JP2008156421A - Oily ink for marking pen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide oily ink for a marking pen, having sufficiently excellent water resistance, especially the water resistance of hardly allowing a written line to be dropped from a written surface soaked in water, and sufficiently suppressing the repellency. <P>SOLUTION: The oily ink for the marking pen contains a pigment, an isoparaffin-based hydrocarbon, and a petroleum resin soluble in the isoparaffin-based hydrocarbon. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an oil-based ink for a marking pen.

  Oil-based inks used for marking pens usually contain a resin for forming a coating film on a writing surface in addition to a colorant and an organic solvent. Examples of the resin include a ketone resin, an acrylic resin, and a polyester resin. When writing with an oil-based marking pen, the resin containing the colorant forms a coating film on the writing surface and becomes a writing line, so that the writing surface hard to penetrate the solvent, for example, the surface of metal, resin and glass Even writing becomes possible.

  However, the conventional marking pen using oil-based ink has a problem that it cannot be written when trying to write on metal, resin, glass, craft tape, etc. wet with water.

  Therefore, various oil-based inks for marking pens that can be written on a writing surface wet with water have been proposed. For example, in Patent Document 1, a specific alkylphenol resin and an oil-soluble dye are dissolved in an isoparaffin solvent in order to provide an ink composition for an oil-based marking pen that can form clear handwriting on a wet surface. Oil-based marking pen inks have been proposed. Patent Document 2 intends to provide an ink composition for an oil-based marking pen that can form a dark black handwriting with excellent color developability and that can be clearly written on a wet surface. A black ink composition for oil-based marking pens, which is prepared by dissolving an oil-soluble black colorant composed of a mixture of an oil-soluble blue dye, a red dye and a yellow dye together with a specific alkylphenol resin in an aliphatic hydrocarbon solvent. Has been.

Furthermore, it is not repelled on the coated surface of the gum tape, and writing is possible even on a surface wet with water, and the ink adheres strongly to the object to be written and can be removed even if it is strongly rubbed with a finger. In order to provide an oil-based ink for marking pens, etc., Patent Document 3 discloses a dye having a phenyl group and / or a dye combined with an alkylphenol resin, an organic solvent composed of an isoparaffin hydrocarbon having 6 to 10 carbon atoms, and alkylphenol. An oil-based ink for marking pen made of resin is described. Similarly, in Patent Document 4, a marking pen formed by blending a dye, an organic solvent composed of an isoparaffin hydrocarbon having 6 to 10 carbon atoms and / or an alkylcyclohexane, a resin soluble in the organic solvent, and an oxidized wax. Oil-based inks have been proposed.
JP 2006-56947 A JP 2006-56946 A JP 2004-231726 A JP 2004-99819 A

However, the present inventors have studied in detail about conventional oil-based inks for marking pens including those described in Patent Documents 1 to 4, and the writing lines of any oil-based ink have water resistance. It has been found that it is not sufficient, or the repelling cannot be sufficiently suppressed.
That is, when water resistance is not sufficient, after writing with a marking pen using these oil-based inks, if the writing line is immersed in water for a while and then rubbed with a finger or the like, the writing line may easily drop. It was revealed. In this case, even when writing on an object installed outdoors or underwater, the writing line disappears from the writing surface in a short period of time.
In addition, when repelling cannot be sufficiently suppressed, writing lines are easily repelled when attempting to write on a writing surface that is easy to repel oil-based ink, such as metal, resin, glass, and craft tape. When this happens, the writing line becomes thinner or drops than the pen tip of the marking pen, and further, it becomes difficult to dry and it tends to fall off the writing surface.

  Therefore, the present invention has been made in view of the above circumstances, and is sufficiently excellent in water resistance, in particular, water resistance such that a writing line does not easily fall off from a writing surface immersed in water, An object is to provide an oil-based ink for a marking pen that can be sufficiently suppressed.

  In order to achieve the above object, the present invention provides an oil-based ink for a marking pen containing a pigment, an isoparaffinic hydrocarbon, and a petroleum resin soluble in the isoparaffinic hydrocarbon.

