JP6733150B2 - Water-based ink composition for ballpoint pens - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention is used in a so-called ball-point pen in which a tip having a ball and a ball holder rotatably wrapping the ball as a writing member for forming a handwriting is attached to an ink containing tube and ink is directly contained in the ink containing tube. A water-based ink composition for a ballpoint pen.

Conventionally, a chip equipped with a ball and a ball holder that rotatably holds the ball as a writing member that forms a handwriting is attached to an ink containing tube, and a dye or pigment as a coloring material, a high-boiling-point organic material for preventing nib drying. A direct-filling type water-based ballpoint pen in which ink containing a solvent is directly contained in an ink container is widely used. Further, in recent years, there has been an increasing number of occasions where handwriting is performed on the color side of various materials such as color copies and color printers, characters, etc., such as letter paper, notebooks, design prints, message cards, and the like. As the ball-point pen to be written on these color surfaces, a ball-point pen filled with the above-mentioned directly-packed water-based ball-point pen capable of designing a large amount of ink discharge with a water-based ink having a hiding property containing titanium oxide is used. Many. With a chip designed to increase the ink discharge amount, the ball moves in the ball holder, and air tends to be entrained from the gap created between the small edge of the ball holder and the ball. If the amount of air increases, there will be a space where the ink is cut off, and the air that has been ejected instead of ink will cause the handwriting to be blurred (air entrapment), and if air penetrates into the chip and the space where the ink runs out expands. In some cases, so-called backflow occurs, in which ink moves rearward in the ink containing tube or ink leaks from the rear end of the ink containing tube.
As an example of preventing the entrapment of air in such a direct-packing type water-based ballpoint pen, polyvinylpyrrolidone increases the viscosity of the ink, and xanthan gum imparts shear thinning viscosity to the ink to prevent leakage of the ink An ink for a water-based ball-point pen that is used by directly packing it in an ink cylinder equipped with a tip having a seat clearance in the range of 10.0 to 40.0 μm and a water-based ball-point pen that directly connects this ink are disclosed (Patent Document 1). ..
As an example in which a water-based ink containing titanium oxide is filled in a direct-packing type water-based ballpoint pen, a specific amount of titanium oxide and hollow resin particles having an average particle size of about 0.4 μm to 0.5 μm, an aqueous organic solvent, a shearing current decreasing viscosity An ink composition containing an imparting agent and a phosphoric acid ester-based activator, which does not cause visible blur or line skipping on black paper, and a knock-type water-based ballpoint pen using the same (Patent Document 2) An ink containing 15 to 25% by weight of titanium oxide and resin particles having an average particle size of about 0.4 to 0.5 μm and having a solid content adjusted to 30 to 55% by weight based on the total amount of the ink is clear on dark colored paper. A ballpoint pen capable of recording handwriting is disclosed (Patent Document 3).
One of the methods to increase the hiding power on dark colored paper is to use a water-soluble gel-like ink containing a metallic luster pigment such as aluminum powder pigment or titanium oxide pigment, which has a chip design that increases the ink discharge amount. Discloses a ball-point pen having a good writing feel without being scratched because the ball can move in the axial direction by 60 to 170 μm (Patent Document 4).

JP, 9-316383, A JP, 2009-185166, A JP, 2001-180177, A JP, 2001-088490, A

JP-A-2009-185166 and JP-A-2001-180177 disclose inks having a masking power containing titanium oxide and resin particles. However, these conventional inks containing titanium oxide and resin particles are titanium oxides. Due to this, the specific gravity of the ink becomes heavy, and since the tip is designed to increase the discharge amount, it is easy to entrap air even in normal writing, and the impact on the ink also becomes large, so not only does the pen fall Even with a slight impact such as hitting the back end of a ballpoint pen on a desk or attaching a cap to the back of a ballpoint pen, air is apt to be entrapped from the tip of the tip, scratches occur at the beginning of writing, and titanium oxide particles are hard particles. There are problems that the rotation of the ball is obstructed, the ball is easily slipped, and a stinging sound is generated from the pen tip during writing (referred to as squeaking).
In Japanese Unexamined Patent Publication No. 9-316383, air entrainment is prevented by controlling the fluctuation of the ink by a film of polyvinylpyrrolidone containing xanthan gum, but it is a general colorant ink. Ink containing titanium oxide to provide hiding power increases the specific gravity of the ink, so the impact on the ink when dropped with a pen also increases, and it is not sufficient to prevent air entrapment with the polyvinylpyrrolidone film, increasing the film strength. Therefore, when polyvinylpyrrolidone is added, there is a problem that ink is likely to be accumulated in the tip of the tip due to the adhesiveness, the handwriting is disturbed, and the viscosity is excessively increased to cause scraping.
In Japanese Patent Laid-Open No. 2001-088490, the movable range of the ball is set to be large in order to prevent scratches and smooth writing, so that air may be entrapped due to the impact when the pen is dropped, or the inside of the chip holder may be damaged. There was a problem such as a squeaking noise when writing due to the large movement of the ball.
The present invention is a water-based ballpoint pen equipped with an ink containing titanium oxide, has a good hiding property, there is no writing scratching due to a squeaking phenomenon or clogging at the time of writing, and of course, there is no entrapment of air by writing, It is an object of the present invention to provide an ink for a water-based ballpoint pen that allows smooth writing from the beginning even if there is an impact such as dropping the pen.

That is, the present invention comprises at least titanium oxide having an oil absorption of 29 g/100 g or more and 35 g/100 g or less, resin particles having an average particle size of 1.0 μm or more and 2.0 μm or less, a silicone activator, a polymeric polysaccharide, and water. A water-based ballpoint pen containing the resin particles and the titanium oxide having an oil absorption of 29 g/100 g or more and 35 g/100 g or less in the ratio of the average particle size of 1.0:0.50 to 1.0:0.16. An ink composition has a first gist, a second gist that the resin particles are resin particles of a styrene-acrylic copolymer, and an ink composition in which the resin particles are hollow resin particles is a third gist. Let's make a summary.

The mechanism by which the ink composition of the present invention has good ink outflow performance without clogging, high impact resistance performance, and noise suppression effect is not clear, but titanium oxide and an average particle size of 1.0 μm or more and 2.0 μm or less are used. The resin particles have a large volume of hydrophobic bonds and hydrogen bonds combined with the high molecular weight polysaccharide that forms an association structure in water, and form a loosely bonded aggregate that does not easily collapse even when impacted. It is thought that the high impact resistance performance is achieved by mitigating the movement of ink due to and preventing air from entering. With this aggregate alone, the aggregate may be caught in the arrow groove in the chip and the handwriting may be scratched, or the chip may be clogged and writing may not be possible, but the loose bond between the silicone activator and the high molecular polysaccharide is due to the polysiloxane structure Titanium oxide and average particle size of 1.0 μm or more because it is easier to separate from the surfactants, it deforms flexibly due to the deformation of the ink during writing, and the lubricity between the silicone surfactant and the metal part of the tip is excellent. It is presumed that resin particles of 2.0 μm or less can keep flowing well. In particular, hollow resin particles of a styrene-acrylic copolymer having an average particle size of 1.0 μm or more and 2.0 μm or less are not so deformed by writing because the styrene-acrylic copolymer contains voids inside the particles. Has a cushioning effect due to its moderate elasticity, interacts with a polymeric polysaccharide that forms an association structure and exhibits elasticity, and is highly effective in alleviating the impact when the ballpoint pen falls. In addition, an assembly that has both the lubricity of the silicone activator and the cushioning properties of the hollow resin particles of the styrene-acrylic copolymer stabilizes the position of the ball between the ball and the inner wall of the ball holder, and rotates the ball smoothly. It also works to prevent squeaking, smoothes the writing feel, and improves ink output. Further, it is considered that the aggregate in which the hollow resin particles, which are relatively large and have a hiding property as a main component, tend to remain on the surface of the paper as a coating film containing titanium oxide and have a high hiding property.

