JP2017155130A - Ink composition for ball point pen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition for ball point pen easily sensing that it can be written lighter and smoother than initial velocity during a process that writing velocity reaches fastest value from the initial velocity and is reduced.SOLUTION: There is provided an ink composition containing a coloring agent and a liquid medium and having a slope of a linear binding a point where a lower limit of friction coefficient at a relative speed in a range of 0.001 m/sec to 1.0 m/sec of friction coefficient at the relative speed of 0.001 m/sec or less and exhibiting friction coefficient at speed by adding 0.4 m/sec to the relative speed from the relative speed representing friction coefficient of the lower limit and a point representing the lower limit of 6.0 or less, by measuring friction coefficient with a measure at least consisting of at least one strike plate 2b in a recess 2a of a pot 2 accommodating the ink composition 3 and a rotor 1 having a ball 1b which is rotatable while contacting the strike plate at a tip.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an ink composition for ballpoint pens that can easily sense a process that allows smooth writing.

  Conventionally, in order to obtain an ink composition for a ballpoint pen with a smooth writing taste, ink compositions having a low viscosity or a specific shear thinning viscosity have been known. Measurement of writing resistance values under specific writing conditions and sensory evaluation based on the writing feeling of the examiner were performed.

  Japanese Patent Application Laid-Open No. 6-256699 (Patent Document 1) discloses a ballpoint pen filled with an aqueous ballpoint pen ink composition using inorganic fine particles as a shear thinning agent, and was selected at random as an evaluation of writing feeling. 50 people are asked to write, and a questionnaire survey is performed to obtain answers in four stages of “good, slightly smooth, normal, bad”, and the result of counting the number of people is described.

Patent No. 2996607 of Patent Document 2 contains a specific amount of a non-Newtonian viscosity imparting agent and a spinnability-imparting resin that imparts a spinnability with a string length of 100 mm or more at 20 ° C. A ballpoint pen filled with oil-based ballpoint pen ink having an index of 0.2 to 0.95 and a viscosity at a shear rate of 500 s ⁻¹ of 1,000 to 10,000 mPa · s (20 ° C.) is disclosed. As a taste, it is shown that the comparison made by the one-pair comparison method with the comparative sample has a superior difference in being smooth and good.

JP-A-8-311388 of Patent Document 3 contains a colorant, a solvent, a non-Newtonian viscosity imparting agent, has a non-Newtonian viscosity index of 0.2 to 0.95, and a viscosity at a shear rate of 500 s ⁻¹ is 1. The results of giving superiority to the smoothness of writing quality by using an oil-based ballpoint pen ink of 10000 to 10,000 mPa · s (20 ° C.) are described.

  In each of the above-mentioned patent documents, it is described that the non-Newtonian viscosity index and viscosity of the ink composition are in a specific numerical range as if there is a correlation with obtaining a smooth writing taste. In addition, each of the ink composition physical property measuring devices (Patent Document 1; EMD viscometer, Patent Documents 2 and 3; CSL rheometer manufactured by Camelli (UK)) is an ink that is a specimen sandwiched between members. It only gives shear to the composition and detects the corresponding stress.

JP-A-6-256699 Japanese Patent No. 2996607 Japanese Patent Application Laid-Open No. 7-143941

  However, when actually writing, contact with the writing object, such as paper, no contact, writing speed, writing load, etc. greatly change in a short time. As the result of measurement of viscosity, etc., assuming that the specimen is not in contact with the ink composition as a sample, there is a limit to assuming the actual writing state. The ink composition is only evaluated for the viscosity itself, such as the overall lightness and good writing taste as the impression after finishing writing, and an ink composition that can sense a good writing feeling during writing is obtained. It was not.

  The present invention relates to an ink composition containing at least a colorant and a liquid medium. The ink composition can be rotated while being in contact with at least one receiving plate in a recessed portion of a pot containing the ink composition. Using a measuring device comprising at least a rotor provided with a ball at the tip, a receiving plate installed at an inclination of 45 degrees with respect to the rotation axis of the rotor in an ink composition bath placed in an appropriate amount in a recess in the pot The bearing is rotated while pressing the ball with a force of 2.12 N in the normal direction of the seat plate, and the friction coefficient is obtained when the relative speed due to the rotation of the rotor is gradually increased to 1.40 m / sec. In the measurement, the lower limit value of the friction coefficient in the range of the relative speed of 0.001 m / sec to 1.0 m / sec is a value less than the friction coefficient at the relative speed of 0.001 m / sec. Coefficient of friction An ink composition in which the slope of a straight line connecting a point indicating a friction coefficient at a speed obtained by adding 0.4 m / sec to the relative speed from the relative speed indicated and a point indicating the lower limit value is 6.0 or less is a gist. To do.

  In general, it is said that the normal writing speed is 0.001 m / sec or more and 0.50 m / sec or less, but this is an average value obtained by dividing the total writing distance written to a certain extent by the required time. Or, it is a central numerical value, and in fact, there is always a deceleration process that is the reverse of the acceleration process from zero speed to the fastest writing speed, and this occurs repeatedly in succession.

  The ink composition for a ballpoint pen according to the present invention exhibits the fluid lubrication action of the ink composition in the relative lubricating relationship between the ball and the ball seat in the process of increasing the writing speed. As the behavior of the coefficient of friction when the ball rotates in contact with the seat plate and the relative speed is gradually increased, the relative speed is in the range of 0.001 m / sec to 1.0 m / sec. As the friction coefficient gradually decreases and passes through the lower limit, there is a point where the writing speed is smooth due to the fluid lubrication action of the ink composition even when the writing speed is slow. Since the slope, which is the rate of increase in the coefficient of friction in a region higher than the relative speed at which the lower limit value is obtained, is 6.0 or less, it is affected by viscoelasticity due to the ink composition even in a scene where the writing speed is high. Ku does not become heavy of writing feeling, it is presumed to be those that easy to sense that the smooth writing is maintained.

Partial cross-sectional schematic diagram of an example of a tribology device The top view explaining the seat in the tribology apparatus shown in FIG. Tribology measurement results

  The invention is described in detail below.

  Test method 1 below is performed on a MCR302 rheometer (Anton Paar, Germany) using the tribology device of the present invention having a ball-on-sleep rate shape measurement system and temperature controlled by a Peltier and temperature control system. did. In this measuring method, sliding speed (unit: m / s), slide amount (unit: m), torque (unit: Nm), vertical load (unit: N), normal load (unit: N), friction Coefficient, friction force (unit: N), friction force (unit: J), friction force (unit: W) are detected on the rotor 1 side, temperature (unit: K) is detected on the pot 2 side, and time (unit) S), interval time (unit; s), the number of data points, etc., can be measured by the MCR302 system to obtain measurement results. The relative speed of the present invention is a value detected as a sliding speed in Test Method 1. In this measurement method, the ball 1b and the three seating plates 2b are in contact with each other at an angle of 45 degrees, and the load in the normal direction can be calculated from vertical load ÷ cos 45 °. Various measurement results such as a friction coefficient, a friction force, and a torque can be obtained while changing a relative speed, a vertical load, a temperature, and the like. The ball 1b may have a diameter of 12.7 mm or 30.0 mm, and any material may be used. Examples of commercially available balls include SUS 316 (manufactured by Anton Paar, Germany), and carbide (manufactured by Tsubaki Nakashima Co., Ltd.). The receiving plate 2b may have a length of 15 mm, a width of 6 mm, and a height of 3 mm, and any material may be used. Examples of the material of the commercially available receiving plate include SUS 316, Teflon (manufactured by Anton Paar, Germany), carbide (manufactured by Nisshin MEC Co., Ltd.), and the like.

  The outline of the above apparatus is as shown in FIGS. 1 and 2 as a schematic diagram. It is comprised from the pot 2 which has arrange | positioned the receiving plate 2b which contacts. The shaft 1a of the rotor 1 is connected to a motor for rotationally driving. In addition, the three receiving plates 2 b are arranged at a circular target position with respect to the rotation center of the rotor 1 in a state of being inclined by 45 degrees with respect to the rotation axis of the rotor 1.

  The metal ball 1b is made of SUS316 having a diameter of 12.7 mm (available from Anton Paar, Grmany), and the receiving plate 2b is made of SUS316 (available from Anton Paar, Grmany).

  The rotor 1 is rotated in a state where the concave portion 2a of the pot 2 is filled with the ink composition as the specimen, and the relative speed is changed from zero to a predetermined speed in a predetermined time.

  The test temperature was set at 25 ° C., and the ink composition 3 was blended with the metal ball 1b, the receiving plate 2b and the ink composition 3 over a period of 1 minute with a normal load of 2.12N without recording. The friction coefficient was recorded in the range of a relative speed of 0.001 m / sec to 1.0 m / sec.

  As the colorant used in the ink composition for ballpoint pens, there are dyes and pigments, either of which can be used. As the dye, water-soluble dyes and oil-soluble dyes can be used.

  As specific examples of the water-soluble dye, any of acid dyes, direct dyes, basic dyes and the like can be used. For example, Japanol Fast Black D Conch (CI Direct Black 17), Water Black 100L (19), Water Black L-200 (19), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black EX (38), Direct Fast Black Conk (51), Kayala Spragley VGN (71), Kayalas Direct Brilliant Yellow G (CI Direct Yellow 4) ), Direct Fast Yellow 5GL (26), Eisen Primula Yellow GCLH (44), Direct Fast Yellow R (50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet G X (4), Direct Fast Scarlet 4BS (23), Eisen Direct Rhodulin BH (31), Direct Scarlet B (37), Kayak Direct Scarlet 3B (39), Eisen Primula Pink 2BLH (75) ), Sumilite Red F3B (80), Eisen Primula Red 4BH (81), Kayara Spral Bin BL (83), Kayara Light Red F5G (225), Kayara Light Red F5B (226), Caillas Light Rose FR (same as 227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (same as 15), Sumilite Splash Blue BRR Conch (same as 71), Dibogen Turquoise Blue S 86), Water Blue # 3 (same as above) 6), direct dyes such as Kayala Star Coyze Blue GL (86), Kayala Supra Blue FF2GL (106), Kayara Supra 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 Conk (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conk (52), Sumilan Black WA (52), Ranil Black BG Extra Conk (107), Kyanol Milling Black TLB (109), Suminol Milling Black B (109), Kaya NORMILLING BLACK TLR ( 110), Eisen Opal Black New Conque (119), Water Black 187-L (154), Kayaku Acid Brilliant Flavin FF (C.I. I. Acid Yellow 7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Daiwa Tarrazine (23), Kayaktor Torazin (23) , Suminol Fast Yellow R (25), Diacid Light Yellow 2GP (29), Suminoll Milling O O (38), Suminol Milling MR MR (42), Water Yellow # 6 (42), 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), Kayanor Yellow NG (same 135), Kayano Lumiling Yellow 5 GW (127), Kayanol Milling 6 GW (142), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (9), Solar Rubin Extra (14), Daiwa New Coxin (18), Eisenbonso RH (26), Daiwa Red No. 2 (27), Suminol Leveling Brilliant Red S3B (35), Kayasil Rubinol 3GS (37), Eisen Erythrosin ( 51), kayak acid rhodamine FB (52), Suminol leveling rubinol 3GP (57), diacid alizarin rubinol F3G 200% (82), Eiseneosin GH (87), water pink # 2 (same) 92), Eisen Acid Phloxin PB 92), Rose Bengal (94), Cyanol Milling Scarlet FGW (111), Cyanol Milling Lubin 3BW (129), Sinoall Milling Brilliant Red 3BN Conch (131), Suminol Milling Brilliant Red BS ( 138), Eisen Opal Pink BH (186), Suminoll Milling Brilliant Red B Conch (249), Kayaku Acid Brilliant Red 3BL (254), Kayaku Acid Brilliant Red Brilliant Red BL (265), Kayanol Milling Red GW (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 1 (same 9), Spranol Blue B (same 15), Orient Solve Blue OBC (22), Suminol Leveling Blue 4GL (23), Mitsui Nylon Fast Blue G (25), Kayasil Blue AGG (40), Kayasil Blue BR (41), Mitsui Alizarin Saphirol SE (43) , Suminol Leveling Sky Blue R Extra Conk (62), Mitsui Nylon Fast Sky Blue B (78), Sumitomo Brilliant Indocyanine 6Bh / c (83), Sandlancyanine N-6B 350% (90), Water Blue # 115 (90), Orient Soluble Blue OBB The same 93), Sumitomo brilliant blue 5G (the 103), Kaya Nord milling Ultra Sky SE (the 112), Kaya Nord milling cyanine 5R (the 113), Aizen Opal Blue 2GLH (the 158), Daiwa Guinea green B (C. I. Acid Green 3), Acid Brilliant Milling Green B (same 9), Daiwa Green # 70 (same 16), Cyanol Cyanine Green G (same 25), Suminol Milling Green G (same 27), etc. Ron Yellow 3GLH (CI Basic Yellow 11), Eisen Cachiron Brilliant Yellow 5GLH (13), Sumiacryl Yellow E-3RD (15), Maxilon Yellow 2RL (19), Astrazone Yellow 7GLL (same) 21), Kayacrill Golden Yellow GL-ED (same 28), Astrazone Yellow 5GL (same 51), Eisen Cachiron Orange GLH (CI Basic Orange 21), Eisen Katyron Brown 3GLH (same 30), Rhodamine 6 GCP (C.I. Cred 1), Eisen Astrafloxin (12), Sumiacryl Brilliant Red E-2B (15), Astrazone Red GTL (18), Eisen Cathlon Brilliant Pink BGH (27), Maxilon Red GRL (same) 46), Eisenmethyl Violet (CI Basic Violet 1), Eisen Crystal Violet (Same 3), Eisen Rhodamine B (Same 10), Astrazone Blue G (CI Basic Blue 1), Astrazone Blue BG (Same 3), methylene blue (same 9), maxilon blue GRL (same 41), Eisen Cachiron blue BRLH (same 54), Eisen Diamond Green GH (CI Basic Green 1), Eisen Malachite Green (same 4) ), Bismarck Blau G (C.I. Basic Brown 1) basic dyes such as, can be mentioned.

