Color ink composition having metallic luster for marking pen

[Technical Field to which the Invention Affiliates] The present invention relates to a metallic luster color ink for a marking pen. For details, it has a metallic luster such as gold, silver, copper, red, and blue on various types of writing objects, and gives a clear and concealing robust brush stroke. The present invention relates to a metallic luster color ink composition for a marking pen, which exhibits the same reflective metallic luster as before long-term storage and has excellent redispersibility of metal powder pigments.

[0002] Examples of the marking pen include a shaft body whose inside is an ink storage tube, a pen body inserted at the tip of the shaft body, and an ink outflow adjusting device that supplies ink from the shaft body to the pen body. There is one equipped with. Examples of the pen body include a fiber convergent body or a plastic rod body through which a hole is penetrated. Further, as the ink outflow adjusting device, a mechanism for operating a valve by a pressing operation to supply ink from the ink accommodating tube to the pen body, or an ink accommodating tube via a spiral guide core to guide the ink to the pen body. It is possible to exemplify a mechanism or the like configured to do so. Further, if necessary, an ink containing ball provided with a ball for stirring ink is used.

PROBLEM TO BE SOLVED: To provide a metallic luster color ink composition for writing a character, a symbol or the like having a metallic luster on the surface of a metal, glass, plastic or the like or paper or the like for a marking pen.

[0004] For example, a plastic foil on which metal is vapor-deposited is pulverized and dispersed in a vehicle in which a resin is dissolved in an organic solvent. However, the characters, symbols, etc. written with ink using a crushed metal vapor-deposited plastic foil to impart metallic luster (hereinafter, the written characters, symbols, etc. are referred to as handwriting) have poor metallic luster.

[0005] In order to improve this, a fine metal powder having a scaly shape and a surface treated with a higher fatty acid or a salt of a higher fatty acid to enhance the metallic luster imparting action, that is, a so-called leafing type fine metal powder is used. Became. For example, Japanese Patent Application Laid-Open No. 1-56109 states that palmitic acid is dissolved in a solution of a hydrocarbon resin or xylene resin in an organic solvent selected from aromatic hydrocarbons, aliphatic or aliphatic hydrocarbons, ketones, and esters. Described are inks having a composition in which leafing-type fine metal powders selected from aluminum, copper, zinc, and copper alloys whose surfaces have been treated with fatty acids such as stearic acid and oleic acid are dispersed.

[0006] [Problems to be Solved by the Invention] In Japanese Patent Publication No. 1-56109, alkylphenol-modified xylene resin, xylene resin or petroleum resin is used as an aromatic solvent such as mineral spirit or xylene and methylisobutylketone, n-. A metallic glossy ink having a composition in which a roofing type metal powder is dispersed in a solution dissolved in a mixed solvent with hexane or methylcyclohexane, and a rust preventive and a dispersant are added is shown. The handwriting written with the ink of the above composition has a clear and highly reflective metallic luster color, but the handwriting written after being stored in the marking pen for a long period of time, for example, 3 months, is compared with the handwriting before storage. This may result in reduced reflectivity, almost no metallic luster, and simply a metallic color. As described above, the ink using the leafing type metal powder may deteriorate during storage and the quality of the handwriting may deteriorate, and the storage deterioration resistance is not sufficient. There is also a problem in the redispersibility of the metal powder.

[0007] The subject of the present invention is that there is almost no deterioration or discoloration even after long-term storage, and the writing object has the same metallic luster as the initial one, such as gold, silver, and copper, and is clear and reflective. It is an object of the present invention to provide a metallic luster color ink for a marking pen which sufficiently expresses a metallic luster and has excellent redispersibility of a metal powder pigment.

[Means for Solving the Problems] As a result of diligent studies to achieve the above problems, the inventor has determined that the resin and solvent used affect the surface treatment agent for the leafing type metal powder and are being stored. It was found that the leafing characteristics of the metal powder were changed, and the present invention was completed.