The invention will be described in detail below.
Titanium oxide is a white colorant that has a concealing property even on dark colored paper, and is used as an element of the composite assembly in the present invention. Specific examples thereof include SR-1 (oil absorption 19 to 21 g/100 g). , R-3L (oil absorption 21-24g/100g), R-5N (oil absorption 19-21g/100g), R-7E (oil absorption 27-31g/100g), R-24 (oil absorption 21-24g/ 100 g), R-61N (oil absorption amount 22 g/100 g), R-62N (oil absorption amount 19 to 21 g/100 g), R-310 (oil absorption amount 21 g/100 g), R-650 (oil absorption amount 20 to 22 g/100 g) , D-918 (oil absorption amount 20 to 24 g/100 g), FTR-700 (oil absorption amount 19 to 23 g/100 g), TCR-52 (oil absorption amount 16 to 19 g/100 g) (above, manufactured by Sakai Chemical Industry Co., Ltd.) , Taipaque R-550 (oil absorption 23g/100g), R-580 (oil absorption 19g/100g), R-630 (oil absorption 19g/100g), R-670 (oil absorption 22g/100g), the same R-680 (oil absorption 19g/100g), R-780 (oil absorption 33g/100g), R-780-2 (oil absorption 40g/100g), R-820 (oil absorption 24g/100g), the same R-830 (oil absorption 21g/100g), R-930 (oil absorption 19g/100g), R-980 (oil absorption 19g/100g), PR-690 (oil absorption 16g/100g), PF- 691 (oil absorption 15 g/100 g), PF-711 (oil absorption 19 g/100 g), PF-736 (oil absorption 15 g/100 g), PF-737 (oil absorption 16 g/100 g), PF-737 ( Oil absorption 21g/100g), PF-739 (oil absorption 14g/100g), PF-740 (oil absorption 16g/100g), PC-3 (oil absorption 16g/100g), S-305 (oil absorption) 23 g/100 g), CR-50 (oil absorption 18 g/100 g), CR-50-2 (oil absorption 17 g/100 g), CR-57 (oil absorption 17 g/100 g), CR-58 (oil absorption) 19g/100g), CR-58-2 (oil absorption 18g/100g), CR-Super70 (oil absorption 16g/100g), CR-80 (oil absorption 20g/100g), CR-85 (oil absorption) 30 g/100 g), CR-90 (oil absorption 21 g/100 g), CR-90-2 (oil absorption 20 g/100 g), CR-93 (oil absorption 20 g/100 g), C R-97 (oil absorption 19 g/100 g), A-100 (oil absorption 22 g/100 g), A-220 (oil absorption 22 g/100 g), (all manufactured by Ishihara Sangyo Co., Ltd.), Kronos KR-270 (Oil absorption 21g/100g), KR-310 (oil absorption 17-22g/100g), KR-380 (oil absorption 18-24g/100g), KR-380-N (oil absorption 18-24g/100g) , KR-480 (oil absorption 19-24g/100g), KA-10 (oil absorption 18-28g/100g), KA-15 (oil absorption 19-24g/100g), KA-20 (oil absorption) 18 to 23 g/100 g), the same KA-30 (oil absorption amount 18 to 23 g/100 g) (above, manufactured by Titanium Industry Co., Ltd.), TITANIX JR-300 (oil absorption amount 18 g/100 g), the same JR-301 (oil absorption amount). 18 g/100 g), the same JR-403 (oil absorption 19 g/100 g), the same JR-405 (oil absorption 15 g/100 g), the same JR-600A (oil absorption 19 g/100 g), the same JR603 (oil absorption 21 g/100 g). , Same JR-605 (oil absorption 19g/100g), same JR-600E (oil absorption 21g/100g), same JR-603 (oil absorption 21g/100g), same JR-800 (oil absorption 29g/100g), same JR-801 (oil absorption 40g/100g), JR-805 (oil absorption 22g/100g), JR-806 (oil absorption 21g/100g), JR-906 (oil absorption 22g/100g), JR- 701 (oil absorption 20g/100g), JRNC (oil absorption 21g/100g), JR (oil absorption 18g/100g), JA-1 (oil absorption 23g/100g), JA-C (oil absorption 23g/100g) 100 g), JA-3 (oil absorption amount 23 g/100 g) (above, manufactured by Teika Co., Ltd.), TA-100 (oil absorption amount 22 g/100 g), TA-200 (oil absorption amount 24 g/100 g), TA-300 ( Oil absorption 21g/100g), TA-400 (oil absorption 24g/100g), TR-600 (oil absorption 19g/100g), TR-700 (oil absorption 23g/100g), TR-840 (oil absorption 24g/100g) ), TR-900 (oil absorption 19 g/100 g) (above, manufactured by Fuji Titanium Industry Co., Ltd.), TYPURE R-700 (oil absorption 13 g/100 g), R-706 (oil absorption 13 g/100 g), R -900, R-901 (oil absorption 14g/100g), R-902 (oil absorption 16g/100g) (above, du Pon Japan Limited) and the like. In order to increase the dispersion efficiency of titanium oxide, a commercially available water-dispersion type titanium oxide is preferably used because it has improved handleability and productivity. Specific examples of the water-dispersed titanium oxide include Fuji SP White #143 (oil absorption 33 g, titanium oxide concentration 50% by weight), the same #552 (oil absorption 17 g/100 g, titanium oxide concentration 50% by weight) the same #553 ( The oil absorption amount is 14 g/100 g, the titanium oxide concentration is 50% by weight), the same #791 (oil absorption amount is 40 g/100 g, the titanium oxide concentration is 50% by weight) and the like. The amount used is preferably 1% by weight or more and 60% by weight or less with respect to the total amount of the ink composition, and more than 5% by weight and less than 40% by weight is more preferable. If the amount used is less than 5% by weight, the handwriting is too thin to be legible. If the amount is more than 40% by weight, the solid content increases and the blur of the handwriting with time tends to occur. Although the reason is not clear, titanium oxide having an oil absorption of 29 g/100 g or more and 35 g/100 g or less is particularly preferable. Titanium oxide having an oil absorption of 29 g/100 g or more and 35 g/100 g or less is a bulky titanium oxide and has many pores on the surface of titanium oxide, so that it promotes the formation of the aggregate of the present invention, prevents air entrapment, and makes noise. It is considered that the prevention effect is further enhanced. Here, the oil absorption means that 2 g of titanium oxide is placed on a glass plate, the oil is dripped little by little into a simmered linseed and mixed well with a metal spatula, and the mixture of the linseed oil and titanium oxide becomes putty-like, and the moldability is improved. It is the amount (grams) obtained by converting the amount of boiled linseed oil added until the product has 100 g of titanium oxide to 100 g.

Resin particles having an average particle size of 1.0 μm or more and 2.0 μm or less are used as an element of the composite aggregate in the present invention, and the material of the resin particles is polyethylene, polypropylene, vinyl chloride, polymethacrylate, benzoguanamine, nylon, Styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-acryl copolymer, silicone resin and the like can be mentioned, and examples of the shape include spherical shapes, crushed shapes, flat shapes, and donut-shaped irregular shapes. .. As the structure, there are a solid structure and a hollow structure. The solid structure means a state in which the resin particles are clogged, and the hollow structure is a resin particle having a small hole void therein. Specific examples of the solid resin particles include Eposter S12 (average particle size 1.5 μm, manufactured by Nippon Shokubai Co., Ltd.), FS-301 (average particle size 1.0 μm), MG-351 (average particle size 1.0 μm). ), BGK-001 (average particle size 1.0 μm), (above, manufactured by Nippon Paint Co., Ltd.), Tospearl 120 (average particle size 2.0 μm, manufactured by Momentive Performance Materials Japan LLC) SSX-101 ( Examples include SSX-102 (average particle size 1.0 μm) (average particle size 2.0 μm, manufactured by Sekisui Plastics Co., Ltd.) and the like. The hollow resin particles are resin particles in which small pores are formed inside the resin particles, and because of the voids, they have a property that they scatter light well and can impart hiding power, opacity, and whiteness. As a specific example thereof, commercially available hollow resin particles can be used, and SX8782 (D) (average particle diameter 1.0 μm, porosity 50%), SX8782 (A) (average particle diameter, 1.1 μm, voids) 55%), SX8782 (P) (average particle size 1.1 μm, porosity 55%), (above, manufactured by JSR Corporation), Rhopaque SN-1055 (average particle size 1.0 μm, porosity 55%, ROHM).・And Haas Japan Co., Ltd.) and the like. As a material for these resin particles, a styrene-acrylic copolymer having a moderate elasticity and a large cushioning property is preferable, and specifically, the above-mentioned FS-301, MG-351, SX8782(D)SX8782(A)SX8782( P) and Lowpaque SN-1055. By using the resin particles in combination with titanium oxide, which has a large oil absorption amount, a silicone activator, and a high molecular weight polysaccharide, an aggregate having a gradual bond composed of a hydrophobic bond and a hydrogen bond is formed, and the handwriting hiding property is improved. Well, when writing, there is no squeaking noise or writing scratches due to clogging, and even when you accidentally drop the pen, you can write smoothly from the beginning, and the hollow resin particles have voids inside, so the cushioning effect is high and shock is high. It has a great effect of relaxing. Hollow resin particles having a porosity of 50% or more are particularly preferable. Even if the average particle size is 1.0 μm or more and 2.0 μm or less, non-resin particles or resin particles having an average particle size of less than 1.0 μm cannot form a complex aggregate in the present invention and are sufficient. Since there is no cushioning property, when ink flows between the seat and the ball, the impact of the movement of the ball at the time of noise makes the writing feel bad, the particles are broken, and the particles and their fragments are clogged in the chip. Then I cannot write anymore. The average particle diameter of these resin particles is an average particle diameter based on volume distribution measured by SALD-7100, a nanoparticle diameter distribution measuring device manufactured by Shimadzu Corporation. These resin particles can be used alone or in combination of two or more, and the amount thereof is preferably 5.0% by weight or more and 25.0% by weight or less with respect to the total amount of the ink composition. The ratio of the average particle size of the resin particles to the titanium oxide is particularly preferably in the range of 1.0:0.50 to 1.0:0.16. By reducing the particle size of titanium oxide in the ink to less than half that of resin particles, the resin particles act as a spacer in the gap between the ball and the ball holder, and titanium oxide is directly sandwiched between the metals to rotate the ball. The possibility of hindering noise is further reduced, and the effect of preventing squeaking can be further enhanced.