Examples of oil-soluble dyes include C.I. I. Solvent Red 49, 109, Aizen Erythrosine (CI Acid Red 51, manufactured by Hodogaya Chemical Co., Ltd.), Kayaku Acid Rhodamine FB (CI Acid Red 52, Nippon Kayaku Co., Ltd.), Aizen Eosine GH (CI Acid Red 87, manufactured by Hodogaya Chemical Co., Ltd.), Aisen Acid Floxine PB (CI Acid Red 92, manufactured by Hodogaya Chemical Co., Ltd.), Floxine PB Conc. (CI. Acid Red 92, manufactured by Kasei Chemical Co., Ltd.), Rose Bengal (CI. Acid Red 94, manufactured by Kasei Chemical Co., Ltd.), VALIFAST Red 1308 (Dye Salt, Basic Red 1 + Acid Yellow 23) , Manufactured by Orient Chemical Industry Co., Ltd.), VALIFAST Red 1320 (Dye Salt, Basic Red 1 + Azo, manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red C-GH (Dye Solt, CI Basic Red 1: 1+) Acid, manufactured by Hodogaya Chemical Co., Ltd.), Spiron Red C-BH (Dye Solt, CI Basic Violet 1+ Acid, manufactured by Hodogaya Chemical Co., Ltd.), C.I. I. Solvent Violet 8, C.I. I. Solvent Blue 2, 73, C.I. I. Basic Blue 7, Acid Violet 6BN (CI Acid Violet 15), Patent Pure Blue VX (CI Acid Blue 1, manufactured by Sumitomo Sangoku Chemical Co., Ltd.), Water Blue # 106 (C.I.Ac. Blue 1), Patent Blue AF (C.I. Acid Blue 7, manufactured by BASF Japan Ltd.), Water Blue # 9 (C.I. Acid Blue 9), Daiwa Blue No. 1 (C.I. Acid Blue 9) ), Super Blue Blue B (CI Acid Blue 15, Farbenfabriken Bayer AG, Leverkusen, Germany), Orient Solve Blue OBC (CI Acid Blue 22). Chemical Industry Co., Ltd.), Sumitomo Brilliant Indocyanine 6B h / c (CI Acid Blue 83, Sumitomo Sangoku Chemical Co., Ltd.), Sandlancyanine N-6B 350% (CI Acid Blue 90), Water Blue # 115 (CI Acid Blue 90), Orient Soluble Blue OBB (CI Acid Blue 93, manufactured by Orient Chemical Industry Co., Ltd.), Sumitomo Brilliant Blue 5G (C.I. Mikuni Chemical Industry Co., Ltd.), Daiwa Guinea Green B (C.I. Acid Green 3, Daiwa Dye Manufacturing Co., Ltd.), Acid Brilliant Milling Green B (C.I. Acid Green) en 9, manufactured by Hodogaya Chemical Co., Ltd.), Daiwa Green # 70 (CI Acid Green 16), Aizen Diamond Green GH (CI Basic Green 1, manufactured by Hodogaya Chemical Co., Ltd.), Aizen Malachite Green (CI Basic Green 4, manufactured by Hodogaya Chemical Co., Ltd.), VALIFAST Violet 1701 (Dye Solt, Acid Yellow 42 + Basic Violet 1, manufactured by ET Chemical Industries, Inc. L, ST 31 V) Acid Violet 17 (triarylmethane acid dye) and onium salt of methine basic dye, manufactured by Orient Chemical Co., Ltd., OIL BLUE 613 (C.I. I. Solvent Blue 5 (triallyl methane dye) and rosin modified resin mixture, manufactured by Orient Chemical Industry Co., Ltd., VALIFAST Blue 1613 (Triphenylmethane Basic Blue 7 + Resin, manufactured by Orient Chemical Industry Co., Ltd.), VALIFAST BLUE 31 Blue UE Blue 7 (trial methane dye) and onium salt of colorless acid radical, manufactured by Orient Chemical Co., Ltd., Spiron Blue C-RH (manufactured by Hodogaya Chemical Co., Ltd.), Spiron Violet C-RH (Dye Solt, C Triarylmethane dyes such as I. Basic Violet 1 + Acid (made by Hodogaya Chemical Co., Ltd.), and Indo such as Spiron Yellow C-GNH (made by Hodogaya Chemical Co., Ltd.) Emissions-based dye, C. I. Solvent Blue 25, 55, Daivogen Turquoise Blue S (CI Direct Blue 86, manufactured by Dainippon Ink & Chemicals, Inc.), Water Blue # 3 (CI Direct Blue 86), KayaruSure L CI Direct Blue 86, manufactured by Nippon Kayaku Co., Ltd., Solar Turquoise Blue FBL (manufactured by CI Direct Blue 199, Snods Ltd., Basle. Sandoz Products, h. , VALIFAST BLUE 1605 (CI Solvent Blue 38 (copper phthalocyanine dye), Orient Chemical Co., Ltd.) Phthalocyanine dyes such as C.I. I. Solvent Yellow 2, 6, 14, 15, 16, 19, 21, 21, 56, 62, 79, 82, C.I. I. Solvent Orange 1, 2, 2, 5, 6, 45, 62, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 83, 84, 100, 109, 121, C.I. I. Solvent Violet 21, C.I. I. Solvent Brown 3, 5, 37, C.I. I. Solvent Black 3, 22, 22, 123, Japanol Fast Black D conc. (CI Direct Black 17, manufactured by Sumitomo Chemical Co., Ltd.), Water Black 100L (CI Direct Black 19), Water Black L-200 (CI Direct Black 19), Direct Fast Black B (CI Direct Black 22, manufactured by Hodogaya Chemical Co., Ltd.), Direct Fast Black AB (CI Direct Black 32, manufactured by Sumitomo Chemical Co., Ltd.), Direct Deep Black EX (C.I. Direct Black 38, manufactured by Sumitomo Chemical Co., Ltd.), Direct Fast Black Conc. (CI Direct Black 51, manufactured by Hodogaya Chemical Co., Ltd.), Kayaru Supra Gray VGN (CI Direct Black 71, manufactured by Nippon Kayaku Co., Ltd.), Direct Fast Yellow 5GL (C.I. Direct Yellow 26, manufactured by Hodogaya Chemical Co., Ltd.), Aizen Primera Yellow GCLH (produced by CI Direct Yellow 44, manufactured by Hodogaya Chemical Co., Ltd.), Direct Fast Yellow R (C.I Direct Yellow 50, manufactured by Hodogaya Chemical Industry Co., Ltd.) Sumitomo Chemical Co., Ltd.), Aizen Direct Fast Red FH (CI Direct Red 1, Hodogaya Chemical Co., Ltd.), Nippon Fast Scallet GSX (CI Direct Red 4, Sumi Chemical Industry Co., Ltd.), Direct Fast SC BSlet BS (CI Direct Red 23, Hodogaya Chemical Industry Co., Ltd.), Aizen Direct Rhodrine Red BH (CI Direct Red 31, Hodogaya Chemical Industries, Ltd.) Co., Ltd.), Direct SCARlet B (CI Direct Red 37, Nippon Kayaku Co., Ltd.), Kayaku Direct SCARlet 3B (CI Direct Red 39, Nippon Kayaku Co., Ltd.), Aizen Primula Pink 2BLH (CI Direct Red 75, manufactured by Hodogaya Chemical Co., Ltd.), Sumitright Red F3B (CI Direct Red 80, manufactured by Sumitomo Chemical Co., Ltd.), Aizen Primula Red 4BH (C.I) .Di rect Red 81, manufactured by Hodogaya Chemical Co., Ltd.), Kayarusu Supra Rubin BL (CI Direct Red 83, manufactured by Nippon Kayaku Co., Ltd.), Kayarus Light Red F5G (C.I. Direct Red 225, Japan) Kayrus Light Red F5B (CI Direct Red 226, manufactured by Nippon Kayaku Co., Ltd.), Kayaru Light Rose FR (CI Direct Red 227, manufactured by Nippon Kayaku Co., Ltd.) ), Direct Sky Blue 6B (CI Direct Blue 1, manufactured by Sumitomo Chemical Co., Ltd.), Direct Sky Blue 5B (C.I.). I. Direct Blue 15, manufactured by Hodogaya Chemical Co., Ltd., Sumitright Super Blue BRR conc. (C.I. Direct Blue 71, manufactured by Sumitomo Chemical Co., Ltd.), Acid Blue Black 10B (C.I. Acid Black 1), Suminol Milling Black 8BX (C.I. Acid Black 24, Sumitomo Chemical Co., Ltd.) )), Kayanol Milling Black VLG (CI Acid Black 26, manufactured by Nippon Kayaku Co., Ltd.), Suminol Fast Black BR conc. (CI Acid Black 31, Sumitomo Chemical Co., Ltd.), Mitsui Nylon Black GL (CI Acid Black 52, Mitsui BASF Co., Ltd.), Aizen Opal Black WH extra conc. (CI Acid Black 52, manufactured by Hodogaya Chemical Co., Ltd.), Sumilan Black WA (CI Acid Black 52, manufactured by Sumitomo Chemical Co., Ltd.), Lanyl Black BG, extra conc. (CI Acid Black 107, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), Kayanol Milling Black TLB (CI Acid Black 109, manufactured by Nippon Kayaku Co., Ltd.), Suminol Milling Black B (CI Acid) Black 109, Sumitomo Chemical Co., Ltd.), Kayanol Milling Black TLR (CI Acid Black 110, manufactured by Nippon Kayaku Co., Ltd.), Aizen Opal Black new conc. (CI Acid Black 119, Hodogaya Chemical Co., Ltd.), Kayacyl Yellow GG (CI Acid Yellow 17, Nippon Kayaku Co., Ltd.), Xylene Light Yellow 2G 140% (CI Acid Yellow 17, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., Suminole Leveling Yellow NR (CI Acid Yellow 19, manufactured by Sumitomo Chemical Co., Ltd.), Daiwa Tartrazine (CI Acid Yellow 23, Daiwa Dye Manufacturing) KK), Kayaku Tartrazine (CI Acid Yellow 23, Nippon Kayaku Co., Ltd.), Suminol Fast Yellow R conc. (CI Acid Yellow 25, manufactured by Sumitomo Chemical Co., Ltd.), Diacid Light Yellow 2GP (CI Acid Yellow 29, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), Suminol Milling Yell

