30 g / 100 g-H 2 O or less, it is difficult to visually recognize the water-soluble surfactant remaining on the writing line after the decoloration of Monascus yellow. There is a tendency that optical erasure becomes possible.
水溶性界面活性剤の含有量は、光消去性水性インキ組成物全量を基準として、３質量％以上であり、３〜３０質量％であることが好ましく、３〜２０質量％であることがより好ましい。水溶性界面活性剤の含有量が３質量％以上であることにより、可視光線照射下での筆記線の消去性が向上する。水溶性界面活性剤の含有量が３０質量％以下であることにより、筆記に用いた光消去性水性インキ組成物が筆記面の裏面まで浸透しにくく、さらに、モナスカスイエローの消色後、筆記線上に残る界面活性剤が目視で認識しにくく、一層明確な光消去が可能となる傾向がある。 The content of the water-soluble surfactant is 3% by mass or more, preferably 3-30% by mass, more preferably 3-20% by mass based on the total amount of the photo-erasable water-based ink composition. preferable. When the content of the water-soluble surfactant is 3% by mass or more, the erasability of the writing line under visible light irradiation is improved. When the content of the water-soluble surfactant is 30% by mass or less, the photo-erasable water-based ink composition used for writing hardly penetrates to the back surface of the writing surface, and after decoloring Monascus yellow, It is difficult to visually recognize the remaining surfactant, and there is a tendency that clearer light erasure is possible.
本実施形態の光消去性水性インキ組成物は、上述の成分の水溶液又は水分散液として、或いは上述の成分とは別に、水を含有することができる。水の含有量は、光消去性水性インキ組成物全量を基準として、好ましくは３０〜９０質量％であり、より好ましくは４０〜７０質量％である。 The photoerasable water-based ink composition of the present embodiment can contain water as an aqueous solution or an aqueous dispersion of the above-described components or separately from the above-described components. The water content is preferably 30 to 90 mass%, more preferably 40 to 70 mass%, based on the total amount of the photoerasable water-based ink composition.
本実施形態の光消去性水性インキ組成物は、本実施形態で得られる効果を損なわない範囲で、上述の成分に加えて、水以外の溶媒、防錆剤、ｐＨ調整剤、増粘剤、防腐剤（防黴剤）、潤滑剤、及び固着樹脂等の添加剤を含有していてもよい。 In addition to the above-mentioned components, the photoerasable water-based ink composition of the present embodiment is within the range not impairing the effects obtained in the present embodiment, a solvent other than water, a rust inhibitor, a pH adjuster, a thickener, Additives such as preservatives (antifungal agents), lubricants, and fixing resins may be contained.
本実施形態の光消去性水性インキ組成物は、モナスカスイエロー、水溶性界面活性剤及び水、必要に応じて添加剤を、例えば、ディゾルバー、ヘンシェルミキサー及びホモミキサーなどの攪拌機を用いて混合することにより得られる。攪拌機の攪拌条件は特に制限されないが、たとえば、ディゾルバー攪拌機を用いて、回転数１００〜１０００ｒｐｍで３０〜１８０分間攪拌することにより、各成分が均一に分散した光消去性水性インキ組成物を得ることができる。以上のようにして得られた光消去性水性インキ組成物の粘度は、１〜２０ｍＰａ・ｓであることが好ましく、１〜１０ｍＰａ・ｓであることがより好ましい。 The photo-erasable water-based ink composition of this embodiment is prepared by mixing Monascus yellow, a water-soluble surfactant and water, and, if necessary, additives using a stirrer such as a dissolver, a Henschel mixer, and a homomixer. Is obtained. Stirring conditions of the stirrer are not particularly limited. For example, by using a dissolver stirrer, stirring for 30 to 180 minutes at a rotation speed of 100 to 1000 rpm, a photo-erasable water-based ink composition in which each component is uniformly dispersed is obtained. Can do. The viscosity of the photoerasable water-based ink composition obtained as described above is preferably 1 to 20 mPa · s, and more preferably 1 to 10 mPa · s.
