JP3486688B2 - Aqueous metallic glossy ink for ballpoint pens - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses aluminum powder as a coloring material, and further uses a coloring material as needed, and the handwriting is silver, gold or copper. The present invention relates to a water-based metallic glossy ink for ball-point pens that can obtain a metallic color of the above, and a deterioration of the ink as much as possible during long-term storage. 2. Description of the Related Art Conventionally, metal powder pigments such as aluminum powder and bronze powder have been used as a coloring material for giving a handwriting a luminous feeling in obtaining a metallic (metallic luster) color of gold or silver. Further, in order to show handwriting of various metallic gloss colors such as copper color, a dye or a pigment is used in combination with a metal powder pigment. For example, a low-viscosity ink for marking pens using aluminum powder is disclosed in Japanese Patent Publication No. Sho 62-376.
There are inks described in JP-B-78-78 and JP-B-1-56109. JP-B-62-37678 discloses a metal powder pigment such as aluminum powder, an oil-soluble dye, a resin, and a solvent, and the dye penetrates and diffuses around a handwriting formed by the metal powder pigment to form a contour. A dual color ink composition that produces a linear effect is disclosed. 1-561
No. 09 discloses a marking pen having fine metal powders such as surface-treated aluminum powder, a resin, and a solvent, which has a smooth ink bleeding property from the marking pen and has an easy dispersibility at the time of use. Metallic gloss inks are disclosed. Since the ink described in the above publication is a low-viscosity ink, the aluminum powder precipitates and separates in a short period of time. Therefore, in these inks, a stirring member such as a metal ball is stored in the ink storage chamber, and the metal powder pigment settled using the stirring member during use is re-dispersed and used. [0004] Unlike the above ink for marking pens,
There has also been proposed an ink having a metallic luster that suppresses sedimentation and separation of aluminum powder by increasing the ink viscosity and does not require a stirring member such as a metal ball. JP-A-60-18657
No. 3 is characterized in that a solvent and a thickening resin soluble in the solvent, a metal powder pigment and a coloring pigment are each contained in at least a required amount, and have a high viscosity not less than a required value. Disclosed is an ink having a metallic color, which has a high viscosity and little sedimentation of a metal pigment, and is suitable for use in a pressure ballpoint pen. As an example of an ink used for a normal ball-point pen which is not a pressurized type, Japanese Patent Publication No. 64-4551 discloses a gelled non-flowable ink. [0005] The ink proposed as the above prior art is an oil-based ink using an organic solvent as a solvent. On the other hand, as an aqueous ink using aluminum powder, Japanese Patent Application Laid-Open No. Hei 1-210478 discloses an ink containing a resin, an aluminum paste, and water, and an acetylene alcohol derivative as an additive. A water-based metallic glossy ink characterized by the above feature is disclosed, in which coating stains due to pinholes are prevented. [0007] However, none of the inks proposed as the above-mentioned prior art has a proposal for an aqueous metallic glossy ink that can be used for ballpoint pens. That is, the ink compositions of the inventions described in JP-B-62-37678 and JP-B-1-56109 are oil-based inks and are intended for use as a marking pen. In this case, the marking pen is, as described above, one in which a stirring member such as a metal ball is stored in the ink storage tube chamber, and the writing tool is shaken at the time of use to redisperse the precipitated aluminum powder. . That is, in these ink compositions for marking pens, the aluminum powder settles in a short time. The ink of the invention described in JP-A-60-186573 is used for a ball-point pen having a pressurized structure, and uses an ink storage tube formed of a hollow cylindrical body which can be written at atmospheric pressure. When used for a ballpoint pen having a structure, practically satisfactory results have not been obtained. Japanese Patent Publication No. 64-4
