JP3890130B2 - Red ink composition for oil-based marking pens - Google Patents

Description

【００４２】
（評価）
実施例１〜４及び比較例１〜２で得られた油性マーキングペン用赤色インキ組成物について、以下の定着性試験、耐水性試験、色調安定性試験により評価した。
【００４３】
（定着性試験）
実施例１〜４および比較例１〜２で得られた油性マーキングペン用赤色インキ組成物を、フェルトをペン先として使用した筆記具（サクラクレパス社製油性マーカー、商品名「ペンタッチ」）に充填し、これを用いて非吸収面（ブリキ板、ポリエチレン板）に直線を筆記して、３０分乾燥した後、筆跡を綿棒で５００ｇ荷重にて擦過する。この擦過により、筆跡の変化を目視にて観察し、以下の評価基準により評価する。それぞれ評価結果を表１の定着性試験の欄に示す。
○：全く筆跡に変化が生じない
△：筆跡に若干きずが付く
×：擦過により筆跡が剥がれ、完全に非吸収面が露出する
【００４４】
（耐水性試験）
実施例１〜４および比較例１〜２で得られた油性マーキングペン用赤色インキ組成物を、フェルトをペン先として使用した筆記具（サクラクレパス社製油性マーカー、商品名「ペンタッチ」）に充填し、これを用いて上質紙に直線を筆記して、筆記１分後に水に１時間浸漬する。浸漬後、その浸漬した上質紙を他の乾燥している上質紙の上に置き、乾燥させる。乾燥後、インキの滲み及び下敷きにした上質紙への滲みだしを目視にて観察し、下記の評価基準により耐水性を評価する。それぞれ評価結果を表１の耐水性試験の欄に示す。
○：筆記線の周辺にインキの滲みがみられない
×：筆記線の周辺にインキの滲みが見られ、下敷きの上質紙にもインキが付着している
【００４５】
（色調安定性試験）
実施例１〜４および比較例１〜２で得られた油性マーキングペン用赤色インキ組成物を、フェルトをペン先として使用した筆記具（サクラクレパス社製油性マーカー、商品名「ペンタッチ」）に充填し、これを用いて上質紙に直線を筆記して、１分間放置する。その筆跡の下又は周辺にさらに直線を筆記し、両者の色調の差を目視にて観察し、以下の評価基準により色調安定性を評価する。それぞれの評価結果を表１の色調安定性試験の欄に示す。
○：２本の線に色調の差がみられない
△：２本の線に若干、色調の差がみられる
×：２本の線にはっきりと明確な色調の差がみられる
【００４６】
本発明の油性マーキングペン用赤色インキ組成物（実施例のインキ組成物）は、比較例のインキ組成物より、筆跡（筆跡）の非吸収面に対する定着性、および筆跡の耐水性が高い。また、筆記直後のインキの色とインキ乾燥後のインキの色にほとんど差がなく、筆記直後の鮮明な赤色をインキ乾燥後も保持できる。
【００４７】
【発明の効果】
本発明のインク組成物は、特定の油溶性染料と、極性有機溶剤と、シリコーン系高分子界面活性剤とを含有する油性マーキングペン用赤色インキ組成物であるので、赤色系の油性マーキングペン用インキであるにもかかわらず、筆跡の耐水性、および筆跡と非吸収面との定着性が高い。また、筆記時とインキ乾燥後とのインキの色に差がほとんどない。
また、キシレンなどの非極性溶剤を用いた場合と同等以上の筆跡の定着性を、金属、プラスチックなどの非吸収面で確保できる。そのため、筆跡の非吸収面に対する定着性、および筆跡の耐水性が優れ、鮮明な赤色をインキ乾燥後も維持でき、かつ色調安全性が高いインキ組成物を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a red ink composition, and more particularly, to a red ink composition for oil-based marking pens that has excellent fixability to a non-absorbing surface of handwriting and high water resistance.
[0002]
[Prior art]
Conventionally, non-polar solvents such as xylene have been used as solvents in oil-based marking pen ink compositions, but in recent years there has been a shift to the use of alcohol-based and glycol ether-based polar solvents from the standpoint of safety. ing.