（マーキングペン）
本実施形態のマーキングペンは、繊維芯又はプラスチック芯からなるペン先と、インキ収容部とを備え、上記光消去性水性インキ組成物が上記インキ収容部に収容されている。
(Marking pen)
The marking pen of this embodiment includes a pen tip made of a fiber core or a plastic core, and an ink storage portion, and the above-mentioned photo-erasable water-based ink composition is stored in the ink storage portion.
図１は本発明の一実施形態に係るマーキングペンの断面図である。図１のマーキングペン１０は中綿式であるが、本実施形態のマーキングペンは直液式であってもよい。また、図１のマーキングペン１０は、その一端にペン先を備えるが、両端にペン先を備えていてもよい。図１のマーキングペン１０は、インキ収容部１、ペン先２、軸体３、中綿４及びキャップ５を備える。マーキングペン１０においては、軸体３内部の空隙がインキ収容部１となっており、このインキ収容部１に本実施形態の光消去性水性インキ組成物を含む中綿４が収容される。なお、軸体３とは別に、軸体３内部に円筒状の中軸を設け、その中軸内部の空隙をインキ収容部１としてもよい。
FIG. 1 is a cross-sectional view of a marking pen according to an embodiment of the present invention. Although the marking
ペン先２は、一般的なマーキングペンのペン先であり、光消去性水性インキ組成物を供給できるような繊維芯又はプラスチック芯で形成されている。マーキングペン１０において、ペン先２の先端形状は、砲弾形状となっている。なお、マーキングペン１０において、ペン先２の先端形状は砲弾形状に限定されず、チゼル形状、筆ペン形状等であってもよい。
The
また、キャップ５は、ペン先２を覆うように配置される。
The cap 5 is disposed so as to cover the
本実施形態のマーキングペンは紙などの非浸透面上への筆記のために好適に使用される。本実施形態のマーキングペンによる筆記線は人体への安全性に優れ、上記筆記線は紫外線を含む太陽光等に曝露した場合だけでなく、可視光線のみを照射した場合でも、短時間で消色することができる。 The marking pen of this embodiment is suitably used for writing on a non-penetrating surface such as paper. The writing line by the marking pen of this embodiment is excellent in safety to the human body, and the writing line can be erased in a short time not only when exposed to sunlight including ultraviolet rays but also when only visible light is irradiated. can do.
本発明に係るインキ組成物は、筆記用具、マーキング用具、及びインキジェット等の印字用具に適用され、特にマーキングペンに好適に適用される。 The ink composition according to the present invention is applied to a writing tool, a marking tool, and a printing tool such as an ink jet, and is particularly preferably applied to a marking pen.
以下に、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to these examples.
［インキ組成物の調製］
（実施例１〜２６及び比較例１〜２７）
下記表１〜４に記載される各材料を混合し、実施例１〜２６及び比較例１〜２７のインキ組成物を得た。表中の数値の単位は、特に断りのない場合は、質量部である。
[Preparation of ink composition]
(Examples 1-26 and Comparative Examples 1-27)
The materials described in Tables 1 to 4 below were mixed to obtain ink compositions of Examples 1 to 26 and Comparative Examples 1 to 27. The unit of numerical values in the table is parts by mass unless otherwise specified.