No. 551, the ink is non-fluid, and the rotation of the ball at the tip of the ballpoint pen causes
Although the ink is turned into a sol at the rotating portion of the ball and is discharged, continuous writing is not disclosed at all. The ink described in Japanese Patent Application Laid-Open No. Hei 1-210478 is intended to prevent coating stains caused by pinholes, and the characteristics of the ink for a ballpoint pen are completely disclosed. Absent. [0010] By the way, aluminum powder reacts with water to generate gas or to lose its metallic luster over time and become white. In order to prevent such a phenomenon, aluminum powder whose surface is treated with a fatty acid, inorganic phosphoric acid, or a salt thereof is usually used. However, as described above, the surface of the aluminum powder having a fatty acid, a fatty acid salt, an inorganic phosphoric acid, or an inorganic phosphate attached thereto is hydrophobic, and therefore, when the aluminum powder is used for an aqueous ink, the aluminum powder is used. A surfactant is required to disperse in water. However, surfactants conventionally used for the purpose of dispersing desorb fatty acids and inorganic phosphoric acids and / or salts thereof adsorbed on the aluminum powder, and as a result, the aluminum powder reacts,
Gas is generated, or the sense of brightness is lost over time. It is an object of the present invention to provide an aqueous metallic glossy ink for ballpoint pens, which is an ink using aluminum powder and in which deterioration of the ink is minimized even during long-term storage. [0012] According to an aspect of the invention, an aluminum powder, and 0.3 to 1.5% by weight of polysaccharide, and 3.0 to 8.0 wt% of polyvinyl pyrrolidone, water-soluble It is an object of the present invention to provide an aqueous metallic glossy ink for a ballpoint pen, which comprises at least an organic solvent and water. Hereinafter, the present invention will be described in detail. The aluminum powder used in the present invention is used as a coloring material that imparts a sense of brightness to handwriting. A scaly shape is particularly preferable because the sense of brightness appears more clearly. For aluminum powder, a stamping method in which aluminum pieces are crushed together with a lubricating agent such as stearic acid by a stamp mill, or an aluminum powder obtained by an injection method, a lubricating material, and an appropriate liquid are put into a drum together with a hard sphere, Is obtained by a ball mill method or the like in which aluminum pieces are crushed by rotating. Usually, it is available as an aluminum paste as a commercial product. The aluminum paste was crushed and polished in a ball mill containing a high-boiling petroleum solvent (mineral spirit) and a lubricating agent such as stearic acid to make very thin flaky aluminum particles. Since the scale-like aluminum fine particles are wet with a petroleum-based solvent, there is little danger of ignition and explosion, storage stability is good, and handling is easy in use. The amount of the aluminum powder used is preferably 1 to 30% by weight based on the total amount of the ink. If the amount used is less than 1% by weight, the handwriting has a low metallic luster and the amount used is 30%.
If the content exceeds% by weight, the solid content increases and the fluidity decreases, so that the ink ejection tends to deteriorate. The average particle size of the aluminum powder is 5 to 3
It is preferable to use one having a thickness of 0 μm. This is because if the average particle size is less than 5 μm, the metallic luster of the handwriting is reduced, and it is easy to produce unclear handwriting without a sense of brightness. This is because there is a tendency. Commercially available aluminum powders include AA12, no. 900, No. 18000 (all manufactured by Fukuda Metal Foil & Powder Co., Ltd.). As the aluminum paste, Super Fine No.