  The reason why such an oil-based ink for marking pens can achieve the object of the present invention has not been clarified in detail at present. However, the present inventors consider the factors as follows. That is, when writing using the oil-based ink of the present invention, the writing line is in a state where the pigment is coated with a petroleum resin dissolved in isoparaffinic hydrocarbon. Thereafter, when the isoparaffinic hydrocarbon as the solvent volatilizes, the petroleum resin coated with the pigment adheres to the writing surface and effectively functions as a protective film for the pigment. As a result, even if the writing surface is immersed in water, the writing line protected by the petroleum resin is firmly fixed to the writing surface, so that it does not easily fall even when rubbed with a finger or the like. Furthermore, by reducing the surface energy of the oil-based ink due to the interaction between the petroleum resin and the isoparaffinic hydrocarbon, the interfacial tension between the writing surface and the surface of the writing surface is reduced, so that it exhibits good writing properties with suppressed repelling. It is estimated that However, the factors are not limited to these.

  The oil-based ink of the present invention is very excellent in adhesion of the pigment to the writing surface even when it is not immersed in water, mainly because it contains a petroleum resin. Therefore, even if the writing line is rubbed with a finger or the like after writing, the pigment does not easily peel off.

  Furthermore, since the oil-based ink of the present invention employs a pigment as a colorant, it exhibits high light resistance. This high light resistance is presumed to be caused by the fact that the oil-based ink of the present invention contains a petroleum resin.

  Moreover, since the oil-based ink of the present invention uses an isoparaffinic hydrocarbon as a solvent, it has excellent quick drying properties. The writing line with this oil-based ink can exhibit sufficiently high water resistance immediately after writing. Moreover, since the isoparaffinic hydrocarbon is adopted as the solvent, the oil-based ink of the present invention has a low odor.

  In the oil-based ink for a marking pen of the present invention, the petroleum resin is preferably a petroleum resin whose monomer component is an aliphatic unsaturated hydrocarbon and / or an aromatic unsaturated hydrocarbon. By containing such a petroleum resin, it is possible to more reliably achieve effects such as water resistance, suppression of repellency and weather resistance (particularly light resistance). From the same viewpoint, the number average molecular weight of the petroleum resin is preferably 500-3500.

  According to the present invention, there is provided an oil-based ink for a marking pen that is sufficiently excellent in water resistance, particularly water resistance such that a writing line does not easily fall from a writing surface immersed in water, and can sufficiently suppress repellency. be able to.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  The oil-based ink for a marking pen according to the present embodiment contains a pigment, an isoparaffinic hydrocarbon, and a petroleum resin that is soluble in the isoparaffinic hydrocarbon.

  The pigment of this embodiment is used as the main component of the colorant. The pigment is not particularly limited as long as it is generally used for oil-based inks. Examples of the pigment include inorganic pigments such as carbon black, titanium oxide, pearl pigments, and metal powder pigments, and organic pigments such as nitroso pigments, nitro pigments, azo pigments, dye lake pigments, and fluorescent pigments. These pigments are commercially available, and may be commercially available in a state dispersed in a solvent. A pigment is used individually by 1 type or in combination of 2 or more types.

  The ratio of the pigment in the colorant is, for example, preferably 80% by mass or more, more preferably 90% by mass or more, with respect to the total mass of the colorant, from the viewpoint of further improving the color developability and light resistance, and the like. More preferably, it is more preferably at least 98% by mass, particularly preferably at least 98% by mass, and most preferably 100% by mass, that is, it contains only pigment. However, the oil-based ink of the present embodiment may contain a colorant other than the pigment, for example, a dye as long as the object of the present invention is not hindered. The dye is not particularly limited as long as it is generally used for oil-based inks.