表１〜４に記載される材料の名称の詳細は以下のとおりである。
ノンサールＬＫ−５（カルボン酸塩型アニオン性界面活性剤、日油株式会社製、有効成分９８質量％以上）
パーソフトＳＫ（硫酸エステル塩型アニオン性界面活性剤、日油株式会社製、３０質量％水溶液）
プライサーフＡ２１５Ｃ（リン酸エステル型アニオン性界面活性剤、第一工業製薬株式会社製、有効成分９９質量％）
カチオーゲンＴＭＬ（アミン塩型カチオン性界面活性剤、第一工業製薬株式会社製、３０質量％水溶液）
ニッサンアノンＢＦ（カルボン酸塩型両性界面活性剤、日油株式会社製、２５質量％水溶液）
ノイゲンＸＬ−１０００（ポリエチレングリコールエーテル型ノニオン性界面活性剤、第一工業製薬株式会社製）
ノニオシドＢ−１５（アルキルグリコシド型ノニオン性界面活性剤、第一工業製薬社製、５０質量％水溶液）
ダイヤノールＣＤＥ（脂肪酸アルカノールアミド型ノニオン性界面活性剤、第一工業製薬社製）
リョートーポリグリエステルＬ−７Ｄ（ポリグリセリン脂肪酸エステル型ノニオン性界面活性剤、三菱化学フーズ株式会社製）
ソルゲンＴＷ−８０（ソルビタン脂肪酸エステル型ノニオン性界面活性剤、第一工業製薬社製）
リョートーシュガーエステルＬ−１６９５（ショ糖脂肪酸エステル型ノニオン性界面活性剤、三菱化学フーズ株式会社製）
ＫＭ−２４４Ｆ（シリコーン系界面活性剤、日信化学工業株式会社製）
サーフロンＳ−２１１（フッ素系界面活性剤、ＡＧＣセイミケミカル株式会社製、有効成分５０質量％）
リオフレッシュ エローＭＡ（モナスカスイエロー、東洋アドレ株式会社製、８０質量％エタノール溶液）
モナスカラー ３００ＬＡ（モナスカスレッド、グリコ栄養食品株式会社製、５０質量％エタノール溶液）
The details of the names of the materials described in Tables 1 to 4 are as follows.
Nonsal LK-5 (carboxylate type anionic surfactant, manufactured by NOF Corporation, active ingredient 98% by mass or more)
Persoft SK (sulfate ester type anionic surfactant, manufactured by NOF Corporation, 30% by mass aqueous solution)
PRISURF A215C (Phosphate ester type anionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 99% by mass of active ingredient)
Cathogen TML (amine salt type cationic surfactant, Daiichi Kogyo Seiyaku Co., Ltd., 30% by weight aqueous solution)
Nissan Anon BF (carboxylate type amphoteric surfactant, manufactured by NOF Corporation, 25% by weight aqueous solution)
Neugen XL-1000 (polyethylene glycol ether type nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Nonioside B-15 (alkyl glycoside type nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 50% by mass aqueous solution)
Diamond CDE (fatty acid alkanolamide type nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Ryoto-polyglycerin L-7D (polyglycerin fatty acid ester type nonionic surfactant, manufactured by Mitsubishi Chemical Foods)
Sorgen TW-80 (Sorbitan fatty acid ester type nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Ryoto Sugar Ester L-1695 (sucrose fatty acid ester type nonionic surfactant, manufactured by Mitsubishi Chemical Foods Corporation)
KM-244F (silicone surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)
Surflon S-211 (Fluorosurfactant, manufactured by AGC Seimi Chemical Co., Ltd., active ingredient 50% by mass)
Rio Fresh Yellow MA (Monascus Yellow, Toyo Adre Co., Ltd., 80% by mass ethanol solution)
Monas Color 300LA (Monasuka Red, Glico Nutrition Foods Co., Ltd., 50% ethanol solution)
［インキ組成物の評価］
図１に示した構造を有する中綿式マーキングペンのインキ収容部に、実施例１〜２６及び比較例１〜２７のインキ組成物を充填し、ペン先にインキ組成物を染み込ませた。ペン先には砲弾形状のポリエステル繊維芯を用いた。得られたインキ組成物及びマーキングペンを用いて、後述の評価を行った。評価結果を表１〜４に示す。
[Evaluation of ink composition]
The ink containing part of the batting type marking pen having the structure shown in FIG. 1 was filled with the ink compositions of Examples 1 to 26 and Comparative Examples 1 to 27, and the pen composition was impregnated with the ink composition. A bullet-shaped polyester fiber core was used for the nib. The following evaluation was performed using the obtained ink composition and marking pen. The evaluation results are shown in Tables 1 to 4.