No. 22000WN, No. 18000WN (all manufactured by Daiwa Metal Powder Co., Ltd.), WB0230, WXM0630
(Both manufactured by Toyo Aluminum Co., Ltd.). The polysaccharide is used to prevent sedimentation of the aluminum powder and further coat the aluminum powder to suppress the reaction with water as much as possible. 1.5% by weight is required. If the amount is less than 0.3% by weight, the effect of preventing the aluminum powder from settling is insufficient. If the amount exceeds 1.5% by weight, the viscosity becomes unsuitable as a ballpoint pen ink. That's why. Examples of the polysaccharides include germ gum, locust bean gum of seed polysaccharide, xanthan gum, welan gum, and ramzan gum of microbial system, carrageenan, alginic acid of seaweed polysaccharide, tarragant gum of resin polysaccharide, and derivatives thereof. Polyvinylpyrrolidone is used to coat aluminum powder and suppress the reaction with water as much as possible. The amount of polyvinylpyrrolidone must be 3.0 to 8.0% by weight based on the total amount of the ink. If the amount used is less than 3.0% by weight, the effect of suppressing the reaction of aluminum powder with water is insufficient, and if it exceeds 8.0% by weight, it is unsuitable as a ballpoint pen ink. This is because of the viscosity. It is necessary to use the polysaccharide and polyvinylpyrrolidone together within the above-mentioned range. This is because the effect of suppressing the reaction of aluminum powder with water is insufficient when only polysaccharides are used, and an appropriate viscosity as an ink for a ballpoint pen cannot be obtained when only polyvinylpyrrolidone is used. The water-soluble organic solvent is used for various qualities as an ink, for example, to prevent the ink from freezing at a low temperature or to prevent the ink from drying at a pen tip when used for a writing instrument. . Specifically, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol 1, 3-butylene glycol, thiodiethylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, triglycol Ethanolamine or the like can be used alone or as a mixture. The amount used is preferably 5 to 40% by weight based on the total amount of the ink. Water is used as the main solvent. The aqueous metallic glossy ink for ballpoint pens according to the present invention basically comprises the above-mentioned components, but may further take various embodiments. For example, aluminum powder can be used in combination with a conventionally known water-soluble dye and / or pigment, such as an acidic dye, a basic dye, or a direct dye, as a coloring material in order to make the handwriting have a colored metallic luster. Acid dyes include C.I. I. Acid Yellow 2
3, C.I. I. Acid Red 52, C.I. I. Acid Blue 1 and the like, and examples of the basic dye include C.I. I.
Basic Blue 7, C.I. I. Basic Red 1 and the like, and examples of the direct dye include C.I. I. Direct Blue 86, C.I. I. Direct Green 6, C.I. I. Direct Orange 8 and the like. The amount of the dye used is preferably 5 to 20% by weight based on the total amount of the ink. As the pigment, C.I. I. 11660, 1167
0, 11680, 11730, 117735, 11740, 12710, 12720, 2004
0, 20220, 21135, 19140, 4
7005, 68420, C.I. I. 1205
5, 12075, 12125, 12305, 2
1165, C.I. I. 12480, 1207
1. Red pigment C.I. I. 12120, 12070, 12085, 12090, 12315, 1231
0, 12335, 12440, 12460, 1
2420, 12320, 12490, 1558
5, 15800 and 46500, purple C.I. I. 425
35, 60010, blue C.I. I. 74100, 7
4160, 74180, green C.I. I. 74260 and the like. These pigments are used by being dispersed in an aqueous medium. Commercially available water-dispersed pigments are preferably used because they increase the handleability and productivity. Specific examples of the water dispersion type pigment include EM YELLOW FG, EM
YELLOW FX-3024, EM SCARRET
2Y, EM PINK 2B, EM GREEN
G, EM BLUE 2G (Toyo Ink Co., Ltd.)