[0003]
However, along with the shift of use from nonpolar solvents to polar solvents, the fixability of handwriting when writing on non-absorbing surfaces such as metals and plastics required for oil-based marking pens tends to be reduced. This is because when nonpolar solvents were used, the etching action and hydrogen bonding on the nonabsorbing surface, which was thought to have been acting on the fixability of handwriting, were weakened by the use of polar solvents. This is thought to be due to the loss of handwriting adhesion and fixability.
[0004]
Therefore, the fixability of handwriting on the non-absorbing surface is improved by adding a resin or the like to the ink composition for an oil-based marking pen containing a polar solvent. However, these ink compositions have low fixability between the handwriting and a non-absorbing surface such as metal or plastic.
[0005]
Further, in the red oil-based marking pen ink composition, a salt-formation product of an acid dye and a basic dye is used as the oil-soluble colorant. However, when an ink in which an oil-soluble colorant based on such a salt-formation product is dissolved in an alcohol-based or glycol ether-based polar solvent is used, the handwriting on the marking pen using this ink has poor water resistance, When the handwriting gets wet with water, it causes a so-called “color crying” that the dye oozes out, and is also the subject of claims. That is, the oil-based marking pen made of the red ink composition not only has low fixability of handwriting on the non-absorbing surface, but also has low water resistance.
[0006]
[Problems to be solved by the invention]
For this reason, in the red ink composition for oil-based marking pens, an ink using a non-polar solvent such as xylene with high toxicity is widely used as a solvent, and an ink using a polar solvent such as alcohol with high safety is used. The current situation is that it has not yet been migrated.
[0007]
Moreover, in the oil-based marking pen using the conventional ink, in order to improve the color development property of the ink, a salt product of an acid dye and a basic dye is used. However, this ink has a problem in water resistance.
[0008]
Therefore, the problem of the present invention is that, even for a red ink composition containing a red dye and a polar organic solvent, the ink composition has excellent fixability to the non-absorbing surface and the water resistance of the ink composition. An object of the present invention is to provide a red ink composition for oil-based marking pens having high properties.
Another object of the present invention is to provide a red ink for oil-based marking pens that maintains the vividness of the handwriting and has high color stability, in addition to the above characteristics, even in a red ink composition containing a red dye and a polar organic solvent. It is to provide a composition.
Another problem of the present invention is that the oil-based ink composition containing a red dye has a fixability of handwriting that is equal to or higher than that when a nonpolar organic solvent such as xylene is used even if it has a polar organic solvent. The present invention provides a red ink composition for an oil-based marking pen in which the water resistance of the ink composition is improved.
[0009]
[Means for Solving the Problems]
In conventional marking pen ink compositions using alcoholic or glycol ether solvents, the main focus is to improve the adhesion and fixing properties between the solid content of the resin and dye in the handwriting and the non-absorbing surface. Therefore, the improvement of the fixability between the handwriting by the ink composition and the non-absorbing surface is not sufficient. Of course, there is no difference in the adhesion and fixability between the solid content of the resin or dye in the handwriting and the surface of the non-absorbing surface playing an important role in improving the fixability of the handwriting. However, the improvement in the adhesion and fixability of the handwriting with respect to the non-absorbing surface leads to the ease with which other substances that contact the handwriting surface adhere to the handwriting surface at the same time. Therefore, as a measure for improving the fixability and adhesion between the handwriting and the non-absorbing surface, combining with various resins improves the adhesion and fixing properties between the handwriting and the non-absorbing surface, but at the same time the surface of the handwriting In addition, the adhesion of other substances in the ink becomes stronger, and when it is rubbed with fingers, cloth, paper, etc., the handwriting tends to adhere, and the fixing property is not substantially improved.