（試験１：消去性Ａ）
実施例１〜２６及び比較例１〜２７のインキ組成物を充填したマーキングペンを用いて筆記したコピー用紙を、温度２５±５℃、湿度６０±２０％ＲＨの室内の、南向きの窓に貼り付けて放置した。筆記線を太陽光に曝露し、曝露して３時間後及び８時間後に筆記線が消去されているかどうかを目視にて確認した。筆記線が消去されるまでの時間を以下の基準に従って評価した。
Ａ：曝露して３時間以内に筆記線が消去した。
Ｂ：曝露して８時間以内に筆記線が消去した。
Ｃ：曝露して８時間が経過しても筆記線が消去しなかった。
(Test 1: Eraseability A)
Copy paper written with a marking pen filled with the ink compositions of Examples 1 to 26 and Comparative Examples 1 to 27 was placed in a south-facing window in a room with a temperature of 25 ± 5 ° C. and a humidity of 60 ± 20% RH. Pasted and left. The writing line was exposed to sunlight, and it was visually confirmed whether the writing line was erased 3 hours and 8 hours after the exposure. The time until the writing line was erased was evaluated according to the following criteria.
A: The writing line disappeared within 3 hours after exposure.
B: The writing line disappeared within 8 hours after exposure.
C: The writing line was not erased even after 8 hours of exposure.
（試験２：消去性Ｂ）
実施例１〜２６及び比較例１〜２７のインキ組成物を充填したマーキングペンを用いて筆記したコピー用紙を、外部光を断った、気温２５±５℃、湿度６０±２０％ＲＨの、外部光を断った室内で、ＬＥＤ蛍光灯（アイリスオーヤマ社製、ＬＤＦＬ２０００ＮＦ-Ｈ５０、２本）直下２ｍの位置に配置した。上記ＬＥＤ蛍光灯から光を照射し、照射して３時間後及び８時間後に筆記線が消去されているかどうかを目視にて確認した。筆記線が消去されるまでの時間を以下の基準に従って評価した。
Ａ：照射して３時間以内に筆記線が消去した。
Ｂ：照射して８時間以内に筆記線が消去した。
Ｃ：照射して８時間が経過しても筆記線が消去しなかった。
(Test 2: Eraseability B)
Copy papers written using the marking pens filled with the ink compositions of Examples 1 to 26 and Comparative Examples 1 to 27, external temperature was 25 ± 5 ° C., humidity was 60 ± 20% RH, external light was cut off Inside the room where light was cut off, the LED fluorescent lamp (Iris Ohyama, LDFL2000NF-H50, 2) was placed at a position 2 m directly below. The LED fluorescent lamp was irradiated with light, and it was visually confirmed whether or not the writing lines were erased 3 hours and 8 hours after the irradiation. The time until the writing line was erased was evaluated according to the following criteria.
A: The writing line disappeared within 3 hours after irradiation.
B: The writing line disappeared within 8 hours after irradiation.
C: The writing line was not erased even after 8 hours of irradiation.
色材にモナスカスレッドを用いた比較例１〜１３では、太陽光に曝露して８時間が経過しても筆記線が消去しきらず、短時間で消去しているとは言い難かった。 In Comparative Examples 1 to 13 using Monasuka thread as the coloring material, the writing lines were not completely erased even after 8 hours had passed after exposure to sunlight, and it was difficult to say that they were erased in a short time.