ow O (CI Acid Yellow 38, manufactured by Sumitomo Chemical Co., Ltd.), Suminoll Milling Yellow MR (CI Acid Yellow 42, manufactured by Sumitomo Chemical Co., Ltd.), Water Yellow # 6 (C.I) Acid Yellow 42), Kayanol Yellow NFG (CI Acid Yellow 49, manufactured by Nippon Kayaku Co., Ltd.), Suminol Milling Yellow 3G (CI Acid Yellow 72, manufactured by Sumitomo Chemical Co., Ltd.), Suminol Fast Yellow G (CI Acid Yellow 61, manufactured by Sumitomo Chemical Co., Ltd.), Suminoll Milling Yellow G (CI Acid Yellow 78, manufactured by Sumitomo Chemical Co., Ltd.), Kayanol Yellow ow N5G (CI Acid Yellow 110, manufactured by Nippon Kayaku Co., Ltd.), Suminol Milling Yellow 4G (CI Acid Yellow 141, manufactured by Sumitomo Chemical Co., Ltd.), Kayanol Fast Yellow NG (CI) Acid Yellow 135, manufactured by Nippon Kayaku Co., Ltd.), Kayanol Milling Yellow 5GW (CI Acid Yellow 127, manufactured by Nippon Kayaku Co., Ltd.), Kayanol Milling Yellow 6GW (CI Acid Yellow 142, Japan) Kaitaku Co., Ltd.), Sumitomo Fast Scallet A (CI Acid Red 8, Sumitomo Chemical Co., Ltd.), Kayaku Silk Scarlet (CI Acid Red 9, Nippon Kayaku Co., Ltd.) ), Solar Rubine extra (CI Acid Red 14, manufactured by Sumitomo Chemical Co., Ltd.), Daiwa New Cocine (CI Acid Red 18, Daiwa Dye Manufacturing Co., Ltd.), Aizen Ponceau RH (C) I. Acid Red 26, manufactured by Hodogaya Chemical Co., Ltd., Daiwa Amaranth (C. I. Acid Red 27, manufactured by Daiwa Dye Manufacturing Co., Ltd.), Suminol Leveling Brilliant Red S3B (C. I. Acid Red 35) , Manufactured by Sumitomo Chemical Co., Ltd.), Kayacyl Rubinol 3GS (CI Acid Red 37, manufactured by Nippon Kayaku Co., Ltd.), Suminol Leveling Rubinol 3GP (C.I. I. Acid Red 57, manufactured by Sumitomo Chemical Co., Ltd.), Kayanol Milling Scarlet FGW (CI Acid Red 111, manufactured by Nippon Kayaku Co., Ltd.), Kayanol Milling Rubine 3BW (C.I. Acid Red 129, Nippon Kayaku) Yakuhin Co., Ltd.), Suminoll Milling Brilliant Red 3BN conc. (C.I. Acid Red 131, manufactured by Sumitomo Chemical Co., Ltd.), Suminol Milling Brilliant Red BS (C.I. Acid Red 138, manufactured by Sumitomo Chemical Co., Ltd.), Aizen Opal Pink BH (C.I. Acid Red 186, manufactured by Hodogaya Chemical Co., Ltd.), Suminol Milling Brilliant Red B conc. (CI Acid Red 249, manufactured by Sumitomo Chemical Co., Ltd.), Kayaku Acid Brilliant Red 3BL (CI Acid Red 254, manufactured by Nippon Kayaku Co., Ltd.), Kayaku Acid Brilliant Red BL (C.I Acid Red 265, manufactured by Nippon Kayaku Co., Ltd., Supronol Brilliant Red GW (CI Acid Red 276, Farbenfabricen Bayer A. G., Leverkusen), Kayanol Milling C. Nippon Kayaku Co., Ltd.), Aizen Opal Blue 2GLH (CI Acid Blue 158, Hodogaya Chemical Co., Ltd.), Aizn Cathilon Blue NBLH ( C. I. Basic Blue 66, manufactured by Hodogaya Chemical Co., Ltd.), Bismarck Brown G conc. (C.I. Basic Brown 1, manufactured by Sumitomo Chemical Co., Ltd.), VALIFAST Yellow 1109 (Acid Yellow 42), VALIFAST Yellow 3150 (Azo Chrome Complex Solvent Yellow 79), VALIFAST Yell 79 (VALIFAST Yell 79) , VALIFAST Black 3804 (Azo Chrome Complex Solvent Black 34 + Amine), VALIFAST Orange 2210 (Azo Chrome Complex), VALIFAST Red 1IF (Dye Solt B, YD) ST Red 1320 (Dye Salt, Basic Red 1 + Azo), VALIFAST YELLOW 1171 (CI. Acid Yellow 42 derivative), VALIFAST YELLOW 1108, VALIFAST BLACK 1807 (Acid Black 38A) 3810 (Solvent Black 29), 3820 (Solvent Black 27), 3830 (Solvent Black 27), 3840 (Solvent Black 27), 3866 (Solvent Black 29), 3870 (Solvent Black 29, and above) Azo dyes such as Orient Chemical Industry Co., Ltd., Spiron Yellow (Manufactured by Hodogaya Chemical Co. (Ltd.)) -2GH, C. I. Solvent Yellow 33, Diacid Azariline Rubinol F3G 200% (CI Acid Red 82, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), Suminol Leveling Sky Blue extra con. Examples include methine dyes such as (CI Acid Blue 62, manufactured by Sumitomo Chemical Co., Ltd.). Triarylmethane dyes, phthalocyanine dyes, xanthene dyes, indolinone dyes, azo dyes, and methine dyes are preferred because the color development of the ink and the stability of the ink over time when the pH changes are good. .

  Oil-soluble dyes include triarylmethane dyes, phthalocyanine dyes, xanthene dyes, indolinone dyes, azo dyes, and methine dyes, such as Orient Nigrosine BR (CI Acid Black 2, Orient). Chemical Industry Co., Ltd.), C.I. I. Solvent Black 5, 7; Nigrosine Base ER (CI Solvent Black 7, manufactured by Orient Chemical Industry Co., Ltd.), Nigrosine Base EX (CI Solvent Black 7, manufactured by Orient Chemical Industry Co., Ltd.), Nigros Nigrosine dyes such as Base EX-BP (CI Solvent Black 7), C.I. I. Disperse Red 9, C.I. I. Solvent Violet 13, 14 and C.I. I. Disperse Violet 1, C.I. I. Solvent Blue 11, 12, 36, C.I. I. Solvent Green 3, Kayarusu Supra Blue FF2GL (CI Direct Blue 106, manufactured by Nippon Kayaku Co., Ltd.), Kayaku Acid Brilliant FF (manufactured by CI Acid Yellow), Nippon Kayaku 7) Leveling Blue 4GL (CI Acid Blue 23, manufactured by Mitsui Chemicals), Mitsui Nylon Fast Blue G (CI Acid Blue 25, manufactured by Mitsui Chemicals), Kayacyl Blue AGG (Ci. Acid Blue 40, manufactured by Nippon Kayaku Co., Ltd.), Kayacyl Blue BR (CI Acid Blue 41, manufactured by Nippon Kayaku Co., Ltd.), Mitsui Alizarine Sap irol SE (CI Acid Blue 43, manufactured by Mitsui Chemicals, Inc.), Mitsui Nylon Fast Sky Blue B (CI Acid Blue 78, manufactured by Mitsui Chemicals, Inc.), Kayanol Milling Ultra Sy (Sky) I. Acid Blue 112, manufactured by Nippon Kayaku Co., Ltd.), Kayanol Cyanine Green G (CI Acid Green 25, manufactured by Nippon Kayaku Co., Ltd.), Suminol Milling Green G (C.I. Acid Green 27, Sumitomo Chemical Co., Ltd.) can be used.

  When the oil-soluble dye is a salt-form of an acid dye and a basic substance, it is more preferable that the basic substance has a methine group in terms of color development. In the case of a salt-form of a basic dye and an acidic substance, it is more preferable that the acidic substance has an alkylbenzenesulfonic acid group in terms of color developability.

  These dyes can be used alone or in combination, and can be used in combination with pigments. The amount of the dye used is preferably 1.0% by weight or more and 40.0% by weight or less based on the total amount of the ink composition. When the amount used is less than 1.0% by weight, the color development is not clear. If it exceeds 40.0% by weight, a problem that the writing quality becomes heavy due to an increase in the solid content in the ink composition tends to occur. For this reason, the amount of the dye used is more preferably from 5.0% by weight to 30% by weight, and most preferably from 10.0% by weight to 25.0% by weight, based on the total amount of the ink composition.

  As pigments, azo pigments, azo lake pigments, condensed azo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, anthraquinone pigments, dioxazine pigments Indigo pigments, thioindigo pigments, quinophthalone pigments, perinones, perylene pigments, nitroso pigments, nitro pigments, basic dye pigments, acid dye pigments, building dye pigments, mordant dye pigments, and Organic pigments such as natural dye-based pigments, ocher, barium yellow, ultramarine, bitumen, cadmium red, barium sulfate, titanium oxide, petals, iron black, carbon black and other inorganic pigments, aluminum powder, gold powder, silver powder, copper powder, Examples thereof include metal powder pigments such as tin powder and brass powder, fluorescent pigments, and mica-based pigments.

  In the present invention, water-based ink refers to an ink composition whose main solvent is water, and oil-based ink refers to an ink composition whose main solvent is other than water. In the present invention, the main solvent refers to the liquid medium that occupies the highest percentage by weight with respect to the total amount of the liquid medium in the ink composition.

  Specific examples of organic pigments that can be used in water-based inks include aniline black (C.I. 50440), cyanine black, naphthol yellow S (C.I. 10316), Hansa Yellow 10G (C.I. 11710), and 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 ( CI 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. 21100), Permanent Yellow NCG (C.I.2 040), Vulcan Fast Yellow 5G (C.I. 21220), Vulcan Fast Yellow R (C.I. 21135), Tartrazine Lake (C.I. 19140), Quinoline Ero Lake (C.I. 47005), Anthra Gene Yellow 6GL (C.I. 60520), Permanent Yellow FGL, Permanent Yellow H10G, Permanent Yellow HR, Anthrapyrimidine Yellow (C.I. 68420), Sudan I (C.I. 12055), Permanent Orange (C.I 12075), Resor Fast Orange (C.I. 12125), Permanent Orange GTR (C.I. 12305), Hansa Yellow 3R (C.I. 11725), Vulcan Fast Orange GG (C.I. 21165), Benzidine Orange G (C.I 21110), Persian Orange (C.I. 15510), Indanthrene Brilliant Orange GK (C.I. 59305), Indanthren Brilliant Orange RK (C.I. 59105), Indanthren Brilliant Orange GR (C.I. 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 ortho aniline red (C.I. 12090), resol fast scarlet, brilliant fast scarlet (C.I. 12315), brilliant carmine BS, permanent red F2R (C.I. 12310), permanent Nintred F4R (C.I. I. 12335), Permanent Red FRL (C.I. 12440), Permanent Red FRLL (C.I. 12460), Permanent Red F4RH (C.I. 12420), Fast Scarlet VD, Vulcan Fast Rubin B (C.I. 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), risol red (C.I. 15630), lake red C (C.I. 15585), lake red D (C.I. 15500), anthosine B (C.I. 18030), Brilliant Scarlet G (C.I. 5800), Risol Rubin GK (C.I. 15825), Permanent Red F5R (C.I. 15865), Brilliant Carmine 6B (C.I. 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 (C.I. 15880), Bon Maroon Wright (C.I. 15825), Bon Maroon Medium (C.I. 15880), Eosin Lake (C.I. 45380), Rhodamine Lake B (C.I. 45170), Rhodamine Lake Y (C.I. 45160) ), Alizarin lake (C.I. 58000), thioin Gored B (C.I. 73300), Thioindigo Maroon (C.I. 73385), Permanent Red FGR (C.I. 12370), PV Carmine HR, Watching Red, Monolite Fast Red YS (C.I. 59300), Permanent Red BL, Fast Violet B, Methyl Violet Lake (C.I. 42535), Dioxazine Violet, Alkaline Blue Lake (C.I. 42750A, C.I. 42770A), Peacock Blue Lake (C.I) 42090), Peacock Blue Lake (C.I. 42025), Victoria Blue Lake (C.I. 44045), Phthalocyanine Blue (C.I. 74160), Fast Sky Blue (C.I. 74180), Indanthrene Blue RS (C.I.6 9800), Indanthrene Blue BC (C.I. I. 69825), Indigo (C.I. 73000), Pigment Green B (C.I. 10006), Naphthol Green B (C.I. 10020), Green Gold (C.I. 12775), Acid Green Lake, Malachite Green Among inorganic pigments such as rake (C.I.42000), phthalocyanine green, and the like, specific examples of carbon black include Mitsubishi Carbon Black # 10B, # 20B, # 14, # 25, # 30, # 33, # 40, # 44, # 45, # 45L, # 50, # 55, # 95, # 260, # 900, # 1000, # 2200B # 2300, # 2350, # 2400B, # 2650, # 2700, # 4000B, CF9, MA8, MA11, MA77, MA100, MA220, MA230, MA600, MCF88 (above, manufactured by Mitsubishi Chemical Corporation), Monarch 120, Monarch 700, Monarch 800, Monarch 880, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Mogal L, Legal 99R, Legal 250R, Legal 300R, Legal 330R, Legal 400R, Legal 500 and Legal 660R (above, 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, manufactured by Degussa Japan Co., Ltd.), Raven 5000 Ultra II, Raven 2500 Ultra, Raven 1250, Raven 760 Ultra (above, Colombian Carbon Japan Etc.).