  The isoparaffinic hydrocarbon of this embodiment is used as a main component of the solvent, and is used alone or in combination of two or more. Isoparaffinic hydrocarbons are obtained by refining and / or synthesizing petroleum raw materials. The isoparaffinic hydrocarbon is preferably an isoparaffinic saturated hydrocarbon from the viewpoint of more reliably obtaining excellent low odor and suppression of repelling. In addition, the boiling range of the isoparaffinic hydrocarbon at normal pressure is preferably 65 to 400 ° C, more preferably 65 to 300 ° C, from the viewpoint of easily ensuring safety and good volatility. More preferably, it is 250 degreeC, and it is especially preferable that it is 65-150 degreeC.

  Commercially available isoparaffinic hydrocarbons include, for example, IP Solvent 1016, IP Solvent 1620, IP Solvent 2028 and IP Solvent 2835 (above, manufactured by Idemitsu Kosan Co., Ltd., trade name), Isosol Series (Shin Nippon Oil Co., Ltd.) Product, trade name), Shellzol TG, Shellzol TK and Shellzol TM (above, Showa Shell Sekiyu KK, trade name), Isopar E and Isopar G (ExxonMobil, trade name), and the like.

  The ratio of isoparaffinic hydrocarbon in the solvent is, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more with respect to the total mass of the solvent, from the viewpoint of further improvement of water resistance. Is more preferable. However, the oil-based ink of the present embodiment may contain an organic solvent other than the isoparaffinic hydrocarbon as long as the achievement of the object of the present invention is not hindered. The organic solvent is not particularly limited as long as it is generally used for oil-based inks.

  Petroleum resins soluble in isoparaffinic hydrocarbons are resins containing petroleum unsaturated hydrocarbons as monomer components. Examples of petroleum resins include aliphatic petroleum resins in which the monomer component is an aliphatic unsaturated hydrocarbon, aromatic petroleum resins in which the monomer component is an aromatic unsaturated hydrocarbon, and monomer components that are alicyclic unsaturated carbon The alicyclic petroleum resin which is hydrogen is mentioned. Alternatively, the petroleum resin may be an aliphatic / aromatic petroleum resin having both an aliphatic unsaturated hydrocarbon and an aromatic unsaturated hydrocarbon as monomer components. Among these, aliphatic petroleum resins, aromatic petroleum resins, or aliphatic / aromatic petroleum from the viewpoints of more reliably achieving the object of the present invention, further effectively suppressing repelling, and improving weather resistance. Resins are preferred, and aliphatic / aromatic petroleum resins are more preferred.

  The number average molecular weight of the petroleum resin is preferably 500 to 3500, more preferably 800 to 1500, and still more preferably 1200 to 1300. When the number average molecular weight is less than 500, the water resistance of the oil-based ink tends to be lower than when the number average molecular weight is within the range of 500 to 3,500. When the number average molecular weight is over 3,500, the number is within the range of 500 to 3,500. In comparison, the fluidity of the oil-based ink tends to decrease.

  Petroleum resins may be synthesized by conventional methods, or commercially available products may be obtained. Commercially available petroleum resins include, for example, Quintone D200, Quintone D100 and Quintone A100 (above, ZEON Corporation, trade name), Nisseki Neopolymer L-90, Nisseki Neopolymer 120 and Nisseki Neopolymer 130 ( As mentioned above, Toho High Resin RS-9 and Toho High Resin # 90 (manufactured by Toho Chemical Industry Co., Ltd., trade name) are listed.

  The above-mentioned petroleum resins are used singly or in combination of two or more.

  In the oil-based ink for marking pens of this embodiment, the blending ratio of the pigment is preferably 4 to 20% by mass and more preferably 6 to 10% by mass with respect to the total amount of the oil-based ink. When the blending ratio of the pigment is less than the lower limit, the colorability of the oil-based ink tends to be lowered. When the pigment content exceeds the upper limit, the viscosity of the oil-based ink is increased and the writing performance tends to be lowered.

  The blending ratio of the solvent is preferably 40 to 80% by mass and more preferably 50 to 70% by mass with respect to the total amount of the oil-based ink. When the blending ratio of the solvent is lower than the above lower limit, the viscosity of the oil-based ink is increased, and there is a tendency to cause inconvenience particularly when used for a batting type marking pen. Moreover, when the mixture ratio of a solvent exceeds the said upper limit, there exists a tendency for the colorability of oil-based ink to fall.

