JP2010168494A - Ink for ball-point pen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink for ball-point pens having extremely light and smooth writing quality even when a strong writing pressure is applied thereto. <P>SOLUTION: The ink for ball-point pens includes a colorant, water and/or an organic solvent, and a mixture of polyoxyethylene castor oil and/or polyoxyethylene hardened castor oil, and a derivative thereof with one or two or more selected from among monoalkyl ether phosphates, polyoxyethylene monoalkyl ether phosphates, dialkyl ether phosphates, polyoxyethylene dialkyl ether phosphates, trialkyl ether phosphates, polyoxyethylene trialkyl ether phosphates, and neutralized materials and solutions thereof. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention provides a ballpoint pen tip comprising at least a ballpoint pen tip composed of a ball for transferring ink to a writing surface such as a paper surface as a writing member, and a ball holder that partially protrudes from the tip opening portion and rotatably holds the ball. The present invention relates to a ballpoint pen ink contained in a ballpoint pen.

In order to obtain a light and smooth writing ink for ballpoint pens, attempts have been made in the past to adjust the viscosity of the ink or add a material imparting lubricity to the ink.
If the viscosity of the ink is lowered by adjusting the addition amount of the thickener, the resistance to the rotation of the ball during writing is reduced, so that there is an advantage that writing can be performed with light writing. However, since the ink has a low viscosity, the ink film formed between the ball and the ball seat is easily moved by the writing pressure, and the ball and the ball seat are directly hit during writing. The crunchy feel of the sound is conveyed to the hand, resulting in a smooth writing experience.
On the other hand, by adding resin or the like to increase the viscosity of the ink and increasing the ink film thickness formed between the ball and the ball seat, smooth writing can be obtained, but the fluidity is low. Since the rotation of the ball was greatly resisted by the ink, it was heavy.

In addition, in order to achieve both light and smooth writing, the viscosity property of the ink is made pseudo-plastic by using a shear thinning agent, and the viscosity is lowered by the high shear force caused by the rotation of the ball applied to the ink during writing. Attempts have been made to reduce the rotational resistance of the ball (Patent Document 1).
Furthermore, when a material imparting lubricity to the ink, such as phosphoric acid ester (Patent Document 2), dipolyoxyethylene alkyl ether phosphoric acid or tripolyoxyethylene alkyl ether phosphoric acid (Patent Document 3) is added to the ink, Since the frictional resistance between the ball and the ball seat during writing is reduced, a smooth writing feel can be obtained. Attempts have been made to obtain a lighter and smoother writing by combining a material that imparts lubricity to such ink and viscosity adjustment with a thickener. (Patent Document 4)

JP 2003-105245 A (the 36th line from the upper right column of page 2 to the 23rd line from the upper right column of page 3) JP 2002-201398 (32nd line from the upper right column of page 2 to 30th line from the upper right column of page 3) Japanese Patent Laid-Open No. 10-279876 (23rd line from the upper right column of page 2 to 15th line from the upper right column of page 3) Japanese Patent Application Laid-Open No. 07-242852 (28th line from the top of the left column on page 2 to 26th line from the top of the left column on page 3)

  In the invention described in Patent Document 1, since the viscosity of the ink is low at the time of writing, a light writing taste is obtained, but the ink film thickness between the ball and the ball seat becomes thin, and the ball and the ball holder There is a problem that the resistance due to the friction that directly comes into direct contact increases, and the ball does not rotate smoothly, resulting in a writing feeling that does not feel smooth.

  The phosphoric acid ester type activators described in Patent Document 2 and Patent Document 3 are present in a form in which the phosphoric acid group is bonded to the ball or the metal surface of the ball seat and the alkyl group is directed toward the ink. The higher the hydrophobicity of the alkyl group, the stronger the hydrophobicity of the alkyl group, so that the metal surface such as balls and ball seats covered with the phosphate ester type activator and water and organic solvents that are the main components in the ink are compatible. It becomes difficult. This reduces the adhesion of ink to the metal surface of the ball or ball seat and makes it difficult for the ink to wet the metal surface.Therefore, the direction of rotation of the ball, the writing angle, and the writing speed change during writing. When there is some change in the discharge flow or when a strong force is applied, there is a part where there is no ink film between the ball and the ball seat, and the ball and the ball seat are instantaneously hit directly. There was a problem that the crisp feel was transmitted to the hand and the writing was smooth. In particular, in the case of an ink having a high viscosity, it is necessary to add a large amount of a lubricant because it tends to be a heavy handwriting. As a result, the ink becomes more difficult to wet on the metal surface, and the problem becomes remarkable. Further, as the writing distance becomes longer, such contact between the ball and the ball seat repeatedly occurs, so that the wear of the seat progresses and the ball sinks, and the retracted ball blocks the ink passage, Distribution volume will decrease. If this happens, less ink will be interposed between the ball and the ball seat, making direct contact between the two more likely to occur and impairing the smoothness. There are also concerns about adverse effects. Furthermore, when the writing tool is tilted and written with the ball retracting, the tip of the ball holder that holds the ball of the ballpoint pen tip touches the surface of the paper and rubs to the hand, and the writing quality deteriorates. was there.

As in Patent Document 4, adding a material that imparts lubricity and adjusting the viscosity of the ink does not improve the wettability of the ink to the metal surface due to the influence of the lubricant. A light and smooth writing taste was not obtained.
Thus, the ink for ball-point pens which can obtain a very light and smooth writing taste and can maintain the writing taste even when the writing distance is long cannot be obtained by the prior art.

  An object of the present invention is to provide a ballpoint pen ink that can obtain a very light and smooth writing taste and that does not deteriorate with the writing distance.