  Specific examples of pigments that can be used in oil-based inks include carbon blacks such as Pigment Black 6, 7 and the like, metal complex pigments such as Pigment Blue 27, 9 and Pigment Violet 15, Pigment Red 259, Pigment White 6, and Pigment Y 6. 42, Pigment Black 11, Pigment Red 101 and other metal oxide pigments, Pigment Yellow 53, Pigment Brown 24 and other complex oxide pigments, etc., Pigment White 21, 22, 27, 28, 19, 19 24, extender pigments such as kaolin clay, calcined clay, talc, bentonite, mica, muscovite, phlogopite, nepheline cinnite, aluminum pace Metal powder pigments such as aluminum flake powder and bronze powder, Pigment White 1, 14, inorganic pigments such as pearlescent pigments such as titanium dioxide and coated mica, Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 82, 83, 84, 90, 90: 1, 151, 169, 172, 173, 174, 191, Pigment Orange 39, Pigment Yellow 18, 100, 104, 115, 117, Pigment Blue 1, 1: 2, 2, 3, 8, 8, 9, 10, 11, 12, 14, 53 62, 63, Pigment Viotel 1, 2, 2, 2: 2, 3, 3: 1, 3: 3, 4, 5, 5, 5: 1, 6 1: 1, 7: 1, 9, 12, 20, 26, 27, 39, Pigment Green 1, 2, 3, 4, 4, 8, 9, 10, 12 45, lake pigments such as Pigment Brown 3, Pigment Red 1, 3, 21, 21, 112, 146, 170, 187, 150, 185, 38, 41, Pigment Orange 5, 38, 36, 16, 16, 13, 34, Pigment Yellow 1, 3, 97, 167, 154, 12, 13, 13, 14, 17, 55, 83, 81, 10, insoluble azo pigments such as Pigment Brown 25, condensed azo pigments such as Pigment Red 144, 166, Pigment Red 53, 53: 1, 53: 3, 50, 50: 1, 49, 49: 1, 49: 2, 49: 3, 57: 1, 48: 1, 48: 2, 48: 3, 48: 4, 52: 1, 63: 1, 63: 2, 58: 2, 58: 4, 51, 60: 1, 64: 1, Pigment Orange 17, 18 and 19, azo lake pigments such as Pigment Yellow 61 and 62, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, Pigment Green 7, 36, 37 and other phthalocyanine pigments, Pigment Red 122, 202, 206, 207, 209, Pigment Orange 48, Pigmen Quinacridone pigments such as t Violet 19, Pigment Red 168, 177, Pigment Orange 51, Pigment Yellow 24, 108, Pigment Blue 60 and other anthraquinone pigments, Pigment Red 123, 149, 178, 178, 178 190, 224, Pigment Violet 29, Pigment Black 31, 32, and other perylene pigments, Pigment Red 194, Pigment Orange 43, and other perinone pigments, Pigment Red 88, 181, Pigment Brown 27, Pigment Brown Indigo pigments such as 63, and geometries such as Pigment Violet 23 and 37 Sagin pigments, quinophthalone pigments such as Pigment Yellow 138, isoindolinone pigments such as Pigment Orange 61, Pigment Yellow 109, 110 and 173, Pigment Red 260, Pigment Orange 66, 69 and Yig. Isoindolin pigments such as 185, azo metal complex pigments such as Pigment Yellow 150, Pigment Green 8, and 10; azomethine metal complex pigments such as Pigment Red 257, Pigment Orange 68, Pigment Yellow 129, 153 and 65; Red 254, 255, 264, 270, 272, Pigme Diketopyrrolopyrrole pigments such as nt Orange 71 and 73, Pigment Blue 18, 19, 56, 57, 61, 56: 1, 61: 1, etc. Alkali blue pigments, Pigment Black 1, etc. Aniline black, Basic Yellow 40, Basic Red 1, Basic Violet 10, Acid Yellow 7, Acid Red 92, Acid Blue 9, Disperse Yellow 121, Disperse Blue 7, Yell Yellow Wright 85 44, Solvent Blue 5, and the like.

  Among these, as the blue pigment, a particularly clear handwriting is obtained with a phthalocyanine pigment. From the crystal stability and dispersion stability in a solvent, C.I. I. Pigment Blue 15: 3 or a pigment derivative treatment type thereof, or C.I. I. Pigment Blue 15: 6 can be preferably used. Examples of pigments capable of obtaining dark handwriting include C.I. I. Pigment Blue 60 is preferred.

  As a red pigment, diketopyrrolopyrrole-based C.I. has good light resistance and solvent resistance, and the appearance color becomes clear red when the ink composition is filled in a refill. I. Pigment Red 254, 255 and 264 can be particularly preferably used. Examples of pigments that have good solvent resistance and can obtain dark handwriting include C.I. I. Pigment Red 170 is preferred.

  For green ink, an ink composition with a clear appearance color is produced by adjusting the color of a blue pigment and a yellow pigment, or by adjusting the color of a blue dye and a yellow pigment. It becomes.

  As commercially available black pigments, Printex 3, 25, 30, 35, 40, 45, 55, 60, 75, 80, 85, 90, 95 300, Special Black 4, 5, 100, 250, 550 (Degussa Huls Japan Co., Ltd.), Mitsubishi Carbon Black # 2700, # 2650, # 2600, # 2400, Same # 2350, Same # 2300, Same # 2200, Same # 1000, Same # 990, Same # 980, Same # 970, Same # 960, Same # 950, Same # 900, Same # 850, Same # 750, Same # 650, # 260, # 95, # 52, # 50, # 47, # 45, # 45L, # 44, # 40, # 33, # 32, # 30, Same # 25, Same # 20, Same # 10, Same # 5, Same F9, same MCF88, same MA7, same MA11, same MA77, same MA100, same MA100R, same MA100S, same MA220, same MA230, same MA600 (above, manufactured by Mitsubishi Chemical Corporation), Tokai Black # 8500 / F, # 8300 / F, # 7550SB / F, # 7400, # 7360SB / F, # 7350 / F, # 7270SB, # 7100 / F, # 7050 (above, manufactured by Tokai Carbon Co., Ltd.) ), Carbon black such as Diamond Black N (manufactured by Tamamone Color Co., Ltd.), bone black (manufactured by Mie Color Techno Co., Ltd.), iron black KN-320 (Nippon Iron & Chemical Co., Ltd.), etc. As iron black and red pigments, Igragin DPP Red BO, BTRR, 2030, 2031, Cro such as optical Red BP, BOC, 2028, 2030, Irgaphor Red-CF, BT-CF (manufactured by CSC), Hostaperm Red D2G70 (manufactured by Clariant), FUJI RED 8800 (manufactured by Fuji Dye Co., Ltd.) Pigment Red 255 (diketopyrrolopyrrole pigment), Irgazin DPP Scallet EK, Chrophtal Coral Red C (manufactured by Central Scientific Trading Co., Ltd.) and the like, and Blue pigment as Blue pigment L6385, L6470, L6480, L6482L, 6495F (above, manufactured by BASF), Chromophthal Blue A3R, A3RJ, Irgazin Blue A3RN (above, Central Scientific Trade Co., Ltd.), DCC Blue A3R (C.I. I. Pigment Blue 60, manufactured by Dominion Color Corporation, U.S. Pat. S. A), Fastage Super Blue 6075, 6070S (above DIC Corporation), Monoblue Blue 3R, 3RFW (above, Heubach, Germany), Lionogen Blue R, 6501, 6505 (above, Toyo Ink (above) Pigment Blue 60 (Anthraquinone Pigment), etc., manufactured by Co., Ltd.), as a green pigment, Monastral Green GN-C, GNX-C, GBN-C, GBX-C, 2GFWC, BEEFWC (above, manufactured by Heubach) Germany), Heliogen Blue L8605, L8690, L8730, 8731, 8735, 8730, 8605DD, D8725, D8730 (above, manufactured by BASF), Phthal Cyanin Green B308, B609, SAX (above, manufactured by Sanyo Dye Co., Ltd.), Cyanine Green 2G-550-D, 2GN, 2GO, 5310 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.) Pigment Green 7 (phthalocyanine pigment) such as Cyanine Green PBN-1 (manufactured by Toyo Ink Co., Ltd.), Sumitone Cyanine Green 2G-HS (Sumitomo Color Co., Ltd.), and the like.

  Specific examples of processed pigments that can be used in oil-based inks include Renol Yellow GG-HW30, HR-HW30, Orange RL-HW30, Red HF2B-HW30, FGR-HW30, F5RK-HW30, and Carmine. FBB-HW30, Violet RL-HW30, Blue B2G-HW30, CF-HW30, Green GG-HW30, Brown HFR-HW30, Black R-HW30 (above, manufactured by Clariant Japan Co., Ltd.), UTCO- 001 yellow, 012 yellow, 021 orange, 031 red, 031 red, 032 red, 042 violet, 051 blue, 052 blue, 061 green, 591 black, 591 black Industry Co., Ltd.), and the like, can be mentioned.

  The amount of these pigments to be used is preferably 1.0% by weight or more and 40.0% by weight or less, more preferably 3.0% by weight or more and 30.0% by weight or less based on the total amount of the ink composition. The weight percent is most preferably 25.0 wt% or less. If the amount used is less than 1.0% by weight, the light resistance of the handwriting becomes weak. On the other hand, when the amount is more than 40.0% by weight, a problem that the writing taste becomes heavy due to writing scraping due to clogging due to sedimentation with time or an increase in solid content in the ink composition tends to occur.