[0010]
Therefore, as a result of intensive studies based on such knowledge, the present inventor has found that when a silicone polymer surfactant is contained in an ink composition containing a red dye and a polar organic solvent, the handwriting and the non-absorbing surface are fixed. I found that I could improve my sex. Silicone polymer surfactants are not completely compatible with polar organic solvents, and because of the specific surface activity of silicone polymer surfactants, when written on non-absorbing surfaces as inks The silicone-based polymeric surfactant migrates to the handwriting surface. As a result, the silicone-based polymeric surfactant hardly affects the fixability between the handwriting and the surface of the non-absorbing surface, and develops difficult adhesion to other substances, which is a feature of the handwriting surface. Therefore, even when the handwriting is rubbed with fingers, cloth, paper, etc., the handwriting is hardly attached, and as a result, the fixing property on the substantially non-absorbing surface is improved. That is, the handwriting by the ink composition containing the silicone polymer surfactant has a high level of adhesion between the handwriting and the surface of the non-absorbing surface, fixing property and difficult adhesion to other materials on the handwriting surface at the same time. Have in.
[0011]
However, in an oil-based ink composition containing a red dye, if a salt-form of a basic dye and an acid dye is used as a red dye, the handwriting with the ink has low water resistance, and the handwriting is wet with water. The free dye (basic dye and / or acid dye) dissolves in water and begins to bleed, resulting in so-called “crying”.
[0012]
Accordingly, the present inventor has made extensive studies to improve the fixability of the handwriting to the non-absorbing surface and the water resistance of the handwriting even with a red ink composition containing a red dye and a polar organic solvent. As a result, when xanthene red oil-soluble dyes are used as red dyes in combination with polar organic solvents and silicone polymer surfactants, they are used for oil-based marking pens that have high fixability on the non-absorbing surface of handwriting and high water resistance. The present invention was completed by finding that a red ink composition was obtained. That is, the red ink composition for oil-based marking pens of the present invention contains a xanthene red oil-soluble dye, a polar organic solvent, and a silicone polymer surfactant.
[0013]
This is because xanthene red oil-soluble dyes are themselves highly water-resistant dyes, but xanthene red oil-soluble dyes have high water resistance even when combined with polar organic solvents and silicone polymer surfactants. This is due to the fact that the silicone-based polymer surfactant can also exhibit the effect of improving the fixability of the handwriting on the non-absorbing surface. In addition, the handwriting by this ink composition can ensure the fixability equivalent to or more than the case where nonpolar solvents, such as xylene, are used as a solvent by non-absorbing surfaces, such as a metal and a plastic.
[0014]
In particular, when at least propylene glycol monomethyl ether is used as the polar solvent, a clear red-colored handwriting can be obtained, and the color change of the ink can be suppressed or prevented immediately after writing and after ink drying. The inventor has found that this is possible. That is, in the present invention, propylene glycol monomethyl ether is used as a polar organic solvent in a red ink for an oil-based marking pen containing a xanthene red oil-soluble dye, a polar organic solvent, and a silicone polymer surfactant. A red ink composition for oil-based marking pens.
[0015]
As the silicone-based polymer surfactant, at least one of polyoxypropylene-modified silicone and carboxy-modified silicone can be suitably used.
[0016]
Further, in the present invention, when a xanthene red oil-soluble dye is used in combination with an azomethine yellow and / or orange oil-soluble dye, the color of the ink is adjusted without deteriorating the excellent characteristics, and a clear Color can be developed.
[0017]
In the present invention, an oil-soluble resin (hereinafter sometimes simply referred to as “resin”) can be used, and the oil-soluble resin is selected from, for example, a ketone-based resin, a phenol-based resin, and a xylene-based resin. At least one kind is included.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
(Red dye)
Examples of xanthene red oil-soluble dyes used as red dyes include C.I. I. Basic Red 1, C.I. I. Basic Violet 10, C.I. I. And oil-soluble dyes using basic dyes such as Basic Violet 11. More specifically, as the xanthene red oil-soluble dye, for example, trade name: Spiron Red C-GH (manufactured by Hodogaya Chemical Co., Ltd.), trade name: oil pink 312 (manufactured by Orient Chemical Co., Ltd.), and the like are commercially available.
[0019]
The xanthene red oil-soluble dye is a dye obtained by salt-forming the basic dye to make it oil-soluble. In the salt formation, for example, a resin having reactivity with the basic dye (for example, , Phenol resin, etc.).