  That is, the present invention is at least one compound selected from the compounds represented by the following general formula (Formula 1) and the compounds represented by any one of the following general formulas (Formula 2), (Formula 3), and (Formula 4). Alternatively, the gist of the ink is a ballpoint pen ink containing a mixture of two or more and a liquid medium.

  The fatty acid group of the compound represented by (Chemical Formula 1) covers a metal surface such as a ball or a ball seat, and the alkyl of the compound represented by any one of (Chemical Formula 2), (Chemical Formula 3), or (Chemical Formula 4) Hydrophobic bonds with each other. Then, the ethylene oxide group of the compound represented by (Chemical Formula 1) interacts with water or an organic solvent present in the ink to form an ink layer on a metal surface such as a ball or ball seat. Since each of the fatty acid groups of the compound represented by (Chemical Formula 1) is sandwiched between two or more ethylene oxide groups, the hydrophilic ethylene oxide groups are contained in the ink while having a highly hydrophobic fatty acid group. Since the molecular chain is easy to extend in the ink and the interaction with water and organic solvents is strong, the ink layer formed on the metal surface is subjected to strong pressure such as writing pressure. In addition to maintaining high lubricity, the wear of the ball seat is also suppressed, the ink discharge amount (circulation amount) does not change significantly, the light and smooth writing taste is maintained, and there are no problems such as blurring. Handwriting lasts.

  Weight ratio in ink of the above general formula (Chemical formula 1) and one or a mixture of two or more selected from the compounds represented by any one of the above general formulas (Chemical formula 2), (Chemical formula 3), and (Chemical formula 4) (Chemical Formula 1) / (Chemical Formula 2) + (Chemical Formula 3) + (Chemical Formula 4) = 0.1 or more and 100 or less, (Chemical Formula 2) + (Chemical Formula 3) + (Chemical Formula 4) ) Is optimal, and the wettability of the ink to the ball seat is maintained, so that an extremely light and smooth writing taste is maintained. As the ink liquid medium, water or an organic solvent may be used. When 50% by weight or more of the total liquid medium is an organic solvent (hereinafter referred to as oil-based ink), When the α + β + γ + δ + ε + ζ of the compound represented by () is less than 80, the affinity between the compound represented by (Chemical Formula 1) and the organic solvent is increased, so that the effect is further exhibited. Further, since the butyral resin, styrene acrylic acid resin, and ketone resin are excellent in solubility in organic solvents, the fluidity of the ink is improved and the ink discharge amount is easily secured, so that a higher effect can be expected.

The invention is described in detail below.
As the colorant, all of dyes and pigments conventionally used in ballpoint pen inks can be used. The dyes and pigments may be used alone or in combination.
Specific examples of oil-soluble dyes include rhodamine B base (CI 45170B, manufactured by Taoka Dye Manufacturing Co., Ltd.), Soldan Red 3R (CI 21260, manufactured by Chugai Kasei Co., Ltd.), methyl violet. 2B base (C.I. 42535B, USA, manufactured by National Aniline Div.), Victoria Blue F4R (C.I. 42563B), Nigrosine Base LK (C.I. 50415) (above, manufactured by BASF, Germany), Bali First Yellow # 3104 (C.I. 13900A), Bali First Yellow # 3105 (C.I. 18690), Orient Spirit Black AB (C.I. 50415), Bali First Black # 3804 (C.I. 12195) , Bali First Yellow # 1109, Bali First Orange 2210, Bali First Red # 1320, Bali First Blue # 1605, Bali First Violet # 1701 (manufactured by Orient Chemical Co., Ltd.), Spiron Black GMH Special, Spiron Yellow C-2GH, Spiron Yellow C-GNH , Spiron Red C-GH, Spiro Red C-BH, Spiro Blue BPNH, Spiro Blue C-RH, Oh Spiro Violet C-RH, S. P. T. T. Orange 6, S. P. T. T. Conventionally known general materials such as Blue 111 (above, manufactured by Hodogaya Chemical Co., Ltd.) and Neo Super Blue C-555 (above, manufactured by Chuo Synthetic Chemical Co., Ltd.) can be used.

As 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), Kayara 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 SX (same 4), Direct Fast Scarlet 4BS (same 23), Eisen Direct Rhodulin BH (same 31), Direct Scarlet B (same 37), Kayak Direct Scarlet 3B (same 39), Eisen Primula Pink 2BLH (same 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 Kayara Star Coyze Blue GL (86), Kayara 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 Nor Milling Black TLR The 110), Aizen Opal black New Conc (the 119), Water Black 187-L (the 154), mosquito yak Acid Brilliant Flavin FF (C. I. Acid Yellow 7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Daiwa 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 5GW (127), Kayanol Milling 6GW (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 Conc (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 Cachilon Orange GLH (CI Basic Orange 21), Eisen Katyron Brown 3GLH (same 30), Rhodamine 6GCP (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 include basic dye (C.I. Basic Brown 1) and the like.
These must be soluble in at least one of water or organic solvents in the ink.