  The blending ratio of the petroleum resin is preferably 250 parts by mass or more and more preferably 350 parts by mass or more with respect to 100 parts by mass of the pigment. When the blending ratio of the petroleum resin is lower than the lower limit, water resistance, adhesion and weather resistance (particularly light resistance) tend to be lowered. Moreover, the blending ratio of the petroleum resin is preferably 15 to 40% by mass and more preferably 20 to 35% by mass with respect to the total amount of the oil-based ink. When the blending ratio of the petroleum resin is less than the lower limit, the effect of suppressing the repelling of the writing line on the writing surface tends to be reduced. On the other hand, when the blending ratio of the petroleum resin exceeds the above upper limit, the viscosity of the oil-based ink tends to increase and the ink dischargeability tends to decrease.

  The oil-based ink for a marking pen according to the present embodiment includes additives such as a viscosity modifier, a pigment dispersant, and a dispersion aid as necessary within the scope of the present invention in addition to the above-described components. You may mix | blend suitably.

  In the oil-based ink for a marking pen of the present embodiment, the writing line thereby is protected by petroleum resin, and the petroleum resin strongly fixes the writing line (pigment) to the writing surface. Therefore, even if the writing line is rubbed with a finger or the like after the writing surface is immersed in water, it does not fall easily. Further, even when the oil-based ink of the present embodiment is not immersed in water, the writing line (pigment) and the writing surface are strongly bonded by the petroleum resin, so that the adhesion of the pigment to the writing surface is improved. Very good. Therefore, even if the writing line of this oil-based ink is rubbed with a finger or the like after writing, the pigment does not easily peel off.

  In addition, the oil-based ink of the present embodiment exhibits good writing properties with sufficiently suppressed repelling even on a writing surface such as metal, resin, glass, and craft tape that is easy to repel oil-based ink.

  Furthermore, since the oil-based ink of the present embodiment employs a pigment as a colorant and contains a petroleum resin, it exhibits high weather resistance, particularly high light resistance. Moreover, since the oil-based ink of this embodiment uses isoparaffinic hydrocarbon as a solvent, it has excellent quick drying properties. Therefore, the writing line with this oil-based ink can exhibit sufficiently high water resistance immediately after writing. In addition, since an isoparaffinic hydrocarbon is employed as the solvent, the oil-based ink of the present embodiment has a low odor compared to an oil-based ink mainly containing an alcohol solvent or an aromatic solvent.

  Next, a marking pen according to a preferred embodiment of the present invention will be described. The marking pen of this embodiment will not be specifically limited if it is provided with the above-mentioned oil-based ink for marking pens. Therefore, the thickness of the nib, the batting type, and the direct liquid type are not limited.

  As an example of the marking pen according to the above-described embodiment, FIG. 1 is a schematic longitudinal sectional view showing the entire marking pen. In the marking pen 100, an ink containing tube 4 having a filling filled with the oil-based ink for a marking pen of the present embodiment is loaded in the shaft cylinder 1. A writing chip 3 is attached to the tip of the shaft cylinder 1 through a tip 17. A tail plug 5 is attached to the rear end of the shaft tube 1. The oil-based ink is supplied to the writing tip 3 from the ink containing tube 4 and is discharged from the tip of the writing tip 3. The marking pen 100 may be detachably mounted with the cap 2 for the purpose of sealing the writing chip 3.

The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

[Preparation of oil-based ink for marking pens]
Examples 1-4 by mixing each component shown in Table 1 by the compounding ratio (mass basis) shown in Table 1, stirring at 50 degreeC for 1 hour or more, and fully dissolving and disperse | distributing other components in a solvent. The oil-based inks for marking pens of Comparative Examples 1 to 5 were obtained. The following components were used. The petroleum resin A is an aliphatic / aromatic petroleum resin, the petroleum resin B is an aliphatic petroleum resin, and the petroleum resin C is an aromatic petroleum resin.