The silicone activator is used for the purpose of exerting the effect of promoting the formation of the composite aggregate of the present invention, the ease of deformation by flow and the effect of lubrication. The silicone activator is not particularly limited, and dimethyl silicone, polyether modified silicone, methylphenyl silicone, alkyl modified silicone, higher fatty acid modified silicone, methylhydrogen silicone, fluorine modified silicone, epoxy modified silicone, carboxy modified silicone, carbinol. Examples include modified silicones and amino-modified silicones. The oil type FA-630, X-50-1039A, and KS-7708 (all manufactured by Shin-Etsu Chemical Co., Ltd.) YSA6403 (all manufactured by Momentive Performance Materiatin Japan K.K.) are preferably used as commercially available products. ), BYK-019, BYK-025 (all manufactured by Big Chemie Japan Co., Ltd.), and as a compound type, KS-66, KS-69, X-50-1105G (all manufactured by Shin-Etsu Chemical Co., Ltd.) TSA750. , TSA750S (above, manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-017, BYK094 (above, manufactured by Big Chemie Japan Co., Ltd.), and as self-emulsifying types, KS-508, KS-530, KS-531, KS-537. , KS-538, KS-540 (all manufactured by Shin-Etsu Chemical Co., Ltd.), YSA6406, TSA780 (all manufactured by Momentive Performance Materia Tins Japan GK), BYK1770 (all manufactured by Big Chemie Japan, Inc.), emulsion. As a mold, KM70, KM-71, KM-72, KM-72F, KM-72S, KM72GS, KM72FS, KM-73, KM-73A, KM-73E, KM-75, KM-85, KM-89, KM-90, KM-98, KM7750, KM-7952, (manufactured by Shin-Etsu Chemical Co., Ltd.), TSA7341, TSA730, TSA732, TSA732A, TSA737, TSA737F, TSA739, TSA770, TSA772, TSA775, YMA6509 (or more. Momentive Performance Materia tin Japan GK) BYK-023, YK-044, BYK-1615, BYK1650, (Made by Big Chemie Japan Co., Ltd.) and other mineral oil mixed types, BYK-035, BYK037. , BYK-038 or more, manufactured by Big Chemie Japan Co., Ltd., etc., and may be used alone or in combination of two or more kinds. The amount used is preferably 0.1% by weight or more and 5.0% by weight or less with respect to the total amount of the ink composition. Since the silicone activator has a low surface tension and has an action of penetrating into and expanding inside the pores, the ink binder containing the silicone activator contains hollow resin particles or an oil absorption amount of 29 g/100 g or more and 35 g/100 g or less of the titanium oxide surface. It is thought that it facilitates penetration and expansion into the pores and enhances the formation of aggregates. Among them, in the emulsion type and the mineral oil mixed type, the silicone-active lipophilic hydrophilic part is bonded to the lipophilic part of the resin particles and the hydrophilic part of the high molecular weight polysaccharide depending on the balance, but the aggregate is formed into a ball or a ball holder metal. It is easy to use as a lubricant between the surface and the ball, and the ball rotates smoothly and makes a squealing noise.

The high molecular polysaccharide is used for the purpose of enhancing the stability of the aggregate by maintaining the network structure. Specific examples of the high molecular weight polysaccharides include pullulan, xanthan gum, welan gum, gellan gum, rhamzan gum, starch, cationic starch, dextrin, sodium starch glycolate and the like and their derivatives, gum arabic, tragacanth gum, locust bean gum, guar gum and its derivatives. , Agar, carrageenan, alginic acid, alginate, pectin, gelatin, casein, sodium caseinate, glucomannan, dextran, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, sodium starch glycolate, lanolin derivative, chitosan derivative, etc. Can be mentioned. These high molecular polysaccharides may be used alone or in combination of two or more. Among these high molecular weight polysaccharides, xanthan gum can be preferably used. The xanthan gum aqueous solution has a high elasticity due to the interaction between titanium oxide and the resin particles, and has a high impact absorbing effect and a high noise suppressing effect. Specific examples of xanthan gum include Kelzan, Kelzan S, Kelzan F, Kelzan AR, Kelzan M, Kelzan D (above, Sansan Co., Ltd.), Kojin, Kojin F, Kojin T, Kojin K (above, Kojin Co., Ltd. Manufactured by Inagel V-7T, Inagel V-7, and Inagel V-7T. The amount used is preferably 0.1% by weight or more and 5.0% by weight or less with respect to the total amount of the ink composition.

Toning can also be performed by using various coloring agents in combination with the above composition. Water-soluble dyes and oil-soluble dyes can be used together as the toning colorant. As specific examples of the water-soluble dye, any of an acid dye, a direct dye, a basic dye and the like can be used. To give an example, Japanol Fast Black D Conc (CI Direct Black 17), Water Black 100L (19 same), Water Black L-200 (19 same), Direct Fast Black B (22 same), Direct Fast Black AB (32 same), Direct Deep Black EX (38 same), Direct Fast Black Conc (51 same), Kayaras Supra Ray VGN (71 same), Kayaras Direct Brilliant Yellow G (CI Direct Yellow 4) ), Direct Fast Yellow 5GL (same as 26), Aizen Primula Yellow GCLH (same as 44), Direct Fast Yellow R (same as 50), Aisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX (same) 4), Direct Fast Scarlet 4BS (23), Aizen Direct Rhodulin BH (31), Direct Scarlet B (37), Kayak Direct Scarlet 3B (39), Aizen Primula Pink 2BLH (75), Sumi Light Red F3B (80), Eysen Primula Red 4BH (81), Kayaras Sprarubin BL (83), Kayaras Light Red F5G (225), Kayaras Light Red F5B (226), Kayaras Light Rose FR (same 227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (same 15), Sumilite Spula Blue BRR Conc (same 71), Dibogen Turquoise Blue S (same 86) , Water blue #3 (86), kayala star turquoise blue GL (86), kayala sprue blue FF2GL (106), kayala splat turquoise blue FBL (199), acid blue black 10B (CI Acid Black 1), Nigrosine (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (26), Suminol Fast Black BR Conc (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conc (52), Sumilan Black WA (52), Ranil Black BG Extra Conc (107), Kayanol Milling Black TLB (109), Suminol Milling Black B (109), Kyanol Milling Black TLR ( 110), Aizen Opal Black New Conc (119), Water Black 187-L (154), and Kayak Acid Brilliant Flavin FF (C. I. Acid Yellow 7:1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Daiwa Tartrazine (23), Kayaactorazine (23) , Suminol Fast Yellow R (25 same), Diacid Light Yellow 2GP (29 same), Suminol Milling Yellow O (38 same), Suminol Milling Yellow MR (42 same), Water Yellow #6 (42 same), Kayanol Yellow NFG (49), Suminol Milling Yellow 3G (72), Suminol Fast Yellow G (61), Suminol Milling Yellow G (78), Kayanol Yellow N5G (110), Suminol Milling Yellow 4G 200% (same 141), Kayanol Milling Yellow NG (same 135), Kayanol Milling Yellow 5GW (same 127), Kayanol Milling Yellow 6GW (same 142), Sumitomo Fast Scarlet A (CI Acid Red 8) ), Kayak Silk Scarlet (9), Solar Rubin Extra (14), Daiwa New Coxin (18), Aizen Bonso RH (26), Daiwa Red No. 2 (27), Suminol Leveling Brilliant Red S3B (35 same), Kayasil Rubinol 3GS (37 same), Aizen Erythrosine (51 same), Kayaqua Acid Rhodamine FB (52 same), Suminol Leveling Rubinol 3GP (57 same), Diacide Alizarin Rubinol F3G 200% (Id. 82), Eisen Eosin GH (Id. 87), Water Pink #2 (Id. 92), Aizen Acid Phloxine PB (Id. 92), Rose Bengal (Id. 94), Kayanol Milling Scarlet FGW (Id. 111), Kayanol Milling Rubin 3BW (129), Suminoall Milling Brilliant Red 3BN Conc (131), Suminol Milling Brilliant Red BS (138), Eisen Opal Pink BH (186), Suminol Milling Brilliant Red B Conc (249) ), kayak acid brilliant red 3BL (the same 254), kayak acid brilliant brilliant red BL (the same 265), kayanol milling red GW (the same 276), Mitsui acid violet 6BN (CI acid violet 15), Mitsui acid Violet BN (17), Sumitomo Patent Pure Blue VX (CI Acid Blue 1), Water Blue #106 (same 1), Patent Blue AF (same 7), Water Blue #9 (same 9), Daiwa Blue No. 1 (same 9), Supranol Blue B (same 15), Orient Solve Blue OBC (22 same), Suminol Leveling Blue 4GL (23 same), Mitsui Nylon Fast Blue G (25 same), Kayacil Blue AGG (40 same), Kayacil Blue BR (41 same), Mitsui Alizarin Sapphirole SE (43 same) , Suminol Leveling Sky Blue R Extra Conc (62), Mitsui Nylon Fast Sky Blue B (78), Sumitomo Brilliant Indocyanine 6Bh/c (83), Sandlancyanin N-6B 350% (90), Water Blue #115 (90), Orient Solble Blue OBB (93), Sumitomo Brilliant Blue 5G (103), Kyanol Milling Ultra Sky SE (112), Kyanol Milling Cyanine 5R (113), Aizen Opal Blue 2GLH (158), Daiwa Guinea Green B (C. I. Acid green 3), acid brilliant milling green B (9), Daiwa Green #70 (16), Kyanol Cyanine Green G (25), Suminol Milling Green G (27) and other acid dyes, Aizen Kachi Ron Yellow 3GLH (CI Basic Yellow 11), Eisencatillon Brilliant Yellow 5GLH (13 same), Sumiacrylic Yellow E-3RD (15 same), Maxiron Yellow 2RL (19 same), Astrazone Yellow 7GLL (same) 21), Kayacryl Golden Yellow GL-ED (28 same), Astrazone Yellow 5GL (51 same), Aizen Catillon Orange GLH (CI Basic Orange 21), Aizen Catillon Brown 3GLH (30), Rhodamine 6GCP (CI Basic Red 1), Aizen Astrafloxin (12 same), Sumiacrylic Brilliant Red E-2B (15 same), Astrazone Red GTL (18 same), Aizen Catillon brilliant pink BGH (27 same) , Maxilon Red GRL (46), Aizen Methyl Violet (CI Basic Violet 1), Aizen Crystal Violet (3 Same), Aizen Rhodamine B (10 Same), Astrazone Blue G (CI Basic Blue) 1), Astrazone Blue BG (the same 3), Methylene Blue (the same 9), Maxilon Blue GRL (the same 41), Aizen Catillon Blue BRLH (the same 54), Aizen Diamond Green GH (CI Basic Green 1). , Eisen Malachite Green (the same 4), Bismarck Brown G (CI Basic Brown 1) and the like. Examples of oil-soluble dyes include rhodamine B base (CI.45170B, Taoka Dye Mfg. Co., Ltd.), solder red 3R (CI.21260, Chugai Kasei Co., Ltd.), methyl violet 2B base (CI). 42535B, United States, National Aniline Div.), Victoria Blue F4R (CI. 42563B), Nigrosine Base LK (CI. 50415) (above, BASF, Germany), Varifast Yellow #3104. (CI. 13900A), Varifast Yellow #3105 (CI. 18690A), Orient Spirit Black AB (CI. 50415), Varifast Black #3804 (CI. 12195), Varifast Yellow #. 1109, Bali First Orange #2210, Bali First Red #1320, Bali First Blue #1605, Bali First Violet #1701 (all manufactured by Orient Chemical Industries, Ltd.), Spiron Black GMH Special, Spiron Yellow C-2GH, Spiron Yellow C-GNH, Spiron Red C-GH, Spiron Red C-BH, Spiron Blue C-RH, Spiron Violet C-RH, S.I. P. T. Orange 6, S.I. P. T. Blue 111 (above, Hodogaya Chemical Co., Ltd. product) etc. are mentioned. .. Furthermore, C.I. I. Basic Blue 1, Same 7, Same 8, C.I. I. Basic Violet 1, 3, 3, C.I. I. A basic dye such as Basic Red 1 and C.I. I. A salt-forming dye with an acid dye selected from Acid Yellow 23, 36 and the like can also be used.