[0020]
The amount of xanthene red oil-soluble dye used is 0.5 to 15% by weight, preferably 1 to 8% by weight, based on the total amount of ink. When there is too much the said usage-amount, a viscosity will rise and writing property will fall. On the other hand, if the amount is too small, the handwriting density (coloring property) is low.
[0021]
(Polar organic solvent)
As the polar organic solvent, alcohol solvents, glycol ether solvents and the like can be used. A polar organic solvent can be used individually or in combination of 2 or more types. Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, and tertiary butyl alcohol. Examples of the glycol ether solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, and diethylene glycol. Examples thereof include monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobumethyl ether acetate.
[0022]
In particular, in the present invention, when propylene glycol monomethyl ether is used as the polar organic solvent, discoloration of the handwriting immediately after writing and after a few minutes after writing (after ink drying) can be suppressed or prevented, and the color tone stability of the handwriting can be improved. . Therefore, when propylene glycol monomethyl ether is used as the polar organic solvent, a clear color handwriting can be obtained. Of course, propylene glycol monomethyl ether may be used in combination with other polar organic solvents, and the proportion of propylene glycol monomethyl ether in the polar solvent is 60% by weight or more, particularly 75% by weight or more with respect to the total amount of the polar organic solvent. Preferably there is. If the proportion of propylene glycol monomethyl ether in the polar solvent is less than the above proportion, the color tone stability of the handwriting is lowered.
[0023]
The amount of the polar organic solvent used is 50 to 95% by weight, preferably about 50 to 90% by weight, based on the total amount of the ink. If the amount of the polar organic solvent used is too large, the concentration of the handwriting is lowered. On the other hand, if the amount is too small, the viscosity increases and the writing property is lowered, and the solubility of other components (colorant, oil-soluble resin, etc.) is lowered.
[0024]
(Silicone-based polymer surfactant)
The silicone-based polymer surfactant is not particularly limited, and modified silicones such as polyether-modified silicone, carboxy-modified silicone, amino-modified silicone, and alkyl-modified silicone can be used. Preferred silicone-based polymeric surfactants include polyether-modified silicones and carboxy-modified silicones. Silicone polymer surfactants can be used alone or in combination.
[0025]
Among polyether-modified silicones, modified silicones with a high content of polyoxypropylene as polyether (for example, the content of polyoxypropylene in the polyether is 50% by weight or more (preferably 70% by weight or more, more preferably 90% by weight). (Polyether-modified silicone), particularly a polyether-modified silicone in which the polyether is composed only of polyoxypropylene (referred to as “polyoxypropylene-modified silicone”) can be suitably used.
[0026]
Polyoxypropylene-modified silicone and carboxy-modified silicone can exhibit extremely high adhesion. This is because, when writing with these modified silicone-containing ink compositions, the modified silicone (polyoxypropylene-modified silicone, carboxy-modified silicone) easily migrates to the handwriting surface as the polar organic solvent evaporates or volatilizes.
[0027]
A commercially available modified silicone oil can be used as the silicone-based polymer surfactant. As the polyoxypropylene-modified silicone oil, for example, the trade name “TSF4460” is commercially available from Toshiba Silicone, and the trade name “Granol 115” is commercially available from Kyoeisha Chemical. As the carboxy-modified silicone, for example, a trade name “TSF4770” is commercially available from Toshiba Silicone, and trade names “X-22-3710”, “X-22-162A”, “X” from Shin-Etsu Chemical Co., Ltd. -22-3701E "is commercially available.
[0028]
The molecular weight (number average molecular weight) of the silicone-based polymer surfactant is not particularly limited, and is, for example, 1,000 to 30,000, preferably 2,000 to 20,000, and more preferably 5,000 to 20,000. About 000. If the molecular weight is too low, the water resistance is lowered. If the molecular weight is too high, it is difficult to migrate to the surface of the handwriting, the difficulty adhesion is low, and the fixability may be lowered.