That is, the invention according to claim 1 is<u style="single">following</u><u style="single">(1)</u><u style="single">~</u><u style="single">(3)</u><u style="single">Is an essential ingredient, and the following</u><u style="single">(3)</u><u style="single">The mixed weight ratio of the two types of hydrocarbon solvents with different vapor pressures is 25 to 400 for the solvent 100 with the lower vapor pressure and 25 to 400 for the solvent with the higher vapor pressure, if necessary.</u><u style="single">(4)</u><u style="single">Contain</u>A metallic luster ink composition for marking pens. ..<u style="single">(1)</u>Leafing-type fine metal powder with an average particle size in the range of 4 to 11 μm, selected from copper alloys, aluminum, copper, and zinc whose surface is treated with saturated fatty acids having 16 to 22 carbon atoms or salts thereof, is added to the total amount of ink. 10-38% by weight,<u style="single">(2)</u>10 to 30% by weight of petroleum resin with iodine value of 30 (g / 100g) or less, based on the total amount of ink.<u style="single">(3)</u><u style="single">Different vapor pressure</u>32 to 80% by weight of two types of hydrocarbon solvents with respect to the total amount of ink<u style="single">(4)</u>Pigments, oil-based dyes, rust preventives, leafing agents, pigment dispersants [0010] [Embodiments of the Invention] Specific examples of the leafing type fine metal powder used in the present invention include palmitic acid and stearic acid. The surface is treated with a saturated higher fatty acid having 16 to 22 carbon atoms or a metal salt thereof, and the average particle size is 4 to 11 μm. Then, this leafing type fine metal powder is blended in the ink, and when writing is given, the property of embossing on the surface of the handwriting is imparted, the reflectivity is increased, and a metallic luster color is developed.

[0011] Further, the petroleum resin used in the present invention uses, for example, an aromatic petroleum resin or an aliphatic resin produced as a by-product during cracking of petroleum, or a higher unsaturated hydrocarbon as a raw material, and uses an acidic catalyst. A hydrogenated petroleum resin obtained by hydrogenating the petroleum resin polymerized using the petroleum resin can be exemplified. Its chemical structure is complex, with most of the structure pendant on long aliphatic saturated hydrocarbon chains with saturated hydrocarbon rings. And, regardless of whether it is an aromatic resin or an aliphatic resin, some carbon-carbon bonds are unsaturated bonds. The content of unsaturated bonds varies depending on the degree of hydrogenation of the petroleum resin, but in the present invention, the content of unsaturated bonds is reduced by using a petroleum resin as much as possible.

[0012] As described above, the petroleum resin having the minimum unsaturated bond content is used for the production of metallic luster color ink with a leafing type fine metal powder and a petroleum resin having a high iodine value, in other words, an unsaturated bond. When a petroleum resin having a high content is used, electrons are transferred between the fine metal powder and the double bond between the saturated higher fatty acid surface-treated on the fine metal powder and the resin, and the fine metal powder is oxidized. This is because it is considered that deterioration such as loss of leafing property occurs, and as a result, deterioration or discoloration such as impaired metallic luster color occurs in the ink.

[0013] Therefore, in order to prevent a decrease in metallic luster and discoloration during storage, an unsaturated bond is formed between the saturated higher fatty acid used for the surface treatment of the fine metal powder or the fine metal powder and the resin in which electrons are transferred. From the finding that it should be reduced, it was confirmed that when a saturated petroleum resin was used, the ink composition could prevent discoloration and deterioration. Therefore, as a result of diligently examining the minimum amount of double bonds of the resin that can substantially obtain this effect, it was found that the iodine value should be 30 (g / 100 g) or less. The iodine value may be 30 (g / 100 g) or less, but a petroleum resin having an iodine value of 15 (g / 100 g) or less is more preferable. Actually, those having an iodine value of 0 to 30 (g / 100 g), particularly those having an iodine value of 0 to 15 (g / 100 g) can be preferably used. The iodine value can be adjusted by hydrogenation.

[0014] As the aromatic petroleum resin, resins such as styrene, α-methylstyrene, and a copolymer of vinyltoluene and α-methylstyrene are particularly effective, and the iodine value thereof is 15 (g / 100 g). ) Below, preferably 0 to 10 (g / 100g). In particular, iodine value of 0 to 5 (g / 100g) is optimal.

[0015] Among aromatic thermal petroleum resins, a resin obtained by polymerizing a high-purity monomer is preferable. In the case of styrene, a styrene-based compound having a molecular weight much smaller than that of ordinary polystyrene, specifically 300 to 1000, and having an iodine value adjusted to 0 to 10 (g / 100 g) is optimal. For example, the trade names "Picolastic A5" and "Picolastic 75" manufactured by Rika Hercules are preferably used. Further, also in the case of α-methylstyrene, for example, one having a small molecular weight of 600 to 1100 is preferable, and one having an iodine value of 0 to 5 (g / 100 g) is optimal. For example, the product names "Crystalex 3085" and "Crystalex 3100" manufactured by Rika Hercules are suitable. In the case of a copolymer of vinyltoluene and α-methylstyrene, one having a molecular weight of 900 to 4000 and an iodine value of 0 to 5 (g / 100 g) is preferable. For example, the product name "Picotex LC" manufactured by Rika Hercules is the most suitable.