Manufactured). The amount of the pigment used is preferably 3 to 20% by weight, based on the total amount of the ink, as the solid content of the pigment. Also, various kinds of agents such as humectants such as urea, ethylene urea and thiourea, preservatives such as benzothiazoline and omazine, rust preventives such as benzotriazole, and surfactants as a dispersant for aluminum powder. Can be added as needed. In producing the aqueous metallic glossy ink for ballpoint pens of the present invention, various methods known in the art can be employed. For example, it can be easily obtained by mixing the above components and stirring and mixing with a stirrer such as a Henschel mixer, or by mixing and pulverizing with a disperser such as a ball mill. In order to prevent the reaction of the aluminum powder with water, the surface of the aluminum powder is treated with a substance such as stearic acid or inorganic phosphoric acid, such as an aluminum paste. However, substances such as stearic acid and inorganic phosphoric acid are easily adsorbed or bonded to the aluminum powder with a weak force, and thus are easily desorbed from the surface of the aluminum powder with time. As a result, the aluminum powder and water react with each other to generate hydrogen gas, and the quality of the ink deteriorates. It is speculated as follows that the ink according to the present invention, in which a polysaccharide and polyvinylpyrrolidone are used in combination, exhibits a viscosity suitable for a ball-point pen, and does not settle to aluminum powder even after long-term storage and does not further react with water. Is done. If the amount of the polysaccharide used is less than 0.3% by weight, sedimentation of the aluminum powder cannot be prevented, and if it exceeds 1.5% by weight, the viscosity properties as a ballpoint pen ink cannot be obtained. In addition, the discharge of ink from the pen tip of a conventionally used ball-point pen is poor, resulting in blurring. However, in order to sufficiently coat the aluminum powder and suppress the reaction with water, the polysaccharide is required to be 1.5% by weight or more based on the total amount of the ink. Therefore, the use of polyvinylpyrrolidone, which has the effect of suppressing the reaction of aluminum powder and has a low viscosity-increasing effect, in the range of 3.0 to 8.0% by weight, makes the ink according to the present invention suitable as a ballpoint pen ink. By suppressing the reaction of the aluminum powder while maintaining high viscosity physical properties, the aluminum powder does not settle and does not further react with water even during long-term storage. The present invention will be described below in more detail with reference to examples. Example 1 Aluminum paste (WXM0630, manufactured by Toyo Aluminum Co., Ltd., aluminum powder content: 60.0% by weight) 8.0 parts by weight Xansan gum 0.8 parts by weight Polyvinylpyrrolidone K-15 (General Aniline & Film Co., USA) 5.0 parts by weight Ethylene glycol 15.0 parts by weight Glycerin 10.0 parts by weight Water 61.0 parts by weight Preservative (Proxel GXL, manufactured by ICI Japan, 1,2-benzoisothiazolin-3-one) 0.2 parts by weight The above components were stirred and mixed with a Henschel mixer for 30 minutes to obtain a viscosity of 260 poise (E-type viscometer, 1 rpm, 25 ° C.)
Ink was obtained. When this ink is filled into a transparent ink container consisting of a polypropylene hollow shaft tube with a stainless steel ballpoint pen tip (ball material; cemented carbide) connected to one end, and written on the paper, a clear silver handwriting is obtained. Gave. Example 2 Aluminum paste (WXM0630, as described above) 5.0 parts by weight Welan gum 0.3 parts by weight Polyvinylpyrrolidone K-15 (as described above) 6.0 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 10.0 parts by weight Parts Water 60.5 parts by weight Water-dispersed pigment (EM YELLOW FX3024, manufactured by Toyo Ink Co., Ltd.) 8.0 parts by weight Preservative (Proxel GXL, as described above) 0.2 parts by weight Each of the above components was stirred for 1 hour using a stirrer. Viscosity 250 by mixing and stirring
An ink of poise (E type viscometer, 1 rpm, 25 ° C.) was obtained. This ink gave clear golden handwriting when written on paper in the same manner as in Example 1. Example 3 Aluminum paste (WB0230, manufactured by Toyo Aluminum Co., Ltd., aluminum powder content: 68.4% by weight) 10.0 parts by weight Ramzan gum 0.5 parts by weight Polyvinyl pyrrolidone K-15 (described above) 0 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 5.0 parts by weight Water 60.3 parts by weight Water-dispersed pigment (produced with the following composition) 10.0 parts by weight Preservatives (Proxel GXL, as described above) 0.2 parts by weight The above components were stirred and mixed with a laboratory mixer for 1 hour to obtain an ink having a viscosity of 250 poise (E-type viscometer, 1 rpm, 25 ° C.). This ink gave a clear metallic glossy blue handwriting when written on paper in the same manner as in Example 1. (Water-dispersed pigment) 30 parts of phthalocyanine blue, 20 parts of ethylene glycol, 45 parts of water, NP-10 (POE (1
0) Nonylphenyl ether, Nikko Chemicals Co., Ltd.