Pigments are added to improve handwriting fastness and ink flow characteristics. Examples include azo pigments, quinacridone pigments, isoindolinone pigments, dioxane pigments, verinone, berylene pigments, diketo Organic pigments such as pyrrolopyrrole pigment, aniline black, nitroso pigment, nitro pigment, iron oxide, carbon black, acetylene black, lamp black, bone black, iron black, titanium oxide, barium sulfate, cadmium red, petal Inorganic pigments such as chrome yellow, ocher, cadmium yellow, barium yellow, ultramarine blue, and bitumen, fluorescent pigments, pigments in which resin particles are colored with dyes, and those in which the resin used does not dissolve in the ink solvent can be used. Can be used by mixing.
Examples of black pigments include 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, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, Same # 950, Same # 900, Same # 850, Same # 750, Same # 650, Same # 52, Same # 52, Same # 50, Same # 47, Same # 45, Same # 45L, Same # 44, Same # 40, Same # # 33, # 32, # 30, # 25, # 20, # 10, # 5, # 95, # 260, CF9, MCF88, MA600, MA77, MA7, MA11, MA100, MA100R, MA100S, MA100S, MA220, MA230 (above, manufactured by Mitsubishi Chemical Corporation), Talker Black # 8500 / F, # 8300 / F, # 7550SB / F, # 7400, # 736 Carbon black such as SB / F, # 7350 / F, # 7270SB, # 7100 / F, # 7050 (above, manufactured by Tokai Carbon Co., Ltd.), etc., and diamond black N (Tamaboku Color Co., Ltd.) Iron black such as aniline black such as Bone Black (manufactured by Mie Color Techno Co., Ltd.) and ironized black KN-320 (manufactured by Nippon Iron Chemical Co., Ltd.).
Examples of blue pigments include C.I. I. Pigment Blue 2, 9, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 16, 17, 28, 29, 36, 60, 68, 76, 80, etc. can be used.
Examples of red pigments include C.I. I. Pigment Red 2, 3, 5, 8, 14, 17, 17, 22, 31, 31, 48: 1, 48: 2, 48: 3, 48: 4, 53 : 1, 53: 2, 57: 1, 112, 122, 144, 146, 149, 166, 170, 175, 176, 177, 179, 184, same 185, 187, 188, 202, 207, 208, 209, 210, 211, 213, 214, 242, 253, 254, 255, 256, 257, 264, 266, 268, 270, 272, etc. can be used.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 79, 81, 83, 93, 94, 95, the same 97, 109, 110, 111, 120, 128, 133, 136, 138, 139, 147, 151, 154, 155, 167, 173, 174, 175, 176, 180, 185, 191, 194, 213, etc. can be used.
Examples of orange pigments include C.I. I. Pigment Orange 5, 13, 13, 16, 34, 36, 38, 43, 62, 68, 72, 74, and the like.
Examples of green pigments include C.I. I. Pigment Green 7, 36, 37, etc. can be used.
Examples of purple pigments include C.I. I. Pigment Violet 19, 23 and the like can be used.
The amount of these colorants to be used is preferably 1 to 40% by weight based on the total ink. If the amount used is less than 1% by weight, the handwriting is too thin and the amount of the colorant remaining on the paper surface when the light resistance test or the solvent resistance test is carried out becomes difficult to read the handwriting. When it is more than 40% by weight, it becomes easy to cause inability to write due to insufficient dissolution during compounding or clogging due to sedimentation over time. These colorants may be used alone or in combination of two or more.

  In addition to these pigments, processed pigments can also be used. For example, Renol Yellow GG-HW30, HR-HW30, Orange RL-HW30, Red HF2B-HW30, FGR-HW30, F5RK-HW30, Carmine FBB-HW30, Violet RL- HW30, Blue B2G-HW30, CF-HW30, Green GG-HW30, Brown HFR-HW30, Black R-HW30 (above, Clariant Japan Co., Ltd.), UTCO-001, 012 021 Orange, 031 Red, 032 Red, 042 Violet, 051 Blue, 052 Blue, 061 Green, 591 Black, 592 Black (above, manufactured by Daiichi Seika Kogyo Co., Ltd.), MICROLI H Yellow 4G-A, MX-A, 2R-A, Brown 5R-A, Scarlet RA, Red 2C-A, 3R-A, Magenta 2B-A, Violet B-A, Blue 4G-A , Green GA (above, manufactured by Ciba Specialty Chemicals Co., Ltd.).

  Further, a water-based ink base dispersed in an aqueous medium can be used. Specifically, Fuji SP Black 8031, 8119, 8167, 8276, 8381, 8406, Fuji SP Red 5096, 5111, 5193 are used. 5220, Fuji SP Bordeaux 5500, Fuji SP Blue 6062, 6133, 6134, 6401, Fuji SP Green 7051, Fuji SP Yellow 4060, 4178, Fuji SP Violet 9524 SP Orange 534, FUji SP Brown 3074, FUJI SP RED 5543, 5544 (manufactured by Fuji Dye Co., Ltd.), Emac ol Black CN, Emacol Blue FBB, FB, KR, Emacol Green LXB, Emacol Violet BL, Ecolol Brown 3101, Emol Carmine FB, Emacol Red BS, Emacol OraD36 , GN, GG, F5G, F7G, 10GN, 10G, Sandy Super Black B, Sandy Super Brown SB, FRL, RR, SandySG Sandy Super Navy Blue HRL, GLL, HB, FBL-H, FBL-160, FBB, Sandy Super Violet BL H / C, BL, Sandy Super Bordeaux FR, Sandy Super Rin FF, F5B, Sandy Super Rubin FR, Sandy Super Rubine FR, Sandy Super Rubine FR, Sandy Super Rubine FR , Sandy Super Orange FL, R, BO, Sandy Gold Yellow 5GR, R, 3R, Sandye Ywlow GG, F3R, IRC, FGN, GN, GRS, GSR-130, GSN- 130, GSN, 10 GN (Sanyo Dye Co., Ltd.), Rio Fast Black Fx 8012, 8313 8169, Rio Fast Red Fx8209, 8172, Rio Fast Red S Fx 8315, 8316, Rio Fast Blue FX 8170, Rio Fast Blue FX 8170, Rio Fast Blue S 8x, Rio Fast Blue S 8x, Rio Fast Blue S 8x Ink Co., Ltd.), NKW-2101, 2102, 2103, 2104, 2105, 2106, 2107, 2108, 2117, 2127, 2137, 2167, 2101P, 2102P, 2103P, 2104P, 2105P, 2105P, 2106P, 2107P, 2108P, 2117P, 2127P, 2137P, 2167P, NKW-3002, 3003 3004, 3005, 3007, 3077, 3008, 3402, 3404, 3405, 3407, 3408, 3477, 3602, 3603, 3604, 3605, 3607, 3607 3608, 3702, 3703, 3704, 3704, 3705, 3777, 3708, 6013, 6038, 6559 (above, manufactured by Nippon Fluorescence Corporation), Cosmo Color S1000F Series (Toyo Soda Co., Ltd.) )), Victoria Yellow G-11, G-20, Victoria Orange G-16, G-21, Victoria Red G-19, G-22, Victoria Pink G-17, G-23, Victoria Green G-18, G-24, Victoria Blue G-15, G-25 (above, Gokoku Dye Co., Ltd. Manufactured), Pollux PC5T1020, Pollux Black PC8T135, Pollux Thread IT1030 and other Pollux series (above, manufactured by Sumika Color Co., Ltd.), and the like. These can be selected and used in combination of one or more. It is.