色材にモナスカスイエローを用い、水溶性界面活性を含有しない比較例１４、水溶性界面活性剤の含有量が少ない比較例１５〜２７では、ＬＥＤ蛍光灯から光を照射して８時間が経過しても筆記線が消去しきらず、短時間で消去しているとは言い難かった。 In Comparative Example 14 that uses Monascus Yellow as a coloring material and does not contain water-soluble surfactant, and Comparative Examples 15 to 27 in which the content of water-soluble surfactant is small, 8 hours have passed since light was emitted from an LED fluorescent lamp. However, it was hard to say that the writing line was not erased and it was erased in a short time.
一方、色材にモスカスイエローを用い、水溶性界面活性剤を３質量％以上含有している実施例１〜１３では、紫外線と可視光線を含む太陽光に曝露した場合のみならず、紫外線を含まないＬＥＤ蛍光灯からの光を照射した場合にも、照射（曝露）して３時間以内に筆記線が消去していた。また、実施例１４〜２６では、ＬＥＤ蛍光灯からの光を照射した場合にも、照射してから８時間以内に筆記線が消去していた。以上より、実施例１〜２６では、紫外線を含む太陽光等に曝露した場合だけでなく、可視光線のみを照射した場合でも短時間で消去することが確認された。 On the other hand, in Examples 1 to 13 using Moscus Yellow as a coloring material and containing 3% by mass or more of a water-soluble surfactant, not only when exposed to sunlight including ultraviolet rays and visible rays, but also ultraviolet rays. Even when light from an LED fluorescent lamp not included was irradiated, the writing lines were erased within 3 hours after irradiation (exposure). Moreover, in Examples 14 to 26, when the light from the LED fluorescent lamp was irradiated, the writing line was erased within 8 hours after the irradiation. From the above, in Examples 1 to 26, it was confirmed that erasing was performed in a short time not only when exposed to sunlight including ultraviolet rays but also when only visible light was irradiated.
次に、実施例１、比較例１及び比較例１４のインキ組成物を充填したマーキングペンを用いて筆記したコピー用紙の、消去性試験開始前、消去性Ａの試験開始３時間後及び８時間後、並びに、消去性Ｂの試験開始３時間後及び８時間後の色目を分光測色計（ＳＰＥＣＴＲＯＰＨＯＴＯＭＥＴＥＲ）（型番：ＣＭ−３７００ｄ、ＭＩＮＯＬＴＡ社製、基準光源Ｄ６５、視野２°）を用い測定した。また、筆記前のコピー用紙の色目を空試験として測定した。色目は、明度Ｌ＊、並びに色相と彩度を示すａ＊及びｂ＊を測定することにより評価した。色目の測定値から下記式に基づいて色差を算出し、光消去性を定量的に評価した。Ｌ＊、ａ＊及びｂ＊の測定値、並びに、色差の計算値を表５に示す。
式中、Ｌ＊及びＬ０ ＊は明度を示し、ａ＊及びａ０ ＊は色相を示し、ｂ＊及びｂ０ ＊は彩度を示す。また、Ｌ０ ＊、ａ０ ＊及びｂ０ ＊は筆記前（空試験）の測定値であり、Ｌ＊、ａ＊及びｂ＊は筆記、照射又は曝露後の測定値である。
Next, the copy paper written using the marking pen filled with the ink composition of Example 1, Comparative Example 1 and Comparative Example 14, before the start of the erasability test, 3 hours after the start of the erasability test and 8 hours After, and after 3 hours and 8 hours after the start of the test for erasability B, the color was measured using a spectrocolorimeter (SPECTROPHOMETER) (model number: CM-3700d, manufactured by MINOLTA, reference light source D65, field of
In the formula, L * and L 0 * indicate lightness, a * and a 0 * indicate hue, and b * and b 0 * indicate saturation. L 0 * , a 0 *, and b 0 * are measured values before writing (blank test), and L * , a *, and b * are measured values after writing, irradiation, or exposure.