Pigment: Carbon black Solvent: IP solvent 1016 (trade name, manufactured by Idemitsu Kosan Co., Ltd.)
Petroleum resin A: Quintone D200 (made by Nippon Zeon Co., Ltd., trade name)
Petroleum resin B: Quintone A100 (product name)
Petroleum resin C: Toho High Resin RS-9 (trade name, manufactured by Toho Chemical Industry Co., Ltd.)
Hydrogenated terpene resin A: CREARON P115 (manufactured by Yasuhara Chemical Co., Ltd., trade name)
Hydrogenated terpene resin B: CREARON K100 (trade name, manufactured by Yasuhara Chemical Co., Ltd.)
Aromatic modified terpene resin: YS RESIN TO-115 (trade name, manufactured by Yashara Chemical Co., Ltd.)
Terpene resin: YS RESIN PX1150 (trade name, manufactured by Yasuhara Chemical Co., Ltd.)
Alkylphenol resin: Tamorol 510 (trade name, manufactured by Arakawa Chemical Co., Ltd.)

[Production of oil-based marking pen]
The oil-based marking pens of Examples 1 to 4 and Comparative Examples 1 to 5 obtained as described above were filled in paint markers made by Zebra Co., respectively, to prepare oil-based marking pens.

[Evaluation of water resistance of writing lines]
Using the oil-based marking pens according to Examples 1 to 4 and Comparative Examples 1 to 5 produced as described above, and a commercially available black oil-based marking pen (commercial name “Sharpy Professional” manufactured by Sanford) as Comparative Example 6 Written on the glass plate surface. Subsequently, the glass plate after writing was immersed in water at room temperature for a predetermined time. And after predetermined time progress, the water resistance was evaluated by rubbing the writing line on the glass surface with a finger in the immersed state, and whether the writing line fell from the glass surface. “D” indicates that the writing line fell off the glass surface immediately without being rubbed with a finger when immersed, and “C” indicates that the writing line fell when rubbed with a finger one hour after immersion. The case where the writing line fell when it was rubbed with a finger after 3 hours passed was evaluated as “B”, and the case where the writing line was not dropped even after being rubbed with a finger after 3 hours passed was evaluated as “A”. The results are shown in Table 2.

[Writing evaluation of writing lines]
First, a commercially available kraft tape having a surface coated with a silicone coating was pasted on a glass plate. Subsequently, it wrote on the surface of the said craft tape using the oil-based marking pen which concerns on Examples 1-4 and Comparative Examples 1-6. At this time, it was evaluated whether the writing line was repelled on the surface of the craft tape. "A" if no repellency is recognized and writing is good, "B" if the writing line is slightly repelled and the writing line is thinner than the pen tip thickness. The case where the ink was repelled and the ink remained in a droplet shape on the part traced with the marking pen was evaluated as “C”. The results are shown in Table 2.

[Evaluation of light resistance of writing lines]
First, it wrote on the writing paper used with the marking pen of JIS-S6037 using the oil-based marking pen which concerns on Examples 1-4 and Comparative Examples 1-6. Next, the writing line was exposed to sunlight until the quaternary blue scale defined in JIS-L0841 faded to about 4-5 grade of the gray scale for color fading defined in JIS-L0804. Then, the degree of color change of the writing line was evaluated by the number (1-5) of the gray scale for color change. The results are shown in Table 2.

It is a model longitudinal cross-sectional view of the marking pen which concerns on embodiment of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Shaft cylinder, 2 ... Cap, 3 ... Writing tip, 4 ... Ink storage tube, 5 ... Tail plug, 100 ... Marking pen.

Claims (3)

  An oil-based ink for a marking pen containing a pigment, an isoparaffinic hydrocarbon, and a petroleum resin soluble in the isoparaffinic hydrocarbon.   The oil ink for a marking pen according to claim 1, wherein the petroleum resin is a petroleum resin having a monomer component of an aliphatic unsaturated hydrocarbon and / or an aromatic unsaturated hydrocarbon. The oil-based ink for marking pens of Claim 1 or 2 whose number average molecular weights of the said petroleum resin are 500-3500.

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