The organic solvent that is the main medium of the oil-based ink can be used without particular limitation as long as it is conventionally used for oil-based inks, and glycol ethers, glycols, and alcohols are particularly preferable.
For example, phenyl glycol, phenyl diglycol, benzyl monoglycol, benzyl diglycol, 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 monomethyl ether, diethylene glycol 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 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 monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, Glycol ethers such as 3-methyl-3-methoxy-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, Glycols such as 1,3-butanediol and 1,5-pentanediol, benzyl alcohol, β-phenylethyl alcohol, α-methylbenzyl alcohol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol Alcohols such as 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, 3-methyl-3-methoxypentanol, lauryl alcohol, tridecyl alcohol, isodecyl alcohol, isotridecyl alcohol , Methyl isopropyl ether, ethyl ether, ethyl propyl ether, ethyl butyl ether, isopropyl ether, butyl ether, hexyl ether, ethers such as 2-ethylhexyl ether, 2-ethylhexyl acetate, isobutyric acid iso Examples thereof include esters such as butyl, ethyl lactate, and butyl lactate.
These solvents can be used alone or in combination, and the amount used is preferably 10% by weight or more and 90% by weight or less based on the total amount of the oil-based ink.

An organic solvent can be added for the purpose of preventing the ink from drying and preventing freezing at low temperatures. Specifically, alcohols such as ethanol, 1-propanol, 2-propanol, butyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, hexylene glycol, 2-ethyl 1,3- Hexane glycol, glycerin, triethylene glycol, dipropylene glycol, diglycerin, polyethylene glycol, polypropylene glycol and other glycols, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether and other ethers, thiodiglycol, N-methylpyrrolidone, 2-phenoxyethanol and the like can be used.
These can be used alone or in combination of two or more. The amount used is preferably 0.5 to 40% by weight based on the total amount of ink. If it is less than 0.5% by weight, the effect of preventing drying of the coated part may be weak and may be unusable. Even if it exceeds 40% by weight, the effect is not improved and the meaning of addition cannot be found.

The compounds represented by (Chemical Formula 1) are polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil and derivatives thereof, and commercially available products include NIKKOL HCO-5, HCO-10, HCO-20, and HCO-30. , HCO-40, HCO-50, HCO-60, HCO-80, HCO-100 (manufactured by Nikko Chemicals Co., Ltd.), EMALEX HC-5, HC-7, HC-10, HC-20, HC- 30, HC-40, HC-50, HC-60, HC-80, HC-100 (above, manufactured by Nippon Emulsion Co., Ltd.), BROWNON BR-404, BR-407, BR-410, BR-4135, BR -417, BR-420, BR-425, BR-430, BR-450, RCW-20, RCW-40, RCW-60, RCW-80, RCW- 00 (above, manufactured by Nihon Kasei Co., Ltd.), UNIOXHC-10, HC-20, HC-40, HC-60, HC-100, HC-20ML, HC-40ML, HC-20MIS, HC-40MIS, HC -60 MIS, HC-50MSU, NONION C-2300 (manufactured by NOF Corporation), and the like, and these are preferably added in an amount of 0.01% by weight to 20% by weight with respect to the total amount of ink. If it is less than 0.01% by weight, the effect of addition is not sufficiently exhibited. If it is added by 20% by weight or more, the content of water and organic solvent in the ink is reduced, and the solubility of solids in the ink such as dyes and resins is reduced. Insufficient characters are prone to occur. These may be used alone or in combination of two or more.
In addition, when α + β + γ + δ + ε + ζ is 80 moles or more in oil-based inks, the ink tends to absorb moisture when stored under high humidity, and the solubility of other materials deteriorates due to moisture in the ink and precipitates. , Less than 80 mol, more preferably 5 mol or more and 40 mol or less. In an ink in which 50% by weight or more of the liquid medium in the ink is water (hereinafter referred to as water-based ink), other materials can be used as water-soluble materials, and precipitation can be prevented even if the ink absorbs moisture. So there are no restrictions on the use.