[0029]
The amount of the silicone-based polymer surfactant used is, for example, 0.01 to 10% by weight with respect to the total amount of ink, preferably 0.00, depending on the type and the type of other components (colorant, resin, etc.). It is about 2 to 4% by weight. If the amount of the silicone polymer surfactant used is excessive, the silicone polymer surfactant moves not only to the surface of the handwriting but also to the vicinity of the handwriting surface, and on the other hand, a side effect such as inhibition of adhesion to the surface of the handwriting. The following effects may occur. On the other hand, if the amount is too small, the sticking property of the handwriting is low and the fixing property is lowered.
[0030]
(Azomethine yellow and / or orange oil-soluble dyes)
In the present invention, the color of the ink is adjusted by combining the xanthene red oil-soluble dye with the azomethine yellow oil-soluble dye and / or the azomethine orange oil-soluble dye, and the ink is colored with a very clear color. Can be made.
[0031]
Examples of the azomethine yellow oil-soluble dye include C.I. I. Basic Yellow 11, C.I. I. Basic Yellow 13, C.I. I. Basic Yellow 14, C.I. I. Basic Yellow 21, C.I. I. Basic Yellow 23, C.I. I. Basic Yellow 24, C.I. I. Basic Yellow 28, C.I. I. Basic Yellow 40, C.I. I. Basic Yellow 44, C.I. I. Basic Yellow 49, C.I. I. Basic Yellow 51, C.I. I. Basic Yellow 52, C.I. I. Basic Yellow 53, C.I. I. Basic Yellow 43, C.I. I. Oil-soluble dyes using basic dyes such as Basic Yellow 45 are included. More specifically, as an azomethine yellow oil-soluble dye, for example, trade name: Spiron Yellow C-GNH (manufactured by Hodogaya Chemical Co., Ltd.) is commercially available.
Examples of azomethine orange oil-soluble dyes include C.I. I. Basic Orange 21, C.I. I. Basic Orange 22, C.I. I. Basic Orange 27, C.I. I. Basic Orange 42, C.I. I. Basic Orange 44, C.I. I. And oil-soluble dyes using basic dyes such as Basic Orange 46.
[0032]
The azomethine yellow and / or orange oil-soluble dye is a dye obtained by salting the above basic dye to make it oil-soluble. For oil-solubilization, for example, using a resin such as a phenol resin, a basic dye is used. Can be salted.
[0033]
Azomethine yellow and / or orange oil-soluble dyes can be used alone or in combination of two or more. The amount of the azomethine yellow and / or orange oil-soluble dye used is 0.5 to 15% by weight, preferably 1 to 8% by weight, based on the total amount of the ink. When there is too much the said usage-amount, a viscosity will rise and writing property will fall. On the other hand, if the amount is too small, the handwriting density (coloring property) is low.
[0034]
(resin)
In the present invention, an oil-soluble resin may be used. The resin is not particularly limited as long as the resin is soluble in a polar organic solvent (particularly propylene glycol monomethyl ether). Preferably it is required to be safe. Examples of the resin include ketone resins, phenol resins (eg, alkylphenol resins, phenol resins, rosin modified phenol resins, etc.), xylene resins (eg, alkylphenol modified xylene resins, rosin modified xylene resins, etc.), styrene-organic Acid copolymers (for example, styrene-acrylic acid copolymers, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, etc.), polyacrylic acid esters and the like are included. Among the resins, ketone resins, phenol resins, and xylene resins are preferably used as the resin.
[0035]
The resins can be used alone or in combination. The amount of resin used is, for example, about 0.5 to 25% by weight, preferably about 1 to 15% by weight, based on the total amount of ink. If the amount of the resin used exceeds these ranges, the viscosity will increase and the writing property will decrease. On the other hand, if it is less than these ranges, the adhesion of the handwriting (handwriting) to the coated surface is low.
[0036]
In addition, various additions such as colorants (for example, other oil-soluble dyes), fillers, leveling agents, viscosity modifiers, structural viscosity imparting agents, drying property imparting agents, etc. are added to the red ink composition for oil-based marking pens. An agent or the like may be blended. Various additives are not specifically limited, A well-known additive can be utilized widely.