A pigment can be used in combination as a toning colorant. As the pigment, an azo pigment, a nitroso pigment, a nitro pigment, a basic dye pigment, an acid dye pigment, a vat dye pigment, a mordant dye pigment, and an organic pigment such as a natural dye pigment, ocher, Inorganic pigments such as barium yellow, ultramarine blue, navy blue, cadmium red, barium sulfate, titanium oxide, rouge, iron black and carbon black, metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, tin powder and brass powder, Examples include fluorescent pigments and mica-based pigments. Specific examples of organic pigments include aniline black (CI. 50440), cyanine black, naphthol yellow S (CI. 10316), Hansa yellow 10G (CI. 11710), Hansa yellow 5G (CI. 11660). ), Hansa Yellow 3G (C.I. 11670), Hansa Yellow G (C.I. 11680), Hansa Yellow GR (C.I. 11730), Hansa Yellow A (C.I. 11735), Hansa Yellow RN (C.I. 11740). ), Hansa Yellow R (C.I. 12710), Pigment Yellow L (C.I. 12720), Benzidine Yellow (C.I. 21090), Benzidine Yellow G (C.I. 21095), Benzidine Yellow GR (C.I. I.21100), Permanent Yellow NCG (C.I.20040), Balkan Fast Yellow 5G (C.I. 21220), Balkan Fast Yellow R (C.I. 21135), Tartrazine Lake (C.I. 19140). , Quinoline Yellow Lake (CI.47005), Anthragen Yellow 6GL (CI.60520), Permanent Yellow FGL, Permanent Yellow H10G, Permanent Yellow HR, Anthrapyrimidine Yellow (CI.68420), Sudan I ( C.I.12055), permanent orange (C.I.12075), resole fast orange (C.I.12125), permanent orange GTR (C.I.12305), Hansaello 3R (C.I.11725), vulcan. Fast Orange GG (CI 21165), Benzidine Orange G (CI 21110), Persian Orange (CI 15510), Indanthrene Brilliant Orange GK (CI 59305), Indanthrene Brilliant Orange RK (C.I. 59105), Indanthrene Brilliant Orange GR (C.I. 71105), Permanent Brown FG (C.I. 12480), Para Brown (C.I. 12071), Permanent Red 4R (C). .I. 12120), Para Red (C.I. 12070), Fire Red (C.I. 12085), Parachlor Orthoaniline Red (C.I. 12090), Resole Fast Scarlet, Brilliant Fast Scarlet (C.I. 12315), Brilliant Carmine BS, Permanent Red F2R (C.I. 12310), Permanent Red F4R( C. I. 12335), Permanent Red FRL (CI.12440), Permanent Red FRLL (CI.12460), Permanent Red F4RH (CI.12420), Fast Scarlet VD, Vulcan Fast Rubin B (CI.12320). ), Vulcan Fast Pink G (C.I. 12330), Light Fast Red Toner B (C.I. 12450), Light Fast Red Toner R (C.I. 12455), Permanent Carmine FB (C.I. 12490). , Pyrazolone Red (C.I. 12120), Resole Red (C.I. 15630), Lake Red C (C.I. 15585), Lake Red D (C.I. 15500), Anthocin B (C.I. 18030), Brilliant Scarlet G (CI.15800), Resol Rubin GK (CI.15825), Permanent Red F5R (CI.15865), Brilliant Carmine 6B (CI.15850), Pigment Scarlet 3B ( C.I. 16105), Bordeaux 5B (C.I. 12170), Toluidine Maroon (C.I. 12350), Permanent Bordeaux F2R (C.I. 12385), Helio Bordeaux BL (C.I. 14830), Bordeaux. 10B (CI.15880), Bon Maroon Light (CI.15825), Bon Maroon Medium (CI.15880), Eosin Lake (CI.45380), Rhodamine Lake B (CI.45170). ), Rhodamine Lake Y (CI.45160), Alizarin Lake (CI.58000), Thioindigo Red B (CI.73300), Thioindigo Maroon (CI.73385), Permanent Red FGR ( CI 12370), PV Carmine HR, Watching Red, Monolight Fast Red YS (CI 59300), Permanent Red BL, Fast Violet B, Methyl Violet Lake (CI 42535), Dioxazine Violet. , Alkali Blue Lake (CI 42750A, CI 42770A), Peacock Blue Lake (CI 42090), Peacock Blue Lake (CI 42025), Victoria Blue Lake (CI 44045) , Phthalocyanine Blue (C.I. 74160), Fast Sky Blue (C.I. 74180), Indanthrene Blue RS (C.I. 6) 9800), indanthrene blue BC (C. I. 69825), indigo (CI. 73000), pigment green B (CI. 10006), naphthol green B (CI. 10020), green gold (CI. 12775), acid green rake, malachite green. Among inorganic pigments such as lake (C.I. 42000) and phthalocyanine green, specific examples of carbon black include Mitsubishi carbon blacks #10B, #20B, #14, #25 and #30, #33, #40, #44, #45, #45L, #50, #55, #95, #260, #900, #1000, #2200B. , #2300, #2350, #2400B, #2650B, #2700, #4000B, CF9, MA8, MA11, MA77, MA100, MA220, MA230, MA600 and MCF88. (Above, manufactured by Mitsubishi Chemical Corporation), Monarch 120, Monarch 700, Monarch 800, Monarch 880, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Mogar L, Regal 99R, Regal 250R, Regal 300R, Regal 330R, Regal 400R, Regal 500 and Regal 660R (above, manufactured by Cabot Corporation, USA), Printex A, Printex G, Printex U, Printex V, Printex 55, Printex 140U, Printex 140V, Printex 35. , Printex 40, Printex 45, Printex Printex 85, Nine Pex 35, Special Black 4, Special Black 4A, Special Black 5, Special Black 6, Special Black 100, Special Black 250, Special Black 350, Special Black 550. , Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160 and Color Black S170 (above, Degussa Japan KK), Raven 5000 Ultra II, Raven 2500. Ultra, Raven 1250, Raven 760 Ultra (above, Colombian Carbon Japan Co., Ltd. product) etc. are mentioned.