  The compound represented by any one of (Chemical Formula 2), (Chemical Formula 3), and (Chemical Formula 4) is monoalkyl ether phosphoric acid, polyoxyethylene monoalkyl ether phosphoric acid, dialkyl ether phosphoric acid, polyoxyethylene dialkyl ether phosphoric acid. , Trialkyl ether phosphoric acid, polyoxyethylene trialkyl ether phosphoric acid, and neutralized products and solutions thereof. As a commercially available product, as a mixture of the compound represented by (Chemical Formula 2) and the compound represented by (Chemical Formula 3), phosphanol BH-650, SM-172, ED-200, GF-339, RA- 600, GF199, ML-200, ML-220, ML-240, RD-510Y, GF-185, RS-410, RS-610, RS-710, RL-210, RL-310, RB-410, RP- 710, AK-25, GF702, RS-610NA, SC-6103, RD-720, LP-700, LS-500, LB400 (above, manufactured by Toho Chemical Co., Ltd.), Prisurf A208B, A219B, A208S, As the compounds represented by A212S, A215C (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and (Chemical Formula 3), NIKKOL DLP-10, As compounds represented by OP-8N, DDP-2, DDP-4, DDP-6, DDP-8, DDP-10 (manufactured by Nikko Chemicals Co., Ltd.), (Chemical Formula 4), TLP-4, TCP -5, TOP-0V, TDP-2, TDP-6, TDP-8, TDP-10 (above, manufactured by Nikko Chemicals Co., Ltd.) and the like. When the compounds represented by any of these (Chemical Formula 2), (Chemical Formula 3), and (Chemical Formula 4) are added in total in an amount of 20.0% by weight or more, the content of water or organic solvent in the ink is reduced. Since the solubility of solids in inks such as dyes and resins is insufficient, and character blurring tends to occur, the amount used is preferably less than 20.0% by weight based on the total amount of oil-based ink.

  Furthermore, the compound represented by any one of (Chemical Formula 2), (Chemical Formula 3), and (Chemical Formula 4) may react with other components in the ink to change the ink state over time. In order to avoid this, it is possible to add it to the ink after previously mixing with a neutralizing agent to neutralize the phosphate group. As the neutralizing agent, amine compounds, amide compounds, amino acid compounds and derivatives thereof, amphoteric surfactants, and the like are used. Specifically, polyamines such as Amite 102, Amite 105, Amite 302, Amite 308, and Amite 320 are used. Fatty amines such as oxyethylene alkylamines, Farmin CS, Farmin 08D, Farmin 20D, Farmin 80, Farmin 86T, Farmin O, Farmin T, and Farmin (above, manufactured by Kao Corporation), Naimine L-201, Naimeen L-202, Naimeen L207, Naimeen F-215, Naimeen S-202, Naimeen S-204, Naimeen S-210, Naimeen S-215, Naimeen S-220, Naimeen T2-206, Naimeen T2-210, Naimeen T2 230, Nymeen T2-260, Nymeen DT-203, Nymeen DT-208 and other alkyl polyetheramines (Nippon Yushi Co., Ltd.), NIKKOL TAMNOS-5, TAMNOS-15, TAMNOS-15, TAMNO- 5, polyoxyethylene alkylamines such as TAMNO-15, polyoxyethylene fatty acid amides such as TAMDS-4, TAMDS-15, and TAMDO-5, and amphoteric surfactants such as NIKKOL AM-301 and AM3130N (above) , Manufactured by Nikko Chemicals Co., Ltd.), diethanolamine, triethanolamine, diisopropanolamine, triethylamine, dimethylaminoethanol, diethylaminoethanol, methyldiethanolamine, butyldiethanolamine Dibutyl ethanolamine, diethyl isopropanolamine, butyl isopropylamine, butyl benzyl amine, butoxypropyl amine (manufactured by Kanto Chemical Co.) and the like.

The viscosity of the ink can be adjusted by appropriately adjusting and using a thickener so as to obtain a desired viscosity. Specific examples include polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose, carboxyethylcellulose, collagen, HPC-SL, L, M, H (above, Nippon Soda Co., Ltd.), Avicel PH-101. , 102, 301, M06, TG-101 (above, manufactured by Asahi Kasei Co., Ltd.), etc., Kelzan, Kelzan S, Kelzan F, Kelzan AR, Kelzan M, Kelzan D (above, Sanki Co., Ltd.) Xanthane gum such as Kojin, Kojin F, Kojin T, Kojin K (manufactured by Kojin Co., Ltd.), succinoglucan such as Leozan (manufactured by Sanki Co., Ltd.), K1A96 (Sanki Co., Ltd.) Welan gum such as K1A112, K7C2433 (above, manufactured by Sanki Co., Ltd.), Jaguar 8111, 860 , HP-8, HP-60, CP-13 (above, manufactured by Sanki Co., Ltd.) and other water-soluble polysaccharides such as pullulan (manufactured by Hayashibara Co., Ltd.), GX-205, NA- Water-soluble synthetic polymers such as N-vinylacetamide polymerization cross-linked products such as 010 (manufactured by Showa Denko KK), Smecton SA (Smectite, manufactured by Kunimine Kogyo Co., Ltd.), Kunipia-F, Kunipia-G (Montmorillonite, Kunimine) Kogyo Co., Ltd.), Wenger HV, FW, 15 and 23 (Bentonite, manufactured by Toyoshun Yoko Co., Ltd.), Sven, C and W, N400 (quaternary ammonium cation modified montmorillonite, Co., Ltd.) Inorganic clay minerals such as Hoyoseyo Yoko).
These may be used alone or in combination of two or more.

In order to improve the dispersibility of the pigment, anionic, cationic, nonionic, amphoteric surfactants and polymer resins can be used supplementarily. Specifically, higher fatty acid, higher alcohol sulfate ester salt, fatty acid sulfate ester salt, alkylallyl sulfonic acid, phosphate ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, sorbitan fatty acid ester, etc. Anionic, nonionic, cationic surfactants, resins and oligomers for pigment dispersion such as polyvinyl butyral resin, polyvinyl pyrrolidone resin, polyacrylic ester resin, polymethacrylic ester resin, styrene-acrylic acid copolymer resin Is mentioned.
These may be used alone or in combination of two or more.
Moreover, it is possible to use the general method generally used for disperse | distributing a pigment. For example, a pigment, a solvent, and a dispersing agent are mixed and uniformly stirred with a propeller stirrer or the like, and then the pigment is dispersed with a disperser. A disperser such as a roll mill, a ball mill, a sand mill, a bead mill, or a homogenizer is appropriately selected depending on the amount of ink water or organic solvent and the pigment concentration.