[0037]
(Production method)
The ink composition can be prepared by mixing the components (xanthene red oil-soluble dye, polar organic solvent, silicone polymer surfactant, azomethine yellow and / or orange oil-soluble dye, resin, etc.). A method for preparing the ink composition is not particularly limited. For example, a polar organic solvent, and if necessary, a resin is stirred and mixed under heating (for example, at 50 ° C.), followed by the oil-solubility. A dye and various additives are added as necessary, and the mixture is stirred and mixed under heating (for example, at 50 ° C.). Examples of the method include preparing after stirring and mixing, stopping heating, adding a silicone-based polymer surfactant, and stirring and mixing.
[0038]
The ink composition of the present invention has high water resistance, and has a non-absorbing surface as ink (a metal plate such as a tin plate, a writing surface such as a plastic film or sheet such as a film or sheet formed of polyethylene or polypropylene, etc. The ink composition is useful as an ink composition for oil-based marking pens because it has excellent fixability of handwriting when written on a surface that hardly absorbs oil-based ink. In addition, in this ink composition, an alcohol-based or glycol ether-based polar organic solvent (mainly propylene glycol monomethyl ether) is used as a solvent, so that a conventional non-polar organic solvent such as xylene is used. Compared to the human body, the safety is extremely high not only for the human body but also in the method of use and the manufacturing method.
[0039]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to these Examples.
(material)
As raw materials, the following oil-soluble dyes, polar organic solvents, silicone polymer surfactants, oil-soluble resins and the like were used.
(Oil-soluble dye)
・ Xanthene red oil-soluble dye 1:
Product name "Spiron Red C-GH" (Hodogaya Chemical Co., Ltd.)
・ Azomethine yellow oil-soluble dyes:
Product name "Spiron Yellow C-GNH" (Hodogaya Chemical Co., Ltd.)
・ Xanthene red oil-soluble dye 2:
Product name "Oil Pink 312" (manufactured by Orient Chemical)
・ Oil-soluble dyes:
Mixed salt-forming oil-soluble dye of xanthene red basic dye and monoazo yellow acid dye Product name “Varifast Red 1308” (manufactured by Orient Chemical Co., Ltd.)
(Polar organic solvent)
・ Propylene glycol monomethyl ether:
Product name "Dawanol PM" (manufactured by Dow Chemical)
・ Dipropylene glycol monomethyl ether:
Product name “Dawanol DPM” (manufactured by Dow Chemical)
・ Ethanol (silicone polymer surfactant)
・ Polyoxypropylene modified silicone 1:
Polyoxypropylene-modified silicone product name “Granol 115” (manufactured by Kyoeisha Chemical Co., Ltd.)
-Polyoxypropylene modified silicone 2:
Polyoxypropylene-modified silicone product name “TSF4460” (manufactured by Toshiba Silicone)
・ Carboxy modified silicone:
Carboxy-modified silicone product name “TSF4770” (manufactured by Toshiba Silicone)
(Oil-soluble resin)
・ Alkylphenol resin:
Product name "Tamanol 510" (Arakawa Chemical Industries)
・ Alkylphenol-modified xylene resin:
Product name “Nikanol HP-100” (Mitsubishi Gas Corporation)
・ Phenolic resin:
Product name “Tamanor 100S” (Arakawa Chemical Industries)
[0040]
(Examples 1-4 and Comparative Examples 1-2)
In each Example and each Comparative Example, red ink compositions for oil-based marking pens were obtained by blending at the ratios shown in Table 1 (the blending amounts of various components in Table 1 are all by weight). Specifically, for each example and each comparative example, a polar organic solvent and an oil-soluble resin were mixed with heating and stirring at 50 ° C. for 1 hour, and then an oil-soluble dye was added, and further at 50 ° C. for 1 hour. Mix with heat. After mixing, heating was stopped, a silicone polymer surfactant was added, and the mixture was stirred and mixed for 10 minutes to obtain a red ink composition for an oil-based marking pen.
[0041]
[Table 1]

[0042]
(Evaluation)
The red ink compositions for oil-based marking pens obtained in Examples 1-4 and Comparative Examples 1-2 were evaluated by the following fixability test, water resistance test, and color tone stability test.