  Specific examples of titanium oxide include SR-1 (oil absorption 19 to 21 g / 100 g), R-3L (oil absorption 21 to 24 g / 100 g), R-5N (oil absorption 19 to 21 g / 100 g), R-7E. (Oil absorption 27 to 31 g / 100 g), R-24 (Oil absorption 21 to 24 g / 100 g), R-61N (Oil absorption 22 g / 100 g), R-62N (Oil absorption 19 to 21 g / 100 g), R-310 (Oil absorption 21 g / 100 g), R-650 (Oil absorption 20-22 g / 100 g), D-918 (Oil absorption 20-24 g / 100 g), FTR-700 (Oil absorption 19-23 g / 100 g), TCR-52 (Oil absorption 16 to 19 g / 100 g) (manufactured by Sakai Chemical Industry Co., Ltd.), Type R-550 (oil absorption 23 g / 100 g), R-580 (oil absorption 19 g / 100 g), R-63 (Oil absorption 19 g / 100 g), R-670 (oil absorption 22 g / 100 g), R-680 (oil absorption 19 g / 100 g), R-780 (oil absorption 33 g / 100 g), R-780-2 (Oil absorption 40 g / 100 g), R-820 (Oil absorption 24 g / 100 g), R-830 (Oil absorption 21 g / 100 g), R-930 (Oil absorption 19 g / 100 g), R-980 (Oil absorption) 19g / 100g), PR-690 (oil absorption 16g / 100g), PF-691 (oil absorption 15g / 100g), PF-711 (oil absorption 19g / 100g), PF-736 (oil absorption 15g) PF-737 (oil absorption 16 g / 100 g), PF-737 (oil absorption 21 g / 100 g), PF-739 (oil absorption 14 g / 100 g), PF-740 (absorption) 16g / 100g), PC-3 (oil absorption 16g / 100g), S-305 (oil absorption 23g / 100g), CR-50 (oil absorption 18g / 100g), CR-50-2 (oil absorption) 17 g / 100 g), CR-57 (oil absorption 17 g / 100 g), CR-58 (oil absorption 19 g / 100 g), CR-58-2 (oil absorption 18 g / 100 g), CR-Super 70 (oil absorption) 16g / 100g), CR-80 (oil absorption 20g / 100g), CR-85 (oil absorption 30g / 100g), CR-90 (oil absorption 21g / 100g), CR-90-2 (oil absorption) 20 g / 100 g), CR-93 (oil absorption 20 g / 100 g), CR-97 (oil absorption 19 g / 100 g), A-100 (oil absorption 22 g / 100 g), A-220 (oil absorption 22) g / 100g), (manufactured by Ishihara Sangyo Co., Ltd.), Kronos KR-270 (oil absorption 21 g / 100 g), KR-310 (oil absorption 17-22 g / 100 g), 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 19-24 g / 100 g), KA-20 (oil absorption 18-23 g / 100 g), KA-30 (oil absorption 18-23 g / 100 g) (manufactured by Titanium Industry Co., Ltd.) , TITANIX JR-300 (oil absorption 18 g / 100 g), JR-301 (oil absorption 18 g / 100 g), JR-403 (oil absorption 19 g / 100 g), JR-405 (oil absorption 15 g) 100 g), JR-600A (oil absorption 19 g / 100 g), JR 603 (oil absorption 21 g / 100 g), JR-605 (oil absorption 19 g / 100 g), JR-600E (oil absorption 21 g / 100 g), JR-603 (oil absorption 21 g / 100 g), JR-800 (oil absorption 29 g / 100 g), JR-801 (oil absorption 40 g / 100 g), JR-805 (oil absorption 22 g / 100 g), JR- 806 (oil absorption 21 g / 100 g), JR-906 (oil absorption 22 g / 100 g), JR-701 (oil absorption 20 g / 100 g), JRNC (oil absorption 21 g / 100 g), JR (oil absorption 18 g / 100 g), JA-1 (oil absorption 23 g / 100 g), JA-C (oil absorption 23 g / 100 g), JA-3 (oil absorption 23 g / 100 g) (above TA-100 (oil absorption 22 g / 100 g), TA-200 (oil absorption 24 g / 100 g), TA-300 (oil absorption 21 g / 100 g), TA-400 (oil absorption 24 g / 100 g) ), TR-600 (oil absorption 19 g / 100 g), TR-700 (oil absorption 23 g / 100 g), TR-840 (oil absorption 24 g / 100 g), TR-900 (oil absorption 19 g / 100 g) (Fuji Titanium) Manufactured by Kogyo Co., Ltd.), Taipure R-700 (oil absorption 13 g / 100 g), R-706 (oil absorption 13 g / 100 g), R-900, R-901 (oil absorption 14 g / 100 g), R- 902 (oil absorption amount 16 g / 100 g) (above, manufactured by DuPont Japan Limited) and the like are used by being dispersed in a liquid medium. The amount of titanium oxide used is preferably 3.0% by weight or more and 15.0% by weight or less based on the total amount of the ink composition. If it is less than 3.0% by weight, the handwriting density is thin and it may be difficult to visually recognize. If it is more than 15.0% by weight, the writing quality may be somewhat heavy.

  As a specific example of the metal powder pigment, commercially available aluminum powder includes Super Fine No. 22000, ibid. 18000, Fine No. 900, ibid. 800 (above, manufactured by Daiwa Metal Powder Industry Co., Ltd.), AA12, AA8, No. 900, no. 18000 (above, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.), aluminum powder 1000, 2700 (above, manufactured by Nakatsuka Metal Foil Powder Industry Co., Ltd.), etc., as the aluminum paste, WB0230, WXM0630 (above, Toyo Aluminum ( Co., Ltd.), Super Fine No. Colored aluminum, such as 22000WN, 18000WN (above, manufactured by Daiwa Metal Powder Industry Co., Ltd.), etc., include Friend Color F350 BL-W, GR-W, F100 BL-W, GR-W (above, Showa Denko ( Etc.). In particular, as crushed fine pieces in which aluminum is coated with a colored resin layer, it is possible to increase the number of colors and to obtain a very large glitter, but as a commercially available one, LNG neo R- GOLD # 35, Elgi neo B-GOLD # 35, Elgi neo S-GOLD # 35, Elgi neo R-GOLD # 100, Elgi neo B-GOLD # 100, Elgi neo S-GOLD # 100, Elgi neo RED # 100, Elgie neo blue # 100, Elgie neo GREEN # 100, Elgie neo VIOLET # 100, Elgie neo BLACK # 100, Elgie neo Copper # 100, Elgie neo PINK # 100, Elgie neo Yellow # 100 00, Elgie neo R-GOLD # 150, Elgie neo B-GOLD # 150, Elgie neo S-GOLD # 150, Elgie neo RED # 150, Elgie neo BLUE # 150, Elgie neo GREEN # 150, Elgie neo VIOLET # 150, Elgie neo BLACK # 150, Elgi neo COPPER # 150, Elgi neo PINK # 150, Elgi neo YELLOW # 150, Elgi neo R-GOLD # 200, Elgi neo B-GOLD # 200, Elgi neo S-GOLD # 200, Elgi neo RED # 200, Elgie neo BLUE # 200, Elgie neo GREEN # 200, Elgie neo VIOLET # 2 00, Elgie neo BLACK # 200, Elgie neo Copper # 200, Elgie neo PINK # 200, Elgie neo YELLOW # 200, Elgie neo R-GOLD # 325, Elgie neo B-GOLD # 325, Elgie neo S-GOLD # 325, Elgie neo RED # 325, Elgie neo BLUE # 325, Elgie neo GREEN # 325, Elgie neo VIOLET # 325, Elgie neo BLACK # 325, Elgie neo COPPER # 325, Elgie neo PINK # 325, Elgie neo YELW25 R-GOLD # 500, Lg neo B-GOLD # 500, Lg neo S-GOLD # 500 (above, manufactured by Oike Imaging Co., Ltd.). Commercially available pearl pigments include Iriodin 205 Rutileplatinum Gold (43% titanium oxide particle size: 10-60 μm), 215 Rutile Red Pearl (47%, particle size: 10-60 μm), 219 Rutile Pearl Pearl ( 48%, particle diameter 10-60 μm), 225 (52%, particle diameter 10-60 μm), 235 (57%, particle diameter 10-60 μm) (above, manufactured by Merck Japan Ltd.), PEARL-GLIZE MB-100R (titanium oxide coverage 52%, particle size 10-60 μm), MG-100R (57%, particle size 10-60 μm), MR-100R (47%, 10-60 μm), MV-100R (48%, particle size 10-60 μm), MRB-100 R (47%, particle diameter 10-60 μm), MY-100R (43%, particle diameter 10-60 μm), MB-100RF (62%, particle diameter 5-30 μm), MG-100RF ( 65%, particle diameter 5-30 μm), MRB-100RF (56, particle diameter 10-30 μm), MY-100RF (57%, particle diameter 5-30 μm), ULTIMICA YB-100 (titanium oxide coating) 43%, particle diameter 5-30 μm), YD-100 (43%, particle diameter 10-60 μm), RB-100 (47%, particle diameter 5-30 μm), RD-100 (47). %, Particle diameter 10-60 μm), VB-100 (48%, 5-30 μm), VD-100 (48%, particle diameter 10-60 μm), GB-100 (65%, same) 5-30 μm), GD-1 0 (the same 65%, 10~60μm) (or more, Japan Koken Kogyo Co., Ltd.), and the like. Among them, the ELG series manufactured by Oike Imaging Co., Ltd. is preferable, and the # 325 series is the most preferable among them, since a very large glitter can be obtained. The amount of these metal pigments to be used is preferably 1.0% by weight or more and 40.0% by weight or less, more preferably 3.0% by weight or more and 30.0% by weight or less, with respect to the total amount of the ink composition. It is most preferably 0% by weight or more and 25.0% by weight or less. If the amount used is less than 1.0% by weight, the light resistance of the handwriting becomes weak. On the other hand, when the amount is more than 40.0% by weight, a problem that the writing taste becomes heavy due to writing scraping due to clogging due to sedimentation with time or an increase in solid content in the ink composition tends to occur.

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

  In order to increase the dispersion efficiency of the pigment used in the water-based ink, a commercially available water-dispersed pigment or a finely dispersed pigment in a polymer compound is preferably used because the handleability and productivity increase. Specific examples of water-dispersed pigments include Fuji SP Black 8031, 8119, 8167, 8276, 8381, 8406, Fuji SP Red 5096, 5111, 5193, 5220, Fuji SP Bordeaux 5500, Fuji. SP Blue 6062, 6133, 6134, 6401, Fuji SP Green 7051, Fuji SP Yellow 4060, 4178, Fuji SP Violet 9011, FujiSP Pink 9524, 9527, Fuji SP OrangeF 34 U 5543, 5544 (Fuji Dye Co., Ltd.), Emacol Black CN, Emacol B ue FBB, FB, KR, Emacol Green LXB, Emacol Violet BL, Emacol Brown 3101, Emacol Carmine FB, Emacol RedBS, Emacol Orange R, Egol NG01, Egol Yellow FD Same F5G, Same F7G, Same 10GN, Same 10G, Sandy Super Black K, Same C, Sandy Super GrayB, Sandy Super Brown SB, FRL, Same RR, Sandy Super G5, L5G , HB, FBL-H, FBL-160, FBB, Sandye S per Violet BL H / C, same BL, Sandy Super Bordeaux FR, Sandy Super Pink FBL, F5B, Sandy Super Rubine FR, Sandy super Carmin FB, Sandy super Carbine FB , R, BO, Sandy Gold Yellow 5GR, R, 3R, Sandye Ywllow GG, F3R, IRC, FGN, GN, GRS, GSR-130, GSN-130, GSN, 10GN (above, manufactured by Sanyo Dye Co., Ltd.), Rio Fast BlackFx 8012, 8313, 8169, Rio Fast ed Fx 8209, 8172, Rio Fast Red S Fx 8315, 8316, RioFast Blue FX 8170, Rio Fast Blue FX 8170, Rio Fast Blue S FX 8312, Rio 83 G Ink Co., Ltd.), NKW-2101, 2102, 2103, 2104, 2105, 2106, 2107, 2108, 2117, 2127, 2137, 2167, 2101P, 2102P, 2103P, 2104P, 2105P, 2106P, 2106P, 2107P, 2108P, 2117P, 2127P, 2137P, 2167P, NKW-3002, 3003, 30 4, 3005, 3007, 3077, 3008, 3402, 3404, 3405, 3407, 3408, 3477, 3602, 3603, 3604, 3605, 3607, 3607, 3608, 3702, 3703, 3704, 3705, 3777, 3708, 6013, 6038, 6559 (manufactured by Nippon Fluorescence Co., Ltd.), Cosmo Color S1000F Series (Toyo Soda Co., Ltd.) Manufactured), 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 (above, Gokoku Dye Co., Ltd.), PO Polx series such as Plux PC5T1020, Pollux Black PC8T135, Polook Thread IT1030 (supplied by Sumika Color Co., Ltd.), and the like. Examples of the finely dispersed pigments in the polymer compound in advance include Microlith Yellow 3G. -K, Yellow 4G-K, Yellow 3R-K, Scarlet RK, DPP Red BK, Magenta 5B-K, Violet BK, Blue A3R-K, Blue 4G- K, Green G-K, Black CK, White RK (pigment finely dispersed in vinyl chloride / vinyl acetate copolymer resin, manufactured by Ciba Specialty Chemicals), 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.), Microlith Yellow 2G-T, Yellow 3R-T, Brown 5R-T, Scarlet RT, Red BR- T, Blue GS-T, Green GT, Black CT (pigment finely dispersed in rosin ester resin, manufactured by Ciba Specialty Chemicals), Microlith Yellow 4G-A, Yellow MX- A, Yellow 2R-A, Brown 5R-A, Scarlet RA, Red 2C-A, Red 3R-A, Magenta 2B-A, Violet B-A, Blue 4G-A, Green G-A, Black C-A, White R-A (Ethyl Cellulo Pigment finely dispersed in resin, manufactured by Ciba Specialty Chemicals), 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 Products Co., Ltd.), Renol Yellow GG-HW, Yellow HR-HW, Orange RL-HW, Red FGR-HW Red HF2B-HW, Red F5RK-HW, Carmin FBB-HW, Violet RL-HW, Blue B2G-HW, Green GG-HW, Brown HFR-HW, Black R-HW, Same White T-HW (pigment finely dispersed in polyvinyl butyral resin, Clariant Manufactured by Capan Co., Ltd.), Fuji AS Black 810, AS Red 575, AS Blue 650, AS Green 737, AS White 165 (pigment finely dispersed in polyvinyl butyral resin, manufactured by Fuji Dye Co., Ltd.), etc. Is mentioned. These colorants can be used alone or in combination of two or more, and the amount used is preferably 1.0% by weight or more and 55.0% by weight or less based on the total amount of the ink composition. It is more preferably 10.0% by weight or more and 50.0% by weight or less. If the amount used is less than 10.0% by weight, the handwriting is too thin and difficult to read. When the amount is more than 50.0% by weight, the handwriting is liable to be lost over time due to an increase in the solid content.