  Other dispersants such as natural resins, synthetic resins, anions, cations, nonions, amphoteric surfactants, rust inhibitors such as benzotriazoles, metal salts and phosphate esters, isothiazolone, oxazolidine Preservatives such as silicone compounds, antifoaming agents such as silicones, mineral oils and fluorine compounds, wetting agents such as glycerin, sorbitans, polysaccharides, urea, ethyleneurea or their derivatives, acetylene glycol, acetylene It is also possible to use leveling property-imparting agents such as alcohol and silicon-based surfactants and conventionally known ink additives such as antifreezing agents in combination.

  In order to produce ink, the pigment dispersed above and other components such as viscosity adjusting resin, solvent, lubricant, water-soluble polysaccharide, etc. are mixed and dissolved with a stirrer such as a homomixer until uniform.・ It can be obtained by mixing, but in some cases, the mixed ink may be further dispersed by a disperser, or the obtained ink may be filtered or centrifuged to remove coarse particles and insoluble components. There is no problem.

Hereinafter, it demonstrates still in detail based on an Example and a comparative example. In each example, “part” simply means “part by weight”.
Example 1
Printex 35 (carbon black, manufactured by Degussa Huls Japan Co., Ltd.) 6.0 parts SPILON VIOLET C-RH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.)
16.3 parts VALIFAST YELLOW C-GNH (oil-based dye, Orient Chemical Co., Ltd.)
3.1 parts diethylene glycol monomethyl ether 50.9 parts ethylene glycol monoisopropyl ether 17.2 parts ESREC BL-1 (polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.) 1.6 parts ESREC BH-3 (polyvinyl butyral, Sekisui Chemical) Industrial Co., Ltd.) 0.4 parts NIKKOL HCO-10 (compound represented by Chemical Formula 1, manufactured by Nikko Chemicals Co., Ltd.)
1.0 part phosphanol LB400 (mixture of the compound shown in Chemical formula 2 and the compound shown in Chemical formula 3, manufactured by Toho Chemical Industry Co., Ltd.) 1.5 parts NIKKOL TOP-0V (shown in Chemical formula 4) Compound, manufactured by Toho Chemical Industry Co., Ltd.)
1.0 part Niimine L201 (PEG-1 laurylamine, manufactured by NOF Corporation) 1.0 part Of the above components, 70 parts of the total amount of diethylene glycol monomethyl ether and ethylene glycol monoisopropyl ether and 70 parts of ESREC BL-1 After stirring and mixing at 0 ° C., the mixture was allowed to cool to room temperature, the entire amount of Printex 35 was added, and 10 times were passed using zirconia beads having a diameter of 0.3 mm with a dyno mill (bead mill, manufactured by Shinmaru Enterprise Co., Ltd.). To obtain a black paste.
Next, the entire amount of the remaining material was added to the paste, and the mixture was stirred at 70 ° C. for 3 hours to obtain a black oil-based ink for ballpoint pens.

(Example 2)
SPILON VIOLET C-RH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.)
13.0 parts SPILON YELLOW C-GNH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.)
7.0 parts diethylene glycol monomethyl ether 27.0 parts ethylene glycol mononormal propyl ether 16.5 parts benzyl glycol 5.0 parts Hilac 110H (ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 6.0 parts PEMULEN TR-2 ( B. F. Goodrich, USA) 1.5 parts NIKKOL HCO-5 (compound represented by Chemical Formula 1, Nikko Chemicals)
2.0 parts NONION C-2300 (compound represented by chemical formula 1, manufactured by NOF Corporation) 1.0 part phosphanol LP710 (compound represented by chemical formula 2 and compound represented by chemical formula 3) Mixture, manufactured by Toho Chemical Co., Ltd.) 20.0 parts Amit 105 (POE coconut amine, manufactured by Kao Corporation) 1.0 parts The above ingredients are stirred at 70 ° C. and dissolved uniformly for a black ballpoint pen An oil-based ink was obtained.

(Example 3)
NOVOPERM RED F3RK70 (C.I. Pigment Red 170,
(Manufactured by Clariant Japan Co., Ltd.) 3.0 parts SPILON RED C-GH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.) 17.6 parts SPILON RED C-BH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.) ) 0.8 parts SPILON YELLOW C-GNH 3.8 parts diethylene glycol monoisobutyl ether 16.6 parts ethylene glycol mononormal propyl ether 43.5 parts propylene glycol monomethyl ether 3.0 parts Joncryl 678 (styrene acrylic acid resin, BASF) 1.0 part ESREC BL-1 0.6 part EMALEX HC-20 (compound represented by Chemical Formula 1, manufactured by Japan Emulsion Co., Ltd.)
10.0 parts Prisurf A208 (a mixture of a compound represented by Chemical Formula 2 and a compound represented by Chemical Formula 3,
Daiichi Kogyo Seiyaku Co., Ltd.) 0.1 part Among the above components, the total amount of ethylene glycol monoisobutyl ether, ethylene glycol mononormal propyl ether and propylene glycol monomethyl ether, and the total amount of SREC BL-1 were stirred at 70 ° C. After mixing and dissolving, this was allowed to cool to room temperature, then the entire amount of NOVOPERM RED F3RK70 was added, and 10 times were passed through a dyno mill (bead mill, manufactured by Shinmaru Enterprise Co., Ltd.) using zirconia beads having a diameter of 0.3 mm. A paste of was obtained.
Next, the entire amount of the remaining material was added to this paste and stirred at 70 ° C. for 3 hours to obtain a red ballpoint pen-based oil ink.