[0043]
(Fixability test)
The red ink composition for oil-based marking pens obtained in Examples 1 to 4 and Comparative Examples 1 to 2 is filled in a writing instrument (Sakura Crepas oil marker, trade name “Pen Touch”) using felt as a pen tip. Using this, a straight line is written on a non-absorbing surface (tin plate, polyethylene plate), dried for 30 minutes, and then the handwriting is rubbed with a cotton swab at a load of 500 g. By this rubbing, the change in handwriting is visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in the column of fixability test in Table 1, respectively.
○: No change in the handwriting Δ: Slight scratching on the handwriting ×: The handwriting is peeled off by rubbing, and the non-absorbing surface is completely exposed.
(Water resistance test)
The red ink composition for oil-based marking pens obtained in Examples 1 to 4 and Comparative Examples 1 to 2 is filled in a writing instrument (Sakura Crepas oil marker, trade name “Pen Touch”) using felt as a pen tip. Using this, a straight line is written on high-quality paper, and after 1 minute of writing, it is immersed in water for 1 hour. After soaking, the soaked fine paper is placed on another dry fine paper and dried. After drying, the ink bleeding and the bleeding on the quality paper underlay are visually observed, and the water resistance is evaluated according to the following evaluation criteria. The evaluation results are shown in the water resistance test column of Table 1, respectively.
○: No ink bleed around the writing line ×: Ink bleed is seen around the writing line, and the ink adheres to the underlying high-quality paper [0045]
(Color stability test)
The red ink composition for oil-based marking pens obtained in Examples 1 to 4 and Comparative Examples 1 to 2 is filled into a writing instrument (Sakura Crepas oil marker, trade name “Pen Touch”) using felt as a pen tip. Using this, write a straight line on fine paper and leave it for 1 minute. A straight line is further written under or around the handwriting, the difference in color tone between the two is visually observed, and the color stability is evaluated according to the following evaluation criteria. Each evaluation result is shown in the column of color tone stability test in Table 1.
○: No difference in color tone between the two lines Δ: Some difference in color tone between the two lines X: Clear difference in color tone between the two lines
The red ink composition for an oil-based marking pen of the present invention (the ink composition of the examples) has higher fixability to the non-absorbing surface of the handwriting (handwriting) and the water resistance of the handwriting than the ink composition of the comparative example. In addition, there is almost no difference between the color of the ink immediately after writing and the color of the ink after ink drying, and a clear red color immediately after writing can be maintained after ink drying.
[0047]
【The invention's effect】
Since the ink composition of the present invention is a red ink composition for an oil-based marking pen containing a specific oil-soluble dye, a polar organic solvent, and a silicone-based polymer surfactant, it is used for a red-based oil-based marking pen. Despite being an ink, the water resistance of the handwriting and the fixability between the handwriting and the non-absorbing surface are high. Also, there is almost no difference in ink color between writing and after ink drying.
Moreover, the fixability of handwriting equivalent to or higher than when a nonpolar solvent such as xylene is used can be secured on a non-absorbing surface such as metal or plastic. Therefore, it is possible to provide an ink composition that has excellent fixability to the non-absorbing surface of the handwriting and water resistance of the handwriting, can maintain a clear red color after ink drying, and has high color safety.

Claims (6)

A dye, and a polar organic solvent, a silicone polymer surfactant seen including,
The dye is
A xanthene red oil-soluble dye,
Azomethine yellow oil-soluble dyes and / or azomethine orange oil-soluble dye and the including oily marking pen red ink composition.   The red ink composition for oil-based marking pens according to claim 1, wherein the polar organic solvent is propylene glycol monomethyl ether.   The red ink composition for oil-based marking pens according to claim 1 or 2, wherein the silicone-based polymer surfactant is at least one of polyoxypropylene-modified silicone and carboxy-modified silicone. The red ink composition for oil-based marking pens according to claim 1 or 2, wherein the silicone-based polymer surfactant is carboxy-modified silicone.   Furthermore, the red ink composition for oil-based marking pens in any one of Claims 1-4 containing oil-soluble resin.   The red ink composition for an oil-based marking pen according to claim 5, wherein the oil-soluble resin is at least one selected from a ketone-based resin, a phenol-based resin, and a xylene-based resin.