[0016] On the other hand, if the marking pen is filled with the above-mentioned metallic glossy color ink of the present invention and left to stand, the fine metal powder dispersed in the organic solvent precipitates during that time. It is necessary to shake the sphere in the ink containing tube to stir the ink by shaking the marking pen to redisperse the precipitated fine metal powder, but the redispersibility deteriorates over a long period of time. Therefore, in order to improve this redispersibility, the present invention uses a mixture of two or more kinds of solvents having different vapor pressures, and the solvent weight of the higher one with respect to the solvent weight of 100 having the lower vapor pressure in terms of weight ratio. When the ratio is 25 to 400, solvent convection occurs, sedimentation of the leafing type fine metal powder is suppressed, sedimentation is less likely to be agglomerated, and redispersibility is improved. If the mixing ratio is out of the range of 100: 25 to 400 shown above even if one type of solvent is used or two or more types are used, the fine metal powder is likely to settle and agglomerate.

[0017] If the blending amount of the leafing type fine metal powder is too small, the handwriting concentration may be insufficient or the hiding property may be poor, and if it is excessive, ink outflow failure may occur or during long-term storage. It precipitates and solidifies. A suitable blending amount is 10 to 38% by weight of the total amount of ink, and a more suitable range is 31 to 35% by weight.

[0018] The blending amount of the petroleum resin is 10 to 30% by weight, preferably 15 to 27% by weight, based on the total amount of the ink. If it is less than 10% by weight, the redispersibility during storage deteriorates, the metallic luster deteriorates, and the adhesion of the handwriting to the object to be written becomes poor and the handwriting disappears, which is more than 31% by weight. As a result, the viscosity of the ink increases, causing poor ink outflow.

[0019] If the amount of the solvent is too small, poor ink outflow occurs, or if it is precipitated and solidified during long-term storage, if it is excessive, the concentration of the handwriting is insufficient and the concealing property is deteriorated. The blending amount is adjusted by the resin dissolving power and vapor pressure of the solvent, but the range of 32 to 80% by weight of the total amount of ink is preferable, and 40 to 60% by weight when an alicyclic saturated hydrocarbon solvent is used. Is preferable.

[0020] In the ink composition of the present invention, various additives such as oil-based dyes, rust preventives, leafing properties, pigment dispersants, and pigments are used as needed, as long as the above-mentioned effects are not impaired. , Colorants such as dyes that are soluble in the organic solvent can be blended.

[Example] According to the formulations (weight ratios) shown in Tables 1 and 2, the resin is added to a solvent, stirred and dissolved while heating at 50 ° C., cooled to room temperature, and then the fine metal is added. In addition, the mixture is stirred and dispersed to obtain a metallic luster ink composition for a marking pen.

Next, this ink composition was used in a marking pen to evaluate the metallic luster of handwriting, the metallic luster of handwriting after long-term storage, and the redispersibility after long-term storage. The results are shown in Tables 1 and 2.

[0023] The marking pen used here is a "paint marker fine print" assembly manufactured by Sakura Color Products Corporation. Explaining the structure, a shaft body having an ink storage tube inside, a pen body of a fiber converging body attached to the tip of the shaft body, and an ink outflow adjustment provided between the pen body and the ink storage tube. It is equipped with a device. Then, this ink outflow adjusting device operates a valve by a pressing operation to supply ink from the ink accommodating tube to the pen body. In addition, a rigid sphere for stirring is enclosed in the ink containing tube.