色材にモナスカスレッドを用いている比較例１では、太陽光曝露８時間後及びＬＥＤ蛍光灯の光照射８時間後と筆記前（空試験）との色差はそれぞれ１．５以上であり、筆記線が消去されているとは言えなかった。 In Comparative Example 1 in which Monasuka red is used as the color material, the color difference between 8 hours after sunlight exposure, 8 hours after LED fluorescent light irradiation and before writing (blank test) is 1.5 or more, respectively. It could not be said that the lines were erased.
色材にモナスカスイエローを用い、水溶性界面活性剤を用いていない比較例１４では、太陽光曝露３時間後と筆記前（空試験）との色差は１．５未満であったが、ＬＥＤ蛍光灯の光照射８時間後の空試験との色差は１．５以上であり、紫外線に曝露されることなく筆記線が消去されているとは言えなかった。 In Comparative Example 14 in which Monascus yellow was used as the coloring material and no water-soluble surfactant was used, the color difference between 3 hours after exposure to sunlight and before writing (blank test) was less than 1.5. The color difference from the blank test after 8 hours of light irradiation was 1.5 or more, and it could not be said that the writing lines were erased without being exposed to ultraviolet rays.
一方、色材にモスカスイエローを用い、水溶性界面活性剤を３質量％以上含有している実施例１では、筆記前後の色差は３０を超えており、比較例１の筆記前後の色差より大きかったが、太陽光曝露３時間後及びＬＥＤ蛍光灯の光照射３時間後と筆記前（空試験）との色差はそれぞれ１．５未満となり、比較例１の色差よりもむしろ小さかった。実施例１では、太陽光曝露後及びＬＥＤ蛍光灯の光照射後の色目は筆記前（空試験）の色目とほぼ同等であり、紫外線の有無によらず筆記線が十分に光消去されていることが確認された。 On the other hand, in Example 1 using Moscus Yellow as a coloring material and containing 3% by mass or more of a water-soluble surfactant, the color difference before and after writing exceeds 30. From the color difference before and after writing in Comparative Example 1 Although the color difference was 3 hours after exposure to sunlight and 3 hours after light irradiation of the LED fluorescent lamp and before writing (blank test), the color difference was less than 1.5, which was rather smaller than the color difference of Comparative Example 1. In Example 1, the color after exposure to sunlight and after light irradiation of the LED fluorescent lamp is almost the same as the color before writing (blank test), and the writing line is sufficiently erased regardless of the presence or absence of ultraviolet rays. It was confirmed.
また、実施例１〜２６で得られたインキ組成物はいずれも人体に対して安全であることが確認された。 Moreover, it was confirmed that all the ink compositions obtained in Examples 1 to 26 are safe to the human body.
１・・・インキ収容部、２・・・ペン先、３・・・軸体、４・・・中綿（インキ組成物）、５・・・キャップ、１０・・・マーキングペン。 DESCRIPTION OF SYMBOLS 1 ... Ink storage part, 2 ... Pen tip, 3 ... Shaft body, 4 ... Filling (ink composition), 5 ... Cap, 10 ... Marking pen.
Claims (3)
前記水溶性界面活性剤の含有量は、光消去性水性インキ組成物の全量を基準として、３質量％以上である、光消去性水性インキ組成物。 Contains Monascus Yellow and a water-soluble surfactant,
Content of the said water-soluble surfactant is a photo-erasable water-based ink composition which is 3 mass% or more on the basis of the whole quantity of a photo-erasability water-based ink composition.
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| JP2013082921A (en) * | 2011-09-29 | 2013-05-09 | Chiba Inst Of Technology | Method for producing ink, printing method |
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| CN113913049A (en) * | 2021-11-25 | 2022-01-11 | 朱政轩 | Photocatalyst fluorescent ink and preparation method thereof |
| CN113913049B (en) * | 2021-11-25 | 2023-08-29 | 河南京硕信息科技有限公司 | Photocatalyst fluorescent ink and preparation method thereof |
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