Example 4
VALIFAST BLUE 1603 (Salt-forming dyes of CI DIRECT BLUE 86 and CI BASIC BLUE 7, manufactured by Orient Chemical Co., Ltd.) 20.0 parts SPILON RED C-GH (oil-based dye, Hodogaya Chemical Industry) 3.0 parts phenyl cellosolve 41.4 parts diethylene glycol monomethyl ether 23.3 parts benzyl alcohol 10.2 parts ESREC BH-3 1.0 part UNIOX HC-50MSU (compound shown in Chemical Formula 1) 0.1 part NIKKOL TOP-0V (compound represented by Chemical Formula 4, manufactured by Nikko Chemicals Co., Ltd.)
1.0 part The above ingredients were stirred at 70 ° C. and dissolved uniformly to obtain a blue oil-based ink for ballpoint pens.

(Example 5)
In Example 4, blue oil-based ink was obtained in the same manner except that UNIOX HC-50MSU was reduced to 0.008 parts and the reduced amount was replaced with diethylene glycol monomethyl ether.

(Example 6)
FUJI SP BLACK 8922 (carbon black 20% dispersion, manufactured by Fuji Dye Co., Ltd.) 25.0 parts ethylene glycol 6.0 parts glycerin 6.0 parts Braunon BR-404 (compound represented by Chemical Formula 1, Nihon Kasei Co., Ltd.) 2.0 parts EMALEX HC-100 (compound represented by Chemical Formula 1, manufactured by Nippon Emulsion Co., Ltd.)
0.5 parts phosphanol RD720 (Na salt of a mixture of the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3, manufactured by Toho Chemical Industry Co., Ltd.) 3.0 parts benzotriazole 0.5 part Proxel GXL 0.2 part Pemulene TR-1 (crosslinked acrylic acid and acrylate copolymer, manufactured by BF Goodrich) 0.3 part sodium hydroxide 0.7 part ion-exchanged water 55.8 parts In the components, the total amount of Pemulen TR-1 and 10 parts of water were stirred for 1 hour with a laboratory mixer to prepare Pemulen TR-1 aqueous solution. The remaining components were mixed and the aqueous solution of Pemulen TR-1 was added to the liquid stirred for 1 hour until uniform, and further mixed and stirred for 2 hours to obtain a black water-based ink for a ballpoint pen.

(Example 7)
Water Red # 2 (CI ACID RED87, manufactured by Orient Chemical Industry Co., Ltd.) 5.0 parts Water Yellow # 6C (CI ACID YELLOW23, manufactured by Orient Chemical Industry Co., Ltd.) 3.0 parts Kelzan AR (Xanthan gum, manufactured by Sanki Co., Ltd.) 0.5 parts ethylene glycol 12.0 parts glycerin 6.0 parts Braunon RCW-40 (compound represented by Chemical Formula 1, manufactured by Nisshinsei Co., Ltd.) 5.0 parts NIKKOL DDP-10 (compound shown in Chemical Formula 3, manufactured by Nikko Chemicals Co., Ltd.)
0.5 part potassium hydroquinone sulfonate 0.3 part benzotriazole 0.5 part Proxel GXL 0.2 part AKP-20 (alumina, particle size 0.5 μm, manufactured by Sumitomo Chemical Co., Ltd.) 0.01 part ion exchange Water 66.99 parts In the said component, the whole quantity of Kelzan AR and 5.0 parts of water were stirred for 30 minutes with the laboratory mixer, and it melt | dissolved uniformly, and prepared Kelzan aqueous solution. Next, the total amount of AKP-20 and glycerin was mixed and stirred uniformly, and then stirred for 15 minutes with a homogenizer to prepare an alumina dispersion. The remaining components were mixed and stirred for 1 hour, and then an aqueous Kelzan AR solution and an alumina dispersion were added and further mixed and stirred for 2 hours to obtain a red water-based ink for ballpoint pens.

(Example 8)
Water Blue 105S (CI ACID BLUE90, manufactured by Orient Chemical Industry Co., Ltd.) 4.0 parts ethylene glycol 5.0 parts glycerin 3.0 parts UNIOX HC-60MIS (compound represented by Chemical Formula 1, NOF ( Co., Ltd.) 3.0 parts Plysurf A219 (mixture of the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 10.0 parts Benzotriazole 0.5 parts Sodium ascorbate 0.4 parts Proxel GXL (1,2-benzisothiazolin-3-one, preservative, ICI Corporation)
(Product made) 0.2 parts ion exchange water 73.9 parts The above components were mixed and stirred for 1 hour in a lab mixer to dissolve uniformly to obtain a blue water-based ink for a ballpoint pen.

Example 9
A black aqueous ink was obtained in the same manner as in Example 5 except that 18.0 parts of ion-exchanged water was replaced with Brownon BR-404.

(Comparative Example 1)
A black oil-based ink was obtained in the same manner as in Example 1, except that NIKKOL HCO-10 was omitted and the amount was replaced with ethylene glycol monoisopropyl ether.

(Comparative Example 2)
In Example 1, except that NIKKOL HCO-10 was removed, instead of NIKKOL GO-460V (polyoxyethylene sorbitol tetraoleate, manufactured by Nikko Chemicals Co., Ltd.), black oil-based ink was prepared in the same manner. Obtained.

(Comparative Example 3)
In Example 3, except that EMALEX HC-20 was removed, instead of NIKKOL TMGS-5V (polyoxyethylene glyceryl monostearate, manufactured by Nikko Chemicals Co., Ltd.), red oil-based ink was prepared in the same manner. Obtained.

(Comparative Example 4)
VALIFAST BLUE 1603 (Salt-forming dyes of CI DIRECT BLUE 86 and CI BASIC BLUE 7, manufactured by Orient Chemical Co., Ltd.) 20.0 parts SPILON RED C-GH (oil-based dye, Hodogaya Chemical Industry) 3.0 parts Phenyl Cellosolve 57.7 parts benzyl alcohol 9.3 parts Hilac 110H 7.0 parts Nomcoat HK-P (behenic acid / eicoic acid polyglyceryl-10, Nisshin Oillio Group ( 1.0 part EXTRA OLEIN 80 2.0 parts The above components were stirred at 70 ° C. and dissolved uniformly to obtain a blue oil-based ink for ballpoint pens.