Resin particles colored with a dye or the like can also be used together as a toning colorant. Specific examples of the resin particles colored with a dye or the like include SF-5012, SF-5013, SF-5014, SF-5015, SF-5017, SF-5027, SF-5037, SF-5018, SF-8012, SF. -8014, SF-8015, SF-8017, SF-8037, SF-8027 (above, Shinrohi Co., Ltd. make), Lumicol NKW-2101E, NKW-2102E, NKW-2103E, NKW-2104E, NKW-2105E, NKW-2106E, NKW-2107E, NKW-2108E, NKW-2117E, NKW-2127E, NKW-2137E, NKW-2167E, NKW-C2102E, NKW-C2103E, NKW-C2104E, NKW-. C2105E, NKW-C2108E, NKW-C2117E, NKW-C2147E, NKW-C2167E, NKW-6200E, NKW-6202E, NKW-6203E, NKW-6204E, NKW-6205E, NKW- 6207E, NKW-6253E, NKW-6258E, NKW-6277E (above, styrene-acrylonitrile copolymer, manufactured by Nippon Fluorescent Chemical Co., Ltd.) and the like.

A metal powder pigment can also be used together as a toning colorant. As a commercially available aluminum powder as a specific example of the metal powder pigment, Super Fine No. 22000, the same No. 18000, Fine No. 900, the same No. 800 (above, manufactured by Daiwa Metal Powder Co., Ltd.), AA12, AA8, No. 900, No. 18000 (or more, manufactured by Fukuda Metal Foil & Powder Co., Ltd.), aluminum powder 1000, 2700 (or more, manufactured by Nakatsuka Metal Foil & Powder Industry Co., Ltd.) and the like, as aluminum pastes, WB0230, WXM0630 (or more, Toyo Aluminum ( Ltd.), Super Fine No. 22000 WN, 18000 WN (above, manufactured by Daiwa Metal Powder Co., Ltd.), and the like, as colored aluminum, Friend Color F350 BL-W, GR-W, F100 BL-W, GR-W (above, Showa Denko ( Co., Ltd.) and the like. In particular, crushed fine pieces in which aluminum is coated with a colored resin layer are mentioned as those capable of multi-coloring and obtaining a very large glittering feeling, and commercially available ones include ERJ neo R- GOLD #35, ERJ neo B-GOLD #35, ERJ neo S-GOLD #35, ERJ neo R-GOLD #100, ERJ neo B-GOLD #100, ERJ neo S-GOLD #100, ERJ neo RED #100, Ergie neo blue #100, ergie neo green #100, ergie neo violet #100, ergie neo black #100, ergie neo copper #100, ergie neo pink #100, ergie neo yellow #100, ergie neo r-gold #150, Ergie neo B-GOLD #150, ergie neo S-GOLD #150, ergie neo RED #150, ergie neo BLUE #150, ergie neo GREEN #150, ergie neo VIOLET #150, ergie neo BLACK #150, ergie neo copper # 150, ergie neo PINK #150, ergie neo YELLOW #150, ergie neo R-GOLD #200, ergie neo B-GOLD #200, ergie neo S-GOLD #200, ergie neo RED #200, ergie neo BLUE #200, Ergie neo green #200, ergie neo VIOLET #200, ergie neo BLACK #200, ergie neo copper #200, ergie neo PINK #200, ergie neo YELLOW #200, ergie neo R-GOLD #325, ergie neo B-GOLD 325, ergie neo S-GOLD #325, ergie neo RED #325, ergie neo BLUE #325, ergie neo GREEN #325, ergie neo VIOLET #325, ergie neo BLA. CK #325, ergie neo copper #325, ergie neo PINK #325, ergie neo YELLOW #325, ergie neo R-GOLD #500, ergie neo B-GOLD #500, ergie neo S-GOLD #500 (above, Oike) Imaging Co., Ltd., and the like. Commercially available pearl pigments include Iriodin 205 Rutileplatinum Gold (titanium oxide coverage 43%, particle diameter 10 to 60 μm), 215 Rutile Red Pearl (47%, particle diameter 10 to 60 μm), and 219 Rutile Lilac Pearl ( 48%, particle size 10 to 60 μm), 225 (52%, particle size 10 to 60 μm), 235 (57%, particle size 10 to 60 μm) (above, manufactured by Merck Japan Ltd.), PEARL-GLAZE MB-100R (titanium oxide coating rate 52%, particle diameter 10-60 μm), MG-100R (57%, particle diameter 10-60 μm), MR-100R (47%, 10-60 μm), MV-100R (48%, particle size 10-60 μm), MRB-100R (47%, particle size 10-60 μm), MY-100R (43%, particle size 10-60 μm), MB -100RF (62%, particle size 5-30 μm), MG-100RF (65%, particle size 5-30 μm), MRB-100RF (56, particle size 10-30 μm), MY-100RF ( 57%, particle size 5-30 μm), ULTIMICA YB-100 (titanium oxide coverage 43%, particle size 5-30 μm), YD-100 (43%, particle size 10-60 μm), RB-100. (The same 47%, particle diameter 5 to 30 μm), the same RD-100 (the same 47%, particle diameter 10 to 60 μm), the same VB-100 (the same 48%, the same 5 to 30 μm), the same VD-100 (the same 48) %, particle diameter 10-60 μm), GB-100 (65%, 5-30 μm), GD-100 (65%, 10-60 μm) (all manufactured by Nihon Koken Kogyo Co., Ltd.), etc. Are listed.

When a pigment is used, a conventionally known surfactant or water-soluble polymer as a dispersion aid and a penetrating agent can be used. For example, salts such as styrene-acrylic acid copolymer, styrene-maleic acid copolymer, acrylic acid-acrylic acid ester copolymer, resins such as shellac and humic acid, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl. Surfactants such as ethers, polyoxyethylene alkyl ether phosphoric acid and salts thereof, polyoxyethylene/polyoxypropylene alkyl ethers, and polyoxyethylene sorbitan fatty acid esters can be used as necessary. In particular, as a dispersion aid and a penetrant that do not inhibit the gelation performance of the lipid peptide of the present invention, polymer dispersants SOLSPERSE 27000 and 54000 (above, manufactured by Nippon Lubrizol Co., Ltd.) and polyoxyalkylene groups are used. The polymeric dispersants of Marialim AKM-0531, AFB-0561, AFB-1521, AEM-3511, AAB-0851, AWS-0851, AKM-1511-60, HKM-50A, HKM. -150A, HFB-150A (above, NOF Corporation make) etc. are mentioned.