  Water is used as one of the solvents, and any of tap water, ion exchange water, purified water, distilled water, pure water, ground water, deep ocean water, and the like may be used. Among these, ion exchange water, purified water, distilled water, and pure water are preferable. In addition, although the addition method of water is not specifically limited, Even if it adds water as it is in the ink composition which mixed components other than water suitably, a coloring agent, resin, surfactant, other additives, etc. The components used in the ink composition may absorb moisture or absorb water in advance.

  Conventionally known organic solvents can be used in combination for various purposes as water-based inks, for example, prevention of ink freezing at low temperatures and prevention of ink drying at the nib. Specific examples of the organic solvent include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, and 3-methyl- Alcohols such as 3-methoxy-pentanol benzyl alcohol, 2-methyl-2,4-pentanediol, β-phenylethyl alcohol, α-methylbenzyl alcohol, lauryl alcohol, tridecyl alcohol, isododecyl alcohol, isotridodecyl alcohol Solvents, 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, diethylene glycol monophenyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl Vinyl ether, tripropylene glycol monobutyl ether, glycol ethers such as tripropylene glycol monomethyl ether, and propylene glycol methyl ether acetate, propylene glycol diacetate, 2-pyrrolidone, N- methyl-2-pyrrolidone. These organic solvents may be used alone or in combination of two or more, and the amount used is preferably 10.0% by weight or more and 90.0% by weight or less based on the total amount of the ink composition. The reason is not clear, but in particular, when hexylene glycol, water, and sugar alcohol are used in combination, fluid lubrication is likely to occur at a lower relative speed. More preferably, it is 8.0 weight% or more.

  Specific examples of organic solvents that can be used in oil-based inks include ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether , Ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol Cole dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, triethylene glycol Ethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether, propylene glycol tertiary butyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene Glycol ethers such as glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butyl acetate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol Hexylene glycol , Octylene glycol, glycerin, polyethylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 1,3-butanediol, glycols such as 1,5-pentanediol, benzyl alcohol, β -Phenylethyl alcohol, α-methylbenzyl alcohol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, 3 -Alcohols such as methoxy-3-methylpentanol, lauryl alcohol, tridecyl alcohol, isodecyl alcohol, isotridecyl alcohol, methyl isopropyl ether, ethyl ether, ethyl propyl ether, ethyl butyl ether, isopropyl Examples thereof include ethers such as ether, butyl ether, hexyl ether and 2-ethylhexyl ether, and esters such as 2-ethylhexyl acetate, isobutyl isobutyrate, ethyl lactate and butyl lactate. Among them, ethylene glycol monophenyl ether, hexylene glycol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, diethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol mono Butyl ether, ethylene glycol monoisobutyl ether, and benzyl alcohol are preferred.

  When a part of the low boiling point organic solvent is used, it is easy to reduce the viscosity of the ink, and it is suitable for reducing the writing quality. Specific examples of low-boiling organic solvents that can be used include organic solvents having a boiling point of 200 ° C. or lower, hexylene glycol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, diethylene glycol monomethyl ether, Examples include ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol monoisobutyl ether.

  In consideration of writing quality and nib drying properties, it is preferable to use a low boiling organic solvent having a boiling point of 200 ° C. or less and a high boiling organic solvent having a boiling point exceeding 200 ° C. in combination. The value of low boiling point organic solvent / high boiling point organic solvent is preferably 1.0 to 30.0, more preferably 1.3 to 6.0, in terms of weight ratio.

  These organic solvents can be used alone or in combination, and the amount used is preferably 10.0% by weight or more and 90.0% by weight or less based on the total amount of the ink composition.

  When water is added to the oil-based ink in an amount of 1.0% by weight or more and 15.0% by weight or less, a smooth writing feeling is obtained. Therefore, it is preferable to add water to the oil-based ink as a solvent. It is more preferable to adjust the water-based ink to a water content of 2.5% by weight or more and 10.0% by weight or less including the water previously contained in the organic solvent by wetting or moisture absorption.

  In addition to the above components, a dispersion resin, a thickening resin, a lubricant, a receiving wear inhibitor, an antifoaming agent, a wetting agent, an antiseptic, a rust preventive, a pH adjuster, a solid lubricant, and an extender pigment, if necessary It is also possible to use additives such as these together.

  When a pigment is used in a water-based ink, a surfactant or a water-soluble polymer as a dispersion aid and a penetrating agent is used. For example, styrene-acrylic acid copolymer, styrene-maleic acid copolymer, acrylic acid-acrylic acid ester copolymer salt, shellac, humic acid resin, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl, etc. Surfactants such as ether, polyoxyethylene alkyl ether phosphoric acid and salts thereof, polyoxyethylene / polyoxypropylene alkyl ether, and polyoxyethylene sorbitan fatty acid esters can be used as necessary. In particular, as dispersion aids and penetrants that do not inhibit the gelation performance of the lipid peptide of the present invention, polymer dispersants SOLPERSE 27000 and 54000 (above, manufactured by Nippon Lubrizol Co., Ltd.), polyoxyalkylene groups are used. Marialim AKM-0531, AFB-0561, AFB-1521, AEM-3511, AAB-0851, AWS-0851, AKM-1511-60, HKM-50A, HKM -150A, HFB-150A (manufactured by NOF Corporation) and the like. Furthermore, as a viscosity modifier, water-soluble synthesis of polyvinyl alcohol, polyacrylic acid soda, polyacrylamide, alkyl acid-alkyl methacrylate copolymer, polyethylene oxide, polyvinyl pyrrolidone, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, cellulose, and derivatives thereof. Polysaccharides such as macromolecules, microorganism-derived xanthan gum, succinoglycan, welan gum (manufactured by Sanki Co., Ltd.), Arcacylan, Arcacy gum, Zeta Seagum (manufactured by Hakuto Co., Ltd.), etc. Further, seed polysaccharides such as guar gum, locust bean gum and derivatives thereof, and resin polysaccharides such as tarragant gum can be used.

  These resins can be used alone or in combination. The amount of these resins used is preferably 0.05% by weight or more and 30.0% by weight or less, and more preferably 1.0% by weight or more and 10.0% by weight or less with respect to the total amount of the ink composition.

  When a pigment is used in the oil-based ink, a dispersion resin or a thickening resin can be used. Dispersion resin and thickening resin are added to disperse solids such as pigments, impart stringing properties, prevent handwriting show-off, adjust viscosity, and promote dissolution of dyes. Ester gum, xylene resin, alkyd resin, polyvinyl pyrrolidone, acrylate resin, melamine resin, cellulose resin, cyclohexanone, acetophenone, urea and other ketone and formaldehyde condensation resins, cyclohexanone condensation resin and hydrogenation of them Resin, maleic acid resin, copolymer of styrene and maleic ester, copolymer of styrene and acrylic acid or ester thereof, polyamide, epoxy resin, polyvinyl alkyl ether which is a condensate of polymerized fatty acid and polyamines , Coumarone-indene resin, polyterpene, rosin resin The hydrogenated product, rosin-modified maleic acid resin, rosin-modified phenol resin, vinylpyrrolidone-vinyl acetate copolymer, polymethacrylic acid ester, polyoxyethylene, polyvinyl butyral resin, polyvinyl alcohol resin, polyvinyl acetal resin, Copolymers of vinyl acetate and polyvinyl pyrrolidone, acrylic resin salts, copolymers of acrylic acid and alkyl methacrylate or salts thereof, cellulose derivatives such as hydroxypropylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, ethylcellulose, hydroxypropylated guar gum, Methyl cellulose, ethyl cellulose, polyvinyl acetamide, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyvinyl alcohol Le acids, polysaccharides such as carboxyvinyl polymers, mention may be made of benzylidene sorbitol. In particular, a polyvinyl butyral resin can be suitably used because it has a small viscosity change with time and is excellent in pigment dispersion stability and fixability. Specific examples of the polyvinyl butyral resin include Mowital B20H, B30B, B30H, B60T, B60H, B60HH, B70H (above, manufactured by Hoechst, Germany), S-REC BH-3, BL-1, BL-2, BL-L, BL-S, BM-1, BM-2, BM-5, BM-S, BL-2H, BL-SH, BX-10, BX-L, BH-3, BH-6, BH-S, BX-1, and BX-5 (Sekisui Chemical Co., Ltd.). Among these, ESREC BL-1, BL-10, BH-3, and BM-1 are preferable as the dispersion stabilizer. Specific examples of polyvinylpyrrolidone include polyvinylpyrrolidone K-30, K-85, K-90 (above, manufactured by Nippon Shokubai Co., Ltd.), PVP K-15, K-30, K-60, The same K-90, the same K-120 (above, ISP Japan Co., Ltd. product) etc. are mentioned. Specific examples of polyvinylacetamide include GE191-000, GE191-053, GE191-103, GE191-104, GE191-107, GE191-405 (Showa Denko Co., Ltd.) and the like. Although the reason is not certain, among them, polyvinylpyrrolidone K-30, K-85, K-90 (above, manufactured by Nippon Shokubai Co., Ltd.), PVP K-15, K-30, K-60, By using K-90 and K-120 (made by ISP Japan Co., Ltd.) together with hexylene glycol, the friction coefficient in the relative speed range of 0.001 m / sec to 1.0 m / sec. The lower limit value is equal to or less than the friction coefficient when the relative speed is 0.001 m / sec, and the friction coefficient at a speed obtained by adding 0.4 m / sec to the relative speed from the relative speed indicating the friction coefficient of the lower limit value. The slope of the straight line connecting the point and the point indicating the lower limit value is 6.0 or less, which is preferable as a spinnability imparting agent.

  These resins can be used alone or in combination. The amount of these resins used is preferably 0.05% by weight or more and 30.0% by weight or less, and more preferably 1.0% by weight or more and 10.0% by weight or less with respect to the total amount of the ink composition.

  The lubricant is added to smooth the rotation of the ball and improve the writing feeling.

  Examples of lubricants that can be used in water-based inks include phosphate esters, neutralized phosphate esters, phosphate derivatives, sugars, sugar alcohols, and the like.

  Phosphoric acid derivatives that can be used in water-based inks are generally used to improve the lubricity between the ball and the chip body and obtain a smooth writing feel. Specific examples of phosphoric acid derivatives include NIKKOL DLP-10, DOP-8NV, DDP-2, DDP-4, DDP-6, DDP-8, DDP-10, TLP-4, TCP-5, TOP-0V, TDP-2, TDP-6, TDP-8, TDP-10 (Nikko Chemicals Co., Ltd.), Phosphanol RB-410, BH-650, ED -200, same ML-220, same ML-240, same RS-410, same RS-610, same RS-710, same RL-210, same RL-310, same RD-720N (Toho Chemical Co., Ltd.), Examples include PRISURF A212C, A215C, A208F, A208N, M208F, A208B, 219B, DB01, A210D, (Dainichi Pharmaceutical).