(Comparative Example 5)
A blue water-based ink was obtained in the same manner as in Example 7 except that the plysurf A219 was removed and replaced with water.

(Comparative Example 6)
In Example 7, blue water-based ink was obtained in the same manner except that PRISURF A219 was removed and EXTRA OLEIN 80 (oleic acid, manufactured by NOF Corporation) was added instead.

  As mentioned above, the following test was done about the ink obtained by the Example and the comparative example. The results are shown in Table 1.

(Production of oil-based ballpoint pen for testing)
The oil-based ink for ballpoint pens obtained in Examples 1 to 5 and Comparative Examples 1 to 4 has the same structure as a commercially available oil-based ballpoint pen (.e-ball, product code BK127, manufactured by Pentel Co., Ltd. (ball diameter φ0.7)). A writing pen was filled with 0.3 g, a centrifugal force (1000 rpm, 5 minutes) was applied in a centrifuge to degas bubbles in the ink, and a test ballpoint pen was produced.

(Production of water-based ballpoint pen for testing)
A writing instrument having the same structure as that of the commercially available water-based ballpoint pen (Energel, product code BL17, manufactured by Pentel Co., Ltd. (ball diameter φ0.7)) obtained from the water-based ink for ballpoint pens obtained in Examples 6 to 9 and Comparative Examples 5 and 6. The test ballpoint pen was manufactured by adding 1.8 g to the mixture and applying centrifugal force (1000 rpm, 5 minutes) in a centrifuge to degas bubbles in the ink.

  Measurement of ball sinking amount: n = 5 ball pens in the above examples and comparative examples each after writing 400 m with a spiral writing tester (writing angle 70 °, load 150 g, writing speed 7 cm / sec). The distance in the direction perpendicular to the cross-section from the tip of the ball holder to be held to the tip of the ball was measured, and the difference from the unwritten time was taken as the amount of sinking of the ball. The numerical value calculated the average value of n = 5.

  Ink discharge amount: n = 5 ball pens of the above examples and comparative examples were written 400 m with a spiral writing tester (writing angle 70 °, load 150 g, writing speed 7 cm / sec), and the ball pen weight was measured every 200 m. The reduced ink weight was taken as the ink discharge amount.

  Measurement of writing resistance value: n = 5 ballpoint pens of the above-mentioned examples and comparative examples, using Tribo-master (Type: TL201Sa) manufactured by Trinity Labs Co., Ltd. After (spiral writing conditions: writing angle 70 °, load 150 g, writing speed 7 cm / sec), the writing resistance value was measured when writing was performed for 15 cm each. The writing angle at the time of measuring the writing resistance value was written under two conditions of 90 ° and 70 °, and the other conditions were a writing load of 150 g and a writing speed of 7 cm / sec. For the measurement of the writing resistance value, the data measured at a measurement frequency of 200 Hz for 2 seconds is averaged to calculate the average writing resistance value for the specimen, and n = from each average writing resistance value for the five specimens. The average value of 5 was calculated and used as the writing resistance value of each example and comparative example.

Sensory test of writing taste (lightness and smoothness of writing taste): Sensory test by handwriting with 20 monitors, unwritten state after writing pen, and after 400m spiral writing (spiral writing condition: writing angle 70 °, load 150g The writing speed was 7 cm / sec) and the writing quality was evaluated.
Evaluation criteria are heavy or not smooth (1 point), light but not smooth or smooth but heavy (2 points), light and smooth (3 points), very light and smooth (4 points), 20 The average value of people was calculated.

  Presence / absence of handwriting: When the number of the ballpoint pens of the above-mentioned examples and comparative examples is written by 400 m using a spiral writing tester (writing angle 70 °, load 150 g, writing speed 7 cm / sec). The presence or absence of was confirmed visually. Of the five pieces, no scrap was found at one place, and no scrap was found.

  Presence / absence of contact of the tip of the ball holder with the paper surface: When writing with the spiral writing tester (writing angle 70 °, load 150 g, writing speed 7 cm / sec) of n = 5 ball pens in the above examples and comparative examples. When writing from 380 m to 400 m, it was confirmed whether or not the tip of the ball holder holding the ball of the ballpoint pen tip was in contact with the paper surface. When even one of the five was found to be in contact with the paper even a little, the contact was “present”, and the contact was not present at all.

  As described above in detail, the ink of the present invention can obtain an extremely light and smooth writing feeling even when a strong writing pressure is applied, and the writing taste does not deteriorate with the writing distance. It is about.

Claims (4)

At least one or a mixture selected from the compounds represented by the following general formula (Chemical Formula 1) and the compounds represented by the following general formulas (Chemical Formula 2), (Chemical Formula 3), and (Chemical Formula 4): Ballpoint pen ink containing a liquid medium.
  Weight ratio in ink of the above general formula (Chemical formula 1) and one or a mixture of two or more selected from the compounds represented by any one of the above general formulas (Chemical formula 2), (Chemical formula 3), and (Chemical formula 4) The ink for a ballpoint pen according to claim 1, wherein is (Chemical Formula 1) / (Chemical Formula 2) + (Chemical Formula 3) + (Chemical Formula 4) = 0.1 or more and 100 or less.   3. The liquid medium according to claim 1, wherein 50% by weight or more of the liquid medium is an alcohol solvent and / or glycol solvent, and the value of α + β + γ + δ + ε + ζ in the compound represented by the general formula (Formula 1) is less than 80. Ballpoint pen ink.   The ink for ball-point pens in any one of Claims 1 thru | or 3 containing a butyral resin, a styrene acrylic acid resin, or a ketone resin.