In order to increase the dispersion efficiency of the pigment, a commercially available water-dispersion type pigment or a polymer in which the pigment is finely dispersed in advance is preferably used because the handleability and the productivity are enhanced. Specific examples of the water-dispersion type pigments include Fuji SP Black 8031, 8119, 8167, 8276, 8381, 8406, Fuji SP Red 5096, 5111, 5193, 5220, Fuji SP Bordeaux 5500, and Fuji. SP Blue 6062, same 6133, same 6134, same 6401, Fuji SP Green 7051, Fuji SP Yellow 4060, same 4178, Fuji SP Violet 9011, FujiSP Pink R34, same SP 9527, Fuji SP JU R74UJUFUUJUU 5543, the same 5544 (above, manufactured by Fuji Dye Co., Ltd.), Emacol Black CN, Emacol Blue FBB, the same FB, the same KR, Emacol Green LXB, Emacol Violet BL, Emacol BrownEmcol BrownEmcol, Emacol RemErmCarmErmolErmCerneErmcolErmErmCerneEmcol , Emacol Yellow FD, same IRN, same 3601, same FGN, same GN, same GG, same F5G, same F7G, same 10GN, same 10G, Sandy Super Black K, same C, Sandye Super Gray
B, Sandy Super Brown SB, the same FRL, the same RR, Sandy Super Green L5G, the same GXB, Sandy Super Never B
lue HRL, the same GLL, the same HB, the same FBL-H, the same FBL-160, the same FBB, the Sandy Super Violet BL H/C, the same BL, the Sandy Super Bordeaux FR, the Sandy Super PunkB, the same FB-160, the Sandy Super PunkB, and the same. , Sandy superCarmmine FB, Sandy Super Red FFG, same RR, same BS, same 1315, Sandy Super Orange FL, same R, same BO, Sandy yellow 5G R, same GR, same 3R, same R, same R, same R, same R , The same FGN, the same GN, the same GRS, the same GSR-130, the same GSN-130, the same GSN, the same 10GN (above, Sanyo Pigment Co., Ltd.), Rio Fast Black.
Fx 8012, 8313, 8169, Rio Fast Red Fx 8209, 8172, Rio Fast Red S Fx 8315, 8316, Rio
Fast Blue Fx 8170, Rio Fast Blue Blue FX 8170, Rio Fast Blue S Fx 8312, Rio Fast Green S Fx 8314, EM green G, (the above, Toyo Ink Co., Ltd. 102, 103, 2), NKW-2, NKW-2, NKW-2, NKW-2. 2104, 2105, 2106, 2107, 2108, 2117, 2127, 2137, 2167, 2101P, 2102P, 2103P, 2104P, 2105P, 2106P, 2107P, 2108P. , 2117P, 2127P, 2137P, 2167P, NKW-3002, 3003, 3004, 3005, 3007, 3077, 3008, 3402, 3404, 3405, 3407, 3408. 3477, 3602, 3603, 3604, 3605, 3607, 3677, 3608, 3702, 3703, 3704, 3705, 3777, 3708, 6013, 6038, 6559. (These are manufactured by Nippon Fluorescence Co., Ltd.), Cosmocolor S1000F series (produced by Toyo Soda Co., Ltd.), Victoria Yellow G-11, G-20, Victoria Orange G-16, G-21, Victoria Red G-. 19, G-22, Victoria Pink G-17, G-23, Victoria Green G-18, G-24, Victoria Blue G-15, G-25 (all manufactured by Mikuni Pigment Co., Ltd.), Examples include Pollux series such as Pollux PC5T1020, Pollux black PC8T135, and Polook Thread IT1030 (all manufactured by Sumika Color Co., Ltd.). Examples of those in which a pigment is finely dispersed in a polymer compound are Microlith Yellow 3G. -K, the same Yellow 4G-K, the same Yellow 3R-K, the same Scarlet R-K, the same DPP Red BK, the same Magenta 5B-K, the same Violet B-K, the same Blue A3R-K, the same Blue 4G-. K, Green G-K, Black CK, White RK (a pigment finely dispersed in vinyl chloride/vinyl acetate copolymer resin, manufactured by Ciba Specialty Chemicals Co., Ltd.), IK yellow, IK red, IK blue, IK green, IK black (pigment finely dispersed in vinyl chloride/vinyl acetate resin, manufactured by Fuji Dye Co., Ltd.), Ichloris Yellow 2G-T, Yellow 3R-T, Brown 5R-T, Scarlet RT, Red BR-T, Blue GS-T, Green GT, Black CT (rosin ester) Pigments finely dispersed in resin, manufactured by Ciba Specialty Chemicals Co., Ltd., Microlith Yellow 4G-A, Yellow MX-A, Yellow 2R-A, Brown 5R-A, Scarlet RA, and Red. 2C-A, the same Red 3R-A, the same Magenta 2B-A, the same Violet B-A, the same Blue 4G-A, the same Green G-A, the same Black C-A, the same White R-A (fine in ethyl cellulose resin Dispersed pigment, Ciba Specialty Chemicals Co., Ltd., L1/S Yellow NIF, L1/8 Red F3RK-70, L1/8 Violet RN50, L1/8 Orange 501, L1/8 Brown 5R, L1/8 Black. MA100, NC790 white (pigment finely dispersed in nitrocellulose resin, manufactured by Taihei Chemical Co., Ltd.), Renol Yellow GG-HW, the same Yellow HR-HW, the same Orange RL-HW, the same Red FGR-HW, the same Red. HF2B-HW, Red F5RK-HW, Carmin FBB-HW, Violet RL-HW, Blue B2G-HW, Green GG-HW, Brown HFR-HW, Black R-HW, White T- HW (pigment finely dispersed in polyvinyl butyral resin, manufactured by Clariant Japan Co., Ltd.), Fuji AS Black 810, AS Red 575, AS Blue 650, AS Green 737, AS White 165 (polyvinyl butyral resin Examples thereof include dispersed pigments and Fuji Dye Co., Ltd. These colorants may be used alone or in combination of two or more, and the amount thereof is preferably 1% by weight or more and 25% by weight or less with respect to the total amount of the ink composition, and is preferably 5% by weight. % Or more and 15% by weight or less is more preferable.

The organic solvent is used for the purpose of preventing ink from drying with a pen tip and preventing ink from freezing at low temperatures. As specific examples, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, 3-methyl-3-methoxy. Alcohol solvents such as pentanol benzyl alcohol, β-phenylethyl alcohol, α-methylbenzyl alcohol, lauryl alcohol, tridecyl alcohol, isododecyl alcohol, isotridodecyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol , Polyethylene glycol, hexylene glycol, 1,3-butylene glycol, thiodiethylene glycol, glycerin, benzyl glycol, glycols such as benzyl diglycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether , Ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether , Glycol ethers such as diethylene glycol monophenyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether, propylene glycol methyl ether acetate, propylene glycol diacetate, 2-pyrrolidone , N-methyl-2-pyrrolidone and the like. These organic solvents may be used alone or as a mixture of two or more kinds, and the use amount thereof is preferably 5% by weight or more and 60% by weight or less with respect to the total amount of the ink.

In producing the water-based ink composition of the present invention, various conventionally known methods can be adopted. For example, it can be easily obtained by mixing and stirring with a stirrer such as a Henschel mixer having a high shearing force, a propeller stirrer, a homogenizer, a turbo mixer, a high-pressure homogenizer. Further, in these preparation steps, the heat of dispersion generated can be used as it is for stirring, or can be stirred while applying heat. Furthermore, heat can be applied after ink preparation.

For the structure of the tip, a conventional general-purpose mechanism is effective. For example, a tip or a metal material in which a ball is held by a ball holding portion in which the vicinity of the tip of a metal pipe is pressed and deformed inward from the outer surface. It is possible to apply a chip in which the ball is held in the ball holding portion by cutting with a drill or the like and the ball holding portion holds the ball, or the ball is biased forward by a spring body. Further, as the balls, those having a diameter of about 0.2 to 2.0 mm, such as cemented carbide, stainless steel, ruby, ceramics, resin and rubber, can be applied. A ball made of a silicon carbide material is particularly preferable because a particularly stable ink discharge can be obtained. The amount of movement of the ball in the front-rear direction is increased as a dimension that greatly affects the clearance between the ball and the ball holder, but in general, it is preferably about 4 to 15% of the ball diameter, and preferably set between 8 μm and 300 μm. In particular, for the ink for a water-based ballpoint pen of the present invention, the optimum balance between the ball diameter and the amount of vertical movement of the ball is 78 μm to 100 μm for a 0.8 mm diameter ball, 96 μm to 118 μm for a 1.0 mm diameter ball, and It is preferable to set 110 μm to 132 μm for a 1.2 mm ball and 121 μm to 143 μm for a 1.4 mm diameter ball.

The ink containing tube may be made of metal or synthetic resin. If it is made of transparent/translucent synthetic resin, the remaining ink amount can be clearly indicated. For example, there are polyethylene, polypropylene, polyurethane, polyethylene terephthalate, polyamide, polyacrylonitrile-based resin, polyarylate, ethylene-vinyl alcohol copolymer, fluororesin, and the like, and polypropylene can be favorably used in terms of price and visibility. Further, it is also possible to use an ink containing tube in which a dye, a pigment, a coloring material having a polarization property, or the like is kneaded. An inner diameter of 1.5 mm to 20.0 mm can be used. A backflow preventing composition may be filled in the rear end of the ink for the purpose of preventing the ink from drying and preventing the backflow. As the ink backflow preventer, various known materials such as a highly viscous non-volatile liquid, a non-volatile liquid gelled, and a sponge-like one can be used, and a float may be used together.

The ball-point pen using the ink containing tube can be applied in any of a cap type and a retractable type. As the retractable ballpoint pen, a ballpoint pen refill is housed in the barrel, and the barrel can be configured to allow the tip to be retracted from the tip hole, and it can be used, and it is a composite type that houses multiple ballpoint refills in the outer shaft. It may be a retractable writing instrument. Further, it may be a ball-point pen that assists ejection of the ink composition at the time of writing by the pressure of compressed gas or the like.

Hereinafter, the present invention will be described in detail with reference to Examples.