[0024] [Table 1]<img file="JP3774514B2_D0001.tif" />[0025] [Table 2]<img file="JP3774514B2_D0002.tif" />Details of the compounding agents used in Tables 1 and 2 are shown below. (1) SUPER 3000: ECKART-WERKE, STANDART BRONZE POWDER SUPER 3000 RICHGOLD (Stearic acid surface treatment, average particle size 4 μm, leafing type fine copper alloy powder) (2) ROTOFLEX: ECKART WERKE, STANDART BRONZE POWDER ROTOFLEX RICHGOLD (Stearic acid surface treatment, average particle size 5 μm, leafing type fine copper alloy powder) (3) RESIST ROTOFLEX: ECKART WERKE, STANDART BRONZE POWDER RESIST ROTOFLEX RICHGOLD (Stearic acid surface treatment, average particle size 5 μm, non-leafing type fine copper) Powder) (4) CHROMAL X: ECKART WERKE, STANDART ALMINIUM POWDER CHROMAL X (Stearic acid surface treatment, average particle size 9 μm, leafing type fine aluminum powder) (5) Alpaste 1230M: Toyo Aluminum Co., Ltd., Alpaste 1230M (palmitic acid surface treatment, average particle size 10 μm) , Non-leafing type fine aluminum powder) (6) Marukaletz H925: Marukaretsu H925 (petroleum resin, iodine value 10g / 100g) (7) Marukaretsu H505: Marukaretsu H505 (petroleum resin, Iodine value 30g / 100g) (8) Neopolymer 170S: Made by Nippon Petroleum Co., Ltd., Nisseki Neopolymer 170S (Petroleum resin, Iodine value 47g / 100g) (9) Marcaretz M845: Marukaretsu M845 (Alicyclic hydrocarbon resin, iodine value 190g / 100g) (10) Marukaretsu S100A: Marukaretsu S100A (aliphatic hydrocarbon resin, iodine value 150g / 100g), manufactured by Maruzen Petrochemical Co., Ltd. ) (11) Rigalite R-90: Riga Hercules, Rigalite R-90 (Alicyclic petroleum resin, iodine value less than 1.6 (g / 100g)) (12) Picorastic A75: Rika Hercules, picorastic A75 (Styrene resin, iodine value 3.2 (g / 100g)) (13) Picotex LC: Rika Hercules, Picotex LC (vinyl toluene and α-methylstyrene polymer, iodine value 3.2 (g / 100g)) ( 14) Crystallex 3085: Rika Hercules, Crystallex 3085 (α-methylstyrene resin, iodine value 4.8 (g / 100g)) (15) MCH: Maruzen Petrochemical, methylcyclohexane, steam pressure at 22.0 ° C 40 mmHg: alicyclic saturated hydrocarbon solvent) (16) ECH: Maruzen Petrochemical Co., Ltd., ethylcyclohexane, vapor pressure at 20.6 ° C: 10 mmHg: alicyclic saturated hydrocarbon solvent) [0027] The evaluation was performed as follows. The initial metallic luster was evaluated visually by writing on black art paper on the day when the ink was sealed in the marking pen, and those judged to have reached the expected level were marked with , those that did not reach x, and those that did not reach. However, the ones judged to be quite good are indicated by Δ. For metallic luster after long-term storage, the marking pen containing ink is stored at a temperature of 50 ° C for one month, and then the marking pen is shaken to shake and stir the steel balls in the ink storage tube to re-precipitate the fine metal powder that has settled. After the dispersion, the same procedure as the initial metallic luster evaluation was performed.

[0028] The redispersibility is such that when the marking pen stored at the above temperature of 50 ° C. for one month is shaken to redisperse the fine metal powder, the number of shakes until the steel ball in the ink containing tube starts to move is 10 times or less. Items are indicated by , and items exceeding 10 times are indicated by ×.

[0029] Comparative Examples 1, 2 and 3 are examples in which a petroleum resin having an iodine value greater than 30 (g / 100 g) is used, and the initial metallic luster is good, but it is deteriorated after long-term storage. In particular, Comparative Example 2 using Marcaretz M-845 having an iodine value of 190 is significantly deteriorated. Comparative Examples 4 and 5 are examples in which non-leaving type fine metal powder is used, and the initial metallic luster is poor. Comparative Examples 6 and 7 use only one type of solvent, and Comparative Examples 8 and 9 use two types of solvents, but they are biased to one side, and both are re-used after long-term storage. Poor dispersibility. On the other hand, all the inks of the examples have good initial metallic luster and metallic luster after long-term storage. It also has good redispersibility after long-term storage.

[Effects of the Invention] As described above, the metallic luster ink composition for a marking pen of the present invention has a metallic luster having excellent reflectivity, and even if stored for a long period of time, discoloration, deterioration of the metallic luster, etc. There is no alteration, and even if the metal powder precipitates, it can be easily redispersed.