  These can be used alone or in combination, and the amount used is preferably 0.3 wt% or more and 5.0 wt% or less, and more preferably 1.0 wt% or more and 3.0 wt%, based on the total amount of the ink composition, as a solid content. More preferred. If it is less than 0.3% by weight, there may be no sufficient effect, and even if added over 5.0% by weight, the effect is not improved and there is no meaning of adding.

  Examples of lubricants that can be used in oil-based inks include cutting oils, higher fatty acids, phosphate esters, neutralized phosphate esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil and derivatives thereof, Examples include acylamino acids, thiazoles, polyethylene glycols, polyol-modified silicones, sugars, and sugar alcohols. It is preferable to use phosphate ester, polyoxyethylene hydrogenated castor oil, and polyol-modified silicone because the writing feeling can be maintained in a good state over a long period of time. These can be used alone or in combination.

  Among lubricants that can be used in oil-based inks, phosphate esters having an unsaturated hydrocarbon group in the molecule are more preferred. Specific examples include monooleyl phosphate, polyoxyethylene monooleyl ether phosphate, dioleyl phosphate, polyoxy Ethylene dioleyl ether phosphate, trioleyl phosphate ester, polyoxyethylene trioleyl ether phosphate, monolinol phosphate ester, polyoxyethylene monolinol ether phosphate, dilinol phosphate ester, polyoxyethylene dilinol ether phosphate, Examples include trilinol phosphate ester and polyoxyethylene trilinol ether phosphate, and commercially available phosphanol RB-410 (polyoxyethylene oleyl ether phosphate), phosphanol. LB-400 (polyoxyethylene oleyl ether phosphate) (manufactured by Toho Chemical Industry Co., Ltd.), NIKKOL DOP-8NV (polyoxyethylene oleyl ether sodium phosphate), NIKKOL TOP-0V (trioleyl phosphate) ( As mentioned above, Nikko Chemicals Co., Ltd.) can be mentioned. The phosphoric acid ester compound having an unsaturated hydrocarbon group in the molecule that can be used in the present invention includes a phosphoric acid ester compound having a benzene ring, such as oxyethylene phenyl ether phosphoric acid, oxyethylene alkyl phenyl ether phosphoric acid, Examples thereof include oxyethylene phenyl ether phosphoric acid and polyoxyethylene alkyl phenyl ether phosphoric acid.

  Although the reason is not clear, the phosphate ester compound having an unsaturated hydrocarbon group in the molecule is better written than the phosphate ester compound having no unsaturated hydrocarbon group in the molecule. These are preferably used in an amount of 0.05 to 20.0% by weight, more preferably 0.1 to 10.0% by weight, based on the total amount of the ink composition. If the amount used is less than 0.05% by weight, the writing quality is not sufficient. The solubility of the solid content in the material is insufficient, and there is a risk that writing scraping is likely to occur or the surface tension of the ink is reduced, and the ink may leak when left with the pen tip facing downward. These can be used alone or in combination.

  Examples of receiving wear inhibitors include alumina, silicon carbide, chromium oxide, boron carbide, zircon, sericite, jadeite, calcium fluoride, tungsten carbide, silica, diamond, garnet, aluminum nitride, and silicon nitride. Can be mentioned. Among these, alumina is preferable as an antiwear agent. The addition amount can be 0.001% by weight or more and 0.1% by weight or less based on the total amount of the ink composition. It is more preferably 0.004% or more and 0.03% or less, and most preferably 0.01% by weight or more and 0.25% by weight or less. These can be used alone or in combination.

  The receiver antiwear agent may be added to the ink as it is, or may be previously dispersed in a solvent with a dispersion resin such as butyral resin or polyvinylpyrrolidone.

  In addition, wetting agents such as urea, ethylene urea and thiourea, antiseptics such as benzothiazoline and omadin, rust inhibitors such as benzotriazole, and styrene-acrylic copolymers for fixing pigments to the writing surface PH adjusters such as sodium salt, 2,2-aminomethyl-1,3-propanediol, triethanolamine, and diethanolamine Various additives such as antifoaming agents such as silicone emulsions, solid lubricants such as alumina and chromium oxide, extender pigments such as aluminum silicate, calcium carbonate, and resin spheres may be used as necessary. These can be used alone or in combination.

  Sugar and sugar alcohol are used to lower the friction coefficient. Specific examples of sugars include aldotriose, erythrose, threose, ribose, lyxose, xylose, arabinose, allose, talose, gulose, glucose, altrose, mannose, galactose, idose, ketotriose, erythrulose, xylulose, ribulose, Psicose, fructose, sorbose, tagatose, deoxyribose, fucose, fucose, rhamnose, cedoheptulose, etc., disaccharides such as sucrose, lactose, maltose, trehalose, tulanose, cellopioth, etc., trisaccharides such as raffinose, melezitose, maltotriose, etc. Acarbose, stachyose, etc. as tetrasaccharides, fructooligosaccharides, galactooligosaccharides, mannan oligosaccharides as oligosaccharides Etc. is, glycogen as polysaccharides, amylose, amylopectin, cellulose, dextrin, glucan, fructans, such as N- acetylglucosamine and the like.

  Sugar alcohol usually refers to a chain polyhydric alcohol in which the carbonyl group of sugar is reduced, xylitol, sorbitol, mannitol, maltitol, lactitol, erythritol, palatinose, low glycated reduced starch syrup, medium saccharified reduced starch syrup, Examples include highly saccharified and reduced starch syrup.

  Commercially available products include SEE 20 (solid content concentration 70%, sugar alcohol composition: monosaccharide alcohol 3% to 7%, disaccharide alcohol 60% to 67%, trisaccharide alcohol 14% to 20%, Sugar alcohol 1% to 5%, pentasaccharide alcohol 5% to 20%, water activity value (70%, 20 ° C.) 0.86, viscosity (25 ° C.) 400 mPa · s), ST 30 (solid content concentration) 70%, sugar alcohol composition: monosaccharide alcohol 4% to 10%, disaccharide alcohol 6% to 12%, trisaccharide alcohol 11% to 16%, tetrasaccharide alcohol 5% to 8%, pentasaccharide alcohol 51% to 68%, water activity value (70%, 20 ° C.) 0.90, viscosity (25 ° C.) 1800 mPa · s), S57 (solid content concentration 70%, sugar alcohol composition: Sugar alcohol 3% to 10%, disaccharide alcohol 43% to 55%, trisaccharide alcohol 15% to 25%, tetrasaccharide alcohol 1% to 5%, pentasaccharide alcohol 5% to 38%, Water activity value (70%, 20 ° C.) 0.87, viscosity (25 ° C.) 500 mPa · s), S100 (solid content concentration 70%, sugar alcohol composition: monosaccharide alcohol 1% to 10%, disaccharide alcohol 6% to 12%, trisaccharide alcohol 7% to 12%, tetrasaccharide alcohol 5% to 10%, pentasaccharide alcohol 64% to 82%, water activity value (70%, 20 ° C.) 91, viscosity (25 ° C.) 4500 mPa · s), 500 (solid content concentration 70%, sugar alcohol composition: monosaccharide alcohol 37% to 43%, disaccharide alcohol 26% to 32 Hereinafter, trisaccharide alcohol 15% to 21%, tetrasaccharide alcohol 6% to 10%, pentasaccharide alcohol 4% to 8%, water activity value (70%, 20 ° C.) 0.80, viscosity (25 ° C) 300 mPa · s), SE 600 (solid content concentration 70%, sugar alcohol composition: monosaccharide alcohol 40% to 50%, disaccharide alcohol 40% to 50%, trisaccharide alcohol 8% to 13%, Tetrasaccharide alcohol 1% to 5%, pentasaccharide alcohol 1% to 5%, water activity value (70%, 20 ° C.) 0.80, viscosity (25 ° C.) 200 mPa · s) (above, food science Diatrole L (solid content 70%, sugar alcohol composition: monosaccharide alcohol 10% or less, disaccharide alcohol 10% to 20%, trisaccharide alcohol 10% to 20%, Tetrasaccharide alcohol to 60% to 70%, viscosity (70% at 25 ° C.) 1100 cP), diatomole (solid content 70%, sugar alcohol composition: monosaccharide alcohol 10% or less, disaccharide alcohol 50% to 56%, Trisaccharide alcohol 15% to 25%, tetrasaccharide alcohol 20% to 25%, viscosity (70% at 25 ° C.) 500 cP), Diatol K (solid content 70%, sugar alcohol composition: monosaccharide alcohol 7% or less , Disaccharide alcohol 61% to 67%, trisaccharide alcohol 20% or less, tetrasaccharide alcohol 20% to 20%, viscosity (70% 25 ° C.) 400 cP), Diatol N (solid content 70%, sugar alcohol composition: simple Sugar alcohol 42% to 48%, disaccharide alcohol 27% to 33%, trisaccharide alcohol 10% to 15%, tetrasaccharide alcohol or more 0% or more and 15% or less, viscosity (70% at 25 ° C.) 200 cP), Diator P (solid content 70%, sugar alcohol composition: monosaccharide alcohol 44% or more and 50% or less, disaccharide alcohol 32% or more and 38% or less, Trisaccharide alcohol 5% or more and 15% or less, tetrasaccharide alcohol or more and 5% or more and 15% or less, viscosity (70% 25 ° C.) 190 cP) (above, manufactured by Sanei Saccharification Co., Ltd.), reduced dextrin, reduced maltodextrin, etc. It is done.

  These sugars and / or sugar alcohols can be used singly or in combination of two or more, and the blending amount can be suitably used at 1.0 wt% or more and 50.0 wt% or less with respect to the total amount of the ink composition. 5.0 wt% or more and 40.0 wt% or less is more preferable, and 10.0 wt% or more and 35.0 wt% or less is most preferable. Sugar alcohol is more preferable because it is less hydrolyzed than sugar and has high stability. The reason is not clear, but sugar alcohols in which the ratio of tetra- or higher sugar alcohols in the sugar-alcohol composition is 50% or more is preferable because it tends to lower the friction coefficient, and more preferably 60% or more. A sugar with a higher water activity value has more free water and is more compatible with water, and the ink flow improves and the coefficient of friction tends to decrease. Therefore, the water activity value is preferably 0.85 or more, more preferably 0.90 or more. .

  The ink composition for ballpoint pens of the present invention is any one of 5% by weight or more of hexylene glycol, 4.0% by weight or more of polyvinylpyrrolidone, 20.0% by weight or more of sugar, and 20.0% by weight or more of sugar alcohol. By using one or more in combination, the lower limit of the friction coefficient in the range of relative speed 0.001 m / sec to 1.0 m / sec is less than the friction coefficient when the relative speed is 0.001 m / sec. The slope of a straight line connecting the point indicating the friction coefficient at a speed obtained by adding 0.4 m / sec to the relative speed from the relative speed indicating the friction coefficient of the lower limit value and the point indicating the lower limit value Can be obtained as an ink composition having a pH of 6.0 or less.

  In producing the ink composition of the present invention, various conventionally known methods can be employed. For example, Henschel mixer, propeller stirrer, homogenizer, turbo mixer, water, solvent, and polysaccharides are added to a stirrer such as Henschel mixer, propeller stirrer, homogenizer, turbo mixer, high pressure homogenizer, etc. It can be easily obtained by adding a colorant dispersed by a dispersing machine such as a high-pressure homogenizer, a ball mill, a bead mill, or a roll mill and other remaining components, and further mixing and stirring.

  In these preparation steps, the generated heat of dispersion can be used as it is, or the mixture can be stirred, heated or cooled. You may perform the removal of the foam by a defoamer, filtration of the coarse thing by a filter, etc. as needed. Further, an aging process may be performed after adjusting the ink in order to make the dispersibility of the polysaccharide sufficient.

Test method 1
The measurement for measuring the relationship between the relative speed and the friction coefficient of the ink composition at a constant load was performed by attaching a tribological cell T-PTD 200 to an MCR302 rheometer (manufactured by Anton Paar, Germany). The ball 1b used had a diameter of 12.7 mm, a material of SUS 316, and a receiving plate 2b of a length of 15 mm, a width of 6 mm, a height of 3 mm, and a material of SUS 316.