(Example 1)
Fuji SP White #143 (dispersion of titanium oxide, oil absorption 33 g/100 g,
(Average particle size 0.4 μm, titanium oxide 50% by weight, manufactured by Fuji Dye Co., Ltd.)
23.00 parts by weight Ropaque SN-1055 (dispersion of hollow resin particles [styrene-acrylic copolymer], average particle size 1.0 μm, solid content 26.5% by weight, manufactured by Rohm and Haas Japan Co., Ltd. ) 40.00 parts by weight Kerzan AR (xanthan gum, manufactured by Sansho Co., Ltd.) 0.50 parts by weight ion-exchanged water 18.90 parts by weight ethylene glycol 12.00 parts by weight Sun Ivac Sodium Omazine (antifungal agent, Sanai) Petroleum Co., Ltd.) 0.30 parts by weight BYK035 (silicone activator, manufactured by Big Chem Japan Co., Ltd.) 0.30 parts by weight JONCRYL 61J (acrylic resin solution, solid content 30.5% by weight, manufactured by BASF Japan Co., Ltd.) 5.00 parts by weight Of the above components, Kerzan AR and 9.50 parts by weight of ion-exchanged water are stirred for 1 hour to prepare a Kerzan AR aqueous solution, and then Fuji SP White #143 and Lowpaque S.
N-1055, ethylene glycol, San Ivac sodium omazine, and BYK-035
And JONCRYL 61J and the rest of ion-exchanged water were added, and the mixture was stirred with a homodisper for 1 hour to obtain a white aqueous ballpoint pen ink composition.

(Example 2)
Fuji SP White #143 (same as above) 23.00 parts by weight SX8782 (P) (hollow resin particles [styrene-acrylic copolymer], average particle size 1.1
μm, powder, manufactured by JSR Stock Association) 15.00 parts by weight Kerzan AR (xanthan gum, manufactured by Sansho Co., Ltd.) 0.50 parts by weight ion-exchanged water 47.90 parts by weight ethylene glycol 12.00 parts by weight Zium omazine (same as above) 0.30 parts by weight BYK035 (same as above) 0.30 parts by weight JONCRYL 61J (same as above) 9.00 parts by weight Among the above components, SX8782 (P), JONCRYL 61J and ion exchanged water 30.00 parts by weight Parts were mixed and stirred with a homodisper for 30 minutes to prepare a dispersion of hollow resin particles. In parallel, Kerzan AR and 9.50 parts by weight of ion-exchanged water were stirred for 1 hour to prepare a Kerzan AR aqueous solution. The dispersion of SX8782(P), Fuji SP #143, the Kerzan AR aqueous solution and the remaining components were prepared. Was added and the mixture was stirred with a homodisper for 1 hour to obtain a white aqueous ink composition for a ballpoint pen.

(Example 3)
TITANIX JR-800 (titanium oxide, oil absorption 29 g/100 g, manufactured by Titanium Industry Co., Ltd.) 11.00 parts by weight Rhopaque SN-1055 (same as above) 34.00 parts by weight Kerzan AR (same as above) 0.50 parts by weight ion-exchanged water 32.80 parts by weight Ethylene glycol 12.00 parts by weight San Ivac Sodium Omazine (same as above) 0.30 parts by weight TSA739 (silicone activator, manufactured by Momentive Performance Materiatin Japan LLC) 0.40 parts by weight JONCRYL 61J (Same as above) 9.00 parts by weight Of the above components, TITANIX JR-800, JONCRYL 61J, ethylene glycol, and 10.00 parts by weight of ion-exchanged water were mixed and stirred, and dispersed by a bead mill for 1 hour to prepare a titanium oxide dispersion. (Average particle size 0.35 μm). In parallel, Kerzan AR and 9.50 parts by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kerzan AR aqueous solution. The dispersion of titanium oxide, Rhopaque SN-1055, Kerzan AR aqueous solution and the remaining components were added and stirred with a homodisper for 1 hour to obtain a white aqueous ballpoint pen ink composition.

(Example 4)
Fuji SP White #143 (same as above) 23.00 parts by weight MG-351 (actual resin particles [styrene-acrylic copolymer, average particle diameter 1.0 μm,
Powder, manufactured by Nippon Paint Co., Ltd. 10.60 parts by weight Kelzan AR (xanthan gum, manufactured by Sansho Co., Ltd.) 0.50 parts by weight ion-exchanged water 44.20 parts by weight ethylene glycol 12.00 parts by weight Sun Ivacsodium Omazine (same as above) 0.30 parts by weight TSA739 (same as above) 0.40 parts by weight JONCRYL 61J (same as above) 9.00 parts by weight Among the above components, MG-351, JONCRYL 61J and ion-exchanged water 30.00 parts by weight are added. Mix and stir for 30 minutes with a homodisper to create a dispersion of MG-351. In parallel, Kelzan AR and 9.50 parts by weight of ion-exchanged water were stirred for 1 hour to prepare a Kerzan AR aqueous solution, and the dispersion of MG-351, Fuji SP #143, the Kerzan AR aqueous solution, and the remaining components were mixed. In addition, the mixture was stirred with a homodisper for 1 hour to obtain a white aqueous ballpoint pen ink composition.

(Example 5)
Fuji SP White #143 (same as above) 23.00 parts by weight Eposter S12 (actual dense resin particles [melamine-formaldehyde condensate, average particle size 1.5 μm, powder, manufactured by Nippon Shokubai Co., Ltd.) 10.60 parts by weight Kelzan AR (Xanthan gum, manufactured by Sansho Co., Ltd.) 0.50 parts by weight ion-exchanged water 45.30 parts by weight ethylene glycol 12.00 parts by weight Sanai Vac Sodium Omazine (same as above) 0.30 parts by weight BYK035 (same as above) 30 parts by weight JONCRYL 61J (same as above) 8.00 parts by weight Of the above components, Eposter S12, JONCRYL 61J and 30.00 parts by weight of deionized water are mixed and stirred for 30 minutes with a homodisper to obtain a dispersion of solid resin particles. Created. In parallel, Kerzan AR and 9.50 parts by weight of ion-exchanged water were stirred for 1 hour to prepare a Kerzan AR aqueous solution, and the dispersion of Eposter S12, Fuji SP #143, the Kerzan AR aqueous solution and the remaining components were added. Then, the mixture was stirred with a homodisper for 1 hour to obtain a white aqueous ballpoint pen ink composition.

(Example 6)
Fuji SP White #143 (same as above) 23.00 parts by weight Rhopaque SN-1055 (same as above) 40.00 parts by weight Kerzan AR (same as above) 0.50 parts by weight deionized water 18.90 parts by weight ethylene glycol 12.00 parts by weight Sun Ibac Sodium Omagine (same as above) 0.30 parts by weight YSA6403 (Silicone activator, Momentive Performance Materia Tin
Japan GK) 0.30 parts by weight JONCRYL 61J (same as above) 5.00 parts by weight Among the above components, Kerzan AR and 9.50 parts by weight of ion-exchanged water are stirred for 1 hour to prepare a Kerzan AR aqueous solution. , Fuji SP White #143, Rhopaque SN-1055, ethylene glycol, San Ivac sodium omazine, YSA6403, JONCRYL 61J, and the rest of ion-exchanged water are added, and the mixture is stirred with a homodisper for 1 hour, for a white aqueous ballpoint pen. An ink composition was obtained.

(Example 7)
TITANIX JR-800 (same as above) 11.00 parts by weight Eposter S12 (same as above) 10.60 parts by weight Kerzan AR (same as above) 0.50 parts by weight ion-exchanged water 54.20 parts by weight ethylene glycol 12.00 parts by weight Zium omazine (same as above) 0.30 parts by weight YSA6403 (same as above) 0.40 parts by weight JONCRYL 61J (same as above) 11.00 parts by weight Among the above components, 7.00 parts by weight of TITANIX JR-800 and JONCRYL 61J and ethylene. Glycol and 10.00 parts by weight of ion-exchanged water were mixed and stirred, and dispersed by a bead mill for 1 hour to prepare a dispersion of titanium oxide (average particle diameter 0.35 μm). Next, 4.00 parts by weight of Eposter S12 and JONCRYL 61J and 30.00 parts by weight of deionized water were mixed and stirred with a homodisper for 30 minutes to prepare a dispersion of Eposter S12. In parallel, Kerzan AR and 9.50 parts by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kerzan AR aqueous solution. The titanium oxide dispersion, the eposter s12 dispersion, the Kerzan AR aqueous solution and the remaining components were added and stirred with a homodisper for 1 hour to obtain a white aqueous ink composition for a ballpoint pen.