Is dispersed by a medium dispersing machine. Example 4 Aluminum paste (Superfine No. 22000WN, manufactured by Daiwa Metal Powder Co., Ltd., aluminum powder content: 70% by weight) 10.0 parts by weight Locust bean gum gum 0.8 parts by weight Polyvinyl pyrrolidone K- 15 (described above) 6.0 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 5.0 parts by weight Water 62.0 parts by weight C.I. I. Direct Green 6 5.0 parts by weight Joncryl J-775 (manufactured by Johnson Polymer Co., Ltd., emulsion of styrene acrylic copolymer) 1.0 part by weight Preservative (Proxel GXL, described above) 0.2 part by weight The components were stirred and mixed by a laboratory mixer for 1 hour to obtain an ink having a viscosity of 300 poise (E-type viscometer, 1 rpm, 25 ° C.). This ink gave green handwriting with a clear metallic luster when written on paper in the same manner as in Example 1. Comparative Example 1 The procedure of Example 1 was repeated, except that polyvinylpyrrolidone K-15 was changed from 5.0 parts by weight to 2.0 parts by weight and the amount of water was increased. An ink having a poise (E-type viscometer, 1.0 rpm, 25 ° C.) was obtained. When this ink was written on paper in the same manner as in Example 1, it gave clear silver handwriting. Comparative Example 2 The procedure of Example 1 was repeated, except that polyvinylpyrrolidone K-15 was changed from 5.0 parts by weight to 9.0 parts by weight, and the amount of water was reduced. An ink of poise (E type viscometer, 1 rpm, 25 ° C.) was obtained. When this ink was written on the paper in the same manner as in Example 1, the central part of the handwriting was thin, and the outside was dark, and a silver ink with marked line breaks was given. Comparative Example 3 An ink having a viscosity of 100 poise was obtained in the same manner as in Example 1 except that the amount of xanthan gum of Example 1 was changed from 0.8 parts by weight to 0.2 parts by weight and the amount of water was increased. . When this ink was written on paper in the same manner as in Example 1, silver ink was given. Comparative Example 4 The procedure of Example 1 was repeated, except that the amount of xanthan gum of Example 1 was changed from 0.8 parts by weight to 1.9 parts by weight, and the amount of water was reduced. The viscosity was 1120 poise (E-type viscometer). , 0.5 rp
m, 25 ° C.). When this ink was written on paper in the same manner as in Example 1, it gave a thin, silvery handwriting. As described above, tests were conducted on the aqueous metallic glossy inks for ballpoint pens obtained in Examples 1 to 4 and Comparative Examples 1 to 4. Table 1 shows the results. [Table 1] Writing test: Examples 1-4 and Comparatives 1-4
0.8 g of the ink obtained in (1) above is filled in a transparent ink container consisting of a polypropylene hollow shaft cylinder having a stainless steel ballpoint pen tip (ball material; cemented carbide) connected at one end, and a backflow preventer is provided on the upper portion thereof. After filling with 0.1 g, the bubbles were centrifugally degassed to prepare a ball-point pen for a writing test. Using this ballpoint pen, handwritten writing is performed on high-quality paper (JIS P3201 writing paper A), and writing is similarly performed after leaving for one month. Compared. In addition, leaving for one month,
The ballpoint pen for the writing test was allowed to stand in a constant temperature room at 50 ° C. with the pen tip facing upward. Observation of ink appearance: The state of the ink in the transparent ink storage tube was compared before and after standing for one month using the ballpoint pen for writing test. In Comparative Examples 1 and 3, the aluminum powder was settled and separated to form two layers, but no change was observed in the other ones before and after standing. As described in detail above, the aqueous metallic glossy ink for ballpoint pens according to the present invention is an excellent one that has almost no deterioration over time such as aluminum powder sedimentation and reaction with water. It is.

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Claims (1)

(57) [Claims 1] An aluminum powder and a polysaccharide of 0.3 to
1.5% by weight and polyvinylpyrrolidone from 3.0 to 8.0%.
An aqueous metallic glossy ink for a ballpoint pen, comprising at least 0 % by weight , a water-soluble organic solvent, and water.