  The measurement conditions were: measurement temperature: 25 ° C., load in the normal direction; 2.12 N, number of measurement points: 300 (time unit: S), measurement point interval fixed, measurement point interval 1 S, interval 300 S, start rotational speed 0. 1 rpm, final rotation speed of 3,000 rpm, variable; speed (unit: rpm), conditions: logarithmic elevation. Regarding the relationship between the rotational speed and the relative speed, the rotational speed of 0.1 rpm to 3,000 rpm corresponds to a relative speed of 0.00001 m / sec to 1.4 m / sec.

  Three receiving plates 2b are set on the surface of the pot 2, and 1.0 g of the ink composition 3 is added, and then a normal load of 2.12N is applied for 1 minute without first recording. The friction coefficient in the range of relative speed 0.00001 m / sec to 1.4 m / sec at a constant load of 2.12 N in the direction was recorded.

Test method 2
Written sensory test In the above-mentioned sensory test, 30 people are selected at random, and a regular triangle with a side of 10 cm is copied five times at an average writing speed of 0.1 m / sec or more and less than 1.0 m / sec on the copy paper. ◎ If you feel that you can write lighter and smoother than the initial speed in the process of reaching the fastest speed and decelerating, ◎, if you feel that you can write lightly and smoothly from the initial speed in the process of reaching the fastest value from the initial speed and decelerating ○ The evaluation was made with x which was not felt. Using an apparatus that detects and outputs the movement of the writer's nib plane as XY coordinates, 60 plots are made per second, and the average writing speed is calculated from the movement distance of the writer's nib and the time taken for the movement.

  The average writing speed in Test Method 2 is a value corresponding to the relative speed in Test Method 1.

  Hereinafter, it demonstrates still in detail based on an Example and a comparative example.

Example 1
C. I. Pigment BLACK 7 (FUJI SP BLACK 8041, pigment, manufactured by Fuji Dye Co., Ltd.) 3.00% by weight
Hexylene glycol (Mitsui Chemicals, Inc.) 10.00% by weight
Ethylene glycol 5.00% by weight
Ion-exchanged water 45.00% by weight
Phosphanol LB-400 (polyoxyethylene oleyl ether phosphate, manufactured by Toho Chemical Industry Co., Ltd.) 1.50% by weight
1,2-Benzisothiazol-3 (2H) -one (Proxel GXL (S), manufactured by Arch Chemicals Japan Ltd.) 0.15% by weight
JPDX7323 (manufactured by BASF Japan Ltd.) 1.00% by weight
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.30% by weight
PVP K-90 (polyvinylpyrrolidone, molecular weight 1300000, manufactured by ISP Japan Co., Ltd.) 4.00% by weight
Sodium hydroxide 0.05% by weight
S100 (saccharified starch, manufactured by Food Science Co., Ltd.) 30.00% by weight
After the above components are dispersed with a homogenizer, the pH is adjusted to 8.3 with a 20% aqueous solution of sodium hydroxide, coarse particles are removed with a filter or the like, defoamed with a defoamer, and black aqueous An ink composition was obtained.
In the measurement of Test Method 1, the lower limit friction coefficient was 0.0631, and the relative speed at that time was 0.191 m / sec. Further, the friction coefficient at a relative speed of 0.591 m / sec obtained by adding 0.4 m / sec to the lower limit relative speed of 0.191 m / sec was 0.128. The slope of the straight line connecting the two points was 0.16.

Example 2
C. I. Pigment BLACK 7 (FUJI SP BLACK 8041, pigment, manufactured by Fuji Dye Co., Ltd.) 3.00% by weight
Hexylene glycol (Mitsui Chemicals, Inc.) 10.00% by weight
Ethylene glycol 5.00% by weight
Ion-exchanged water 45.00% by weight
Phosphanol LB-400 (polyoxyethylene oleyl ether phosphate, manufactured by Toho Chemical Industry Co., Ltd.) 1.50% by weight
1,2-Benzisothiazol-3 (2H) -one (Proxel GXL (S), manufactured by Arch Chemicals Japan Ltd.) 0.15% by weight
JPDX7323 (manufactured by BASF Japan Ltd.) 1.00% by weight
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.30% by weight
Sodium hydroxide 0.03% by weight
S100 (saccharified starch, manufactured by Food Science Co., Ltd.) 34.00% by weight
After the above components are dispersed with a homogenizer, the pH is adjusted to 8.4 with a 20% aqueous solution of sodium hydroxide, coarse particles are removed with a filter or the like, defoamed with a defoamer, and black aqueous An ink composition was obtained.

  In the measurement of Test Method 1, the lower limit friction coefficient was 0.0287, and the relative speed at that time was 0.252 m / sec. Further, the friction coefficient at a relative speed of 0.652 m / sec obtained by adding 0.4 m / sec to the lower limit relative speed of 0.252 m / sec was 0.0485. The slope of the straight line connecting the two points was 0.06.

Example 3
C. I. Pigment BLACK 7 (FUJI SP BLACK 8041, pigment, manufactured by Fuji Dye Co., Ltd.) 5.00% by weight
Hexylene glycol (Mitsui Chemicals) 15.00% by weight
Ethylene glycol 7.00% by weight
Ion-exchanged water 60.80% by weight
Phosphanol LB-400 (polyoxyethylene oleyl ether phosphoric acid, manufactured by Toho Chemical Industry Co., Ltd.) 2.00% by weight
1,2-Benzisothiazol-3 (2H) -one (Proxel GXL (S), manufactured by Arch Chemicals Japan Ltd.) 0.15% by weight
JPDX7323 (manufactured by BASF Japan Ltd.) 1.50% by weight
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.50% by weight
PVP K-90 (polyvinylpyrrolidone, molecular weight 1300000, manufactured by ISP Japan Co., Ltd.) 8.00% by weight
Sodium hydroxide 0.05% by weight
After the above components are dispersed with a homogenizer, the pH is adjusted to 8.2 with a 20% aqueous solution of sodium hydroxide, coarse particles are removed with a filter or the like, defoamed with a defoamer, and black aqueous An ink composition was obtained.

  In the measurement of Test Method 1, the lower limit friction coefficient was 0.0696, and the relative speed at that time was 0.332 m / sec. The friction coefficient at a relative speed of 0.732 m / sec obtained by adding 0.4 m / sec to the lower limit relative speed of 0.332 m / sec was 0.0924. The slope of the straight line connecting the two points was 0.05.

Comparative Example 1
Ethylene glycol 80.0% by weight
Water Black 256L (manufactured by Orient Chemical Co., Ltd.) 20.0% by weight
The above components were stirred with a magnetic stirrer for 10 minutes, coarse particles were removed with a filter or the like, and defoamed with a defoamer to obtain a black aqueous ink composition.

Comparative Example 2
Ion exchange water 80.0% by weight
Water Black 256L (manufactured by Orient Chemical Co., Ltd.) 20.0% by weight
The above components were stirred with a magnetic stirrer for 10 minutes, coarse particles were removed with a filter or the like, and defoamed with a defoamer to obtain a black aqueous ink composition.

Comparative Example 3
Water Black 256L (manufactured by Orient Chemical Co., Ltd.) 35.0% by weight
Water Yellow 1 (CI Acid Yellow 23, manufactured by Orient Chemical Co., Ltd.) 2.00% by weight
Glycerin 10.0% by weight
Ion-exchanged water 25.0% by weight
Ethylene glycol 24.2% by weight
Sodium hydroxide 0.30% by weight
Oleoyl sarcosine 3.00% by weight
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.50% by weight
After the above components are dispersed with a homogenizer, the pH is adjusted to 8.2 with a 20% aqueous solution of sodium hydroxide, coarse particles are removed with a filter or the like, defoamed with a defoamer, and black aqueous An ink composition was obtained.

  In FIG. 3, the result of having measured Examples 1-3 and Comparative Examples 1-3 with the test method 1 was shown. Table 1 shows the results of evaluating Examples 1 to 3 and Comparative Examples 1 to 3 using Test Method 2.

以下、図３、表１の結果から、実施例１〜３、比較例１〜３の測定結果、評価結果を詳細に説明する。

Hereinafter, from the results of FIG. 3 and Table 1, the measurement results and evaluation results of Examples 1 to 3 and Comparative Examples 1 to 3 will be described in detail.

  In Examples 1 to 3, the lower limit of the friction coefficient in the range of the relative speed of 0.001 m / sec to 1.0 m / sec is a value equal to or less than the friction coefficient when the relative speed is 0.001 m / sec. The slope of the straight line connecting the point indicating the friction coefficient at the speed obtained by adding 0.4 m / sec to the relative speed from the relative speed indicating the friction coefficient of the lower limit value and the point indicating the lower limit value is 6.0 or less. Therefore, I felt that I could write lighter and smoother than the initial speed in the process of reaching the maximum speed from the initial speed and decelerating.

  In Examples 1 to 3, the lower limit of the friction coefficient in the range of the relative speed of 0.001 m / sec to 1.0 m / sec is a value equal to or less than the friction coefficient when the relative speed is 0.001 m / sec. In addition, the slope of a straight line connecting the point indicating the friction coefficient at a speed obtained by adding 0.4 m / sec to the relative speed from the relative speed indicating the friction coefficient of the lower limit value and the point indicating the lower limit value is 6.0. The range of the slope of a straight line connecting the point indicating the friction coefficient at a speed obtained by adding 0.4 m / sec to the relative speed from the relative speed indicating the friction coefficient of the lower limit value and the point indicating the lower limit value. Although the coefficient of friction was high, it had a smooth writing feeling with no clogging. In Examples 1 to 3, since the ink film is continuously broken on the ball surface and the ball holder surface without being broken by shearing due to the rotation of the ball, the wear of the ball holder by the ball does not proceed. This is because the ball holder could be rotated without being caught.

  In Comparative Examples 1 to 3, the lower limit value of the friction coefficient in the range of the relative speed of 0.001 m / sec to 1.0 m / sec does not become the value of the friction coefficient or less when the relative speed is 0.001 m / sec. Since the coefficient of friction continued to increase from the initial speed to the fastest value, the writing taste was heavy and crisp, and I could not feel light and smooth writing. In Comparative Example 2, the friction coefficient began to increase at a low relative speed among the Comparative Examples, so that the writing feeling was heavier than that of Comparative Examples 1 and 3, and the writing feeling was caught.

  In Comparative Examples 1 to 3, the lower limit value of the friction coefficient in the range of the relative speed of 0.001 m / sec to 1.0 m / sec is a value equal to or less than the friction coefficient when the relative speed is 0.001 m / sec. Although there was a relative speed that the coefficient of friction was lower than that of the example in the range, the writing feeling was crisp and it was not a smooth writing feeling. This is because in Comparative Examples 1 to 3, the ink film is easily broken by shearing due to the rotation of the ball, so that it hardly remains on the surface of the ball or the ball holder, and as the relative speed increases, wear of the ball holder by the ball progresses. This is because the friction coefficient increased.

  INDUSTRIAL APPLICABILITY The present invention can be used as a ballpoint pen. More specifically, it is widely used as a water-based ballpoint pen such as a cap type or knock type filled with a ballpoint pen ink composition, an oil-based ballpoint pen, or an emulsion ballpoint pen (O / W ink and W / O ink). Can be used.

DESCRIPTION OF SYMBOLS 1 Rotor 1a Shaft 1b Metal ball 2 Pot 2a Recessed part which accommodates ink composition 3 2b Seat plate 3 Ink composition

Claims (1)

  In an ink composition containing at least a colorant and a liquid medium, at least one seating plate in a recess of a pot containing the ink composition, and a ball that is rotatable while being in contact with the seating plate at the tip Using a measuring instrument comprising at least a rotor provided with a rotor, the seat is placed on a seating plate installed at an inclination of 45 degrees with respect to the rotation axis of the rotor in an ink composition bath placed in an appropriate amount in a recess in the pot. In the measurement to obtain the coefficient of friction when rotating the ball while pressing the ball with a force of 2.12N in the normal direction of the plate and gradually increasing the relative speed by the rotation of the rotor to 1.40 m / sec. The lower limit value of the friction coefficient in the range of speed 0.001 m / sec or more and 1.0 m / sec or less is equal to or less than the friction coefficient when the relative speed is 0.001 m / sec, and the friction coefficient of this lower limit value is shown. relative A point indicating the coefficient of friction in the rate of adding 0.4 m / sec to the relative speed from the time, the slope of the line connecting the points representing the lower limit of the ink composition is 6.0 or less

Images