(Example 8)
Fuji SP White #143 (same as above) 23.00 parts by weight Rhopaque SN-1055 (same as above) 26.40 parts by weight Kerzan AR (xanthan gum, manufactured by Sansho Co., Ltd.) 0.50 parts by weight ion-exchanged water 20.50 parts by weight Ethylene glycol 12.00 parts by weight Sun-Ivac Sodium Omazine (same as above) 0.30 parts by weight BYK035 (same as above) 0.30 parts by weight JONCRYL 61J (same as above) 5.00 parts by weight Lumicol NKW-C2102E (green colored resin particles) Dispersion, manufactured by Nippon Fluorescent Co., Ltd.)
8.00 parts by weight Of the above components, Kelzan AR and 9.50 parts by weight of ion-exchanged water are stirred for 1 hour to prepare an aqueous solution of Kelzan AR, and then Fuji SP White #143, Lopaque SN-1055, and Lumicol NKW-. C2102E, ethylene glycol, San Ivac sodium omazine, BYK-035, JONCRYL 61J and the rest of the ion-exchanged water were added, and the mixture was stirred with a homodisper for 1 hour to obtain a green aqueous ballpoint pen ink composition.

(Comparative Example 1)
In place of Rhopaque SN-1055 in Example 1, Matsumoto Microspheres MHB-R (hollow resin particles [methyl methacrylate crosspolymer], average particle diameter 10.0 μm, manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) was used 10.6. Parts by weight, JONCRYL 61J at 8.0 parts by weight and ion-exchanged water at 30 parts by weight are mixed and stirred with a homodisper for 30 minutes to prepare a dispersion of Matsumoto Microspheres MHB-R. Subsequently, Kerzan AR and 9.50 parts by weight of ion-exchanged water were stirred for 1 hour to prepare a Kerzan AR aqueous solution. A dispersion of Fuji SP White #143, Matsumoto Microspheres MHB-R and the remaining components were added, and the mixture was stirred with a homodisper for 1 hour to obtain a white aqueous ink composition for a ballpoint pen.

(Comparative example 2)
In place of Rhopaque SN-1055 in Example 1, Rhopaque OP-84J (hollow resin particles [styrene-acrylic copolymer, average particle diameter 0.55 μm, manufactured by Rohm and Haas Japan Co., Ltd.] was used. A white aqueous ballpoint pen ink was obtained in the same manner as in Example 1 except that 9 parts by weight was used.

(Comparative example 3)
Example 5 was repeated in the same manner as in Example 5 except that the eposter MA1004 (actual dense resin particles [polymethylmethacrylate crosslinked product], average particle size 4.5 μm, Nippon Shokubai Co., Ltd.) was used instead of the eposter S12. A white aqueous ballpoint pen ink was obtained.

(Comparative Example 4)
In Example 5, 20.8 parts by weight of Lumicor NKW2109 (solid resin particles [styrene-acrylonitrile copolymer], average particle size 0.4 μm, Nippon Fluorescent Co., Ltd.) was used instead of Eposter S12, and Kelzan AR and ion exchange were used. 9.50 parts by weight of water was stirred for 1 hour to prepare a Kelzan AR aqueous solution, and then Fuji SP White #143, ethylene glycol, San Ivac sodium omazine, BYK-035, JONCRYL 61J, and the remaining ion-exchanged water were added. The mixture was added and stirred with a homodisper for 1 hour to obtain a white aqueous ballpoint pen ink composition.

(Comparative example 5)
A white water-based ballpoint pen ink was obtained in the same manner as in Example 5 except that Sirenax (silica balloon, average particle size 1.5 μm, manufactured by Nittetsu Mining Co., Ltd.) was used instead of the eposter S12.

(Comparative example 6)
A white water-based ballpoint pen ink was obtained in the same manner as in Example 2 except that ion-exchanged water was used instead of BYK035.

(Comparative Example 7)
In Example 8, the use of Fuji SP White #143 was stopped, 21.6 parts by weight of Eposter S12, 11.6 parts by weight of JONCRYL 61J and 30.0 parts by weight of deionized water were mixed, and the mixture was mixed with a homodisper. Stir for 30 minutes to create a dispersion of solid resin particles. In parallel, Kelzan AR and 9.50 parts by weight of ion-exchanged water were stirred for 1 hour to prepare a Kelzan AR aqueous solution, and Lumicol-NKW2102E (green colored resin particle dispersion, manufactured by Nippon Fluorescent Co., Ltd.) was used. Parts by weight and the remaining components were added, and the mixture was stirred with a homodisper for 1 hour in the same manner as in Example 5 to obtain a green aqueous ballpoint pen ink composition.

(Test sample ballpoint pen)
The aqueous ink compositions for ball-point pens obtained in Examples 1 to 8 and Comparative Examples 1 to 7 were filled with KF8 refill (stainless ball-point pen tip, ball material: cemented carbide, ball diameter: 0.8 mm, ball) manufactured by Pentel Co., Ltd. Transfer amount: 90 μm, polypropylene ink container, backflow preventer composition) was filled in an amount of about 0.6 g, and the backflow preventer composition in which α-olefin was gelled at the ink interface was arranged in a layer, and then the pen tip was A test ballpoint pen was prepared by centrifuging and defoaming so as to face the outside.

(Air entrainment test)
After writing a straight line with a length of 10 cm on black fine paper (thick mouth, YCP, 3-4-23, manufactured by Yamasakura Co., Ltd.), drop the pen on the cedar board from 1 cm above and impact it with the pen tip facing upward. Add. After that, a straight line having a length of 10 cm was again written to confirm whether the handwriting was continuous. When it was continuous, the height from the cedar board was increased by 1 cm and the same test was performed, and the test was continuously performed until the handwriting became discontinuous. The higher the height until the discontinuous handwriting is generated, the less the air is entrained in the ink.

(Sound test)
Prepare the same black fine paper as above. Put the pen upright at an angle of 90 degrees with respect to the paper, and write a circle of about 3 cm five times repeatedly so that the position of the ball changes in the ball holder, and there are several places where it makes a clicking noise. To count.

(Written test)
Using a self-rotating continuous writing tester (spiral machine, manufactured by Seiki Kogyo Laboratories), continuous writing was performed at a writing speed of 7 cm/sec, a load of 100 g, and an angle of 70° to measure the writing distance at which a handwriting density difference and a blur occurred.

(Hiding test)
Prepare the same black fine paper as above. With the same pen, write vertically and horizontally in an area of width 15 mm and length 50 mm. After drying, the surface concealed with the ink was measured for Y values at 5 points with a colorimeter (Spectrophotometer SE6000, manufactured by Nippon Denshoku Co., Ltd.) to obtain an average. The larger the value, the whiter the opacity is.

As shown in Table 1, the aqueous ink compositions for ball-point pens of Examples 1 to 8 contained titanium oxide, resin particles having an average particle size of 1.0 μm or more and 2.0 μm or less, a silicone activator, a high molecular polysaccharide and water. As a result, a loosely-bonded aggregate is formed in the ink, air due to impact enters, and there is no squeaking during writing, and there is no scratching or clogging in writing. In addition, titanium oxide remains well on the paper surface in the handwriting, and the ink followability is good, so the surface to be coated is uniform and the hiding property is high. The effects of preventing entrapment of air and noise in Examples 1, 2, 3, 6, 8 in which hollow resin particles of styrene-acrylic copolymer are used are particularly good.

On the other hand, in Comparative Examples 1 and 3, the resin particles were too large and ink clogging and ejection instability occurred. When the ball rotates with no ink, noise is generated, air is entrapped, the filled surface in writing is disturbed, and many uneven surfaces cannot be hidden. In Comparative Examples 2 and 4, the size and stability of the aggregate are not sufficient because the resin particles are too small, and therefore the effect of preventing contact between metals and the effect of mitigating impact are small, and the permeability to the paper surface is also large. Sounds and air entrapment occur, and the filled surface in writing cannot be hidden.
Since Silinax of Comparative Example 5 is a silica balloon, it is hard, has no cushioning property, and is transparent. Therefore, the aggregate formation is insufficient, there is no cushioning property, and the hiding property is also small, so it will be destroyed by the impact of squealing noise, so that air entrapment occurs and the filled surface for writing can also be hidden. No, the broken silica becomes clogged and writing becomes impossible. Since Comparative Example 6 does not contain a silicone activator, it produces noise and air entrapment, and has a small filled surface and hiding power in writing. In Comparative Example 7, since titanium oxide was not used, the aggregate formation was insufficient, the hiding property was small, noise was produced, air was entrained, and the hiding property on the painted surface was not possible.
As described above in detail, the oil-based ink for a ball-point pen of the present invention has a good concealing property, there is no squeaking noise or a writing scratch due to clogging during writing, and even when the pen is accidentally dropped, it is smooth from the beginning. It is a water-based ink composition for ballpoint pens that can be written on.

Claims (3)

At least, the oil absorption is contained and water 29 g / 100 g or more 35 g / 100 g or less of titanium oxide with an average particle diameter of 1.0μm or more 2.0μm or less of the resin particles and silicone active agent and a polymer polysaccharide, the resin particles And an average particle size ratio of titanium oxide having an oil absorption of 29 g/100 g or more and 35 g/100 g or less is in the range of 1.0:0.50 to 1.0:0.16 . The water-based ink composition for a ballpoint pen according to claim 1, wherein the resin particles are a styrene-acrylic copolymer. The water-based ink composition for a ballpoint pen according to claim 1 or 2, wherein the resin particles are hollow resin particles.