JP2020203969A - Aqueous ink composition for ball point pen - Google Patents

Abstract

To provide an aqueous ink composition for ball point pen which prevents line skipping phenomenon in writing on a page surface stained by a hand grease component after even long-distance writing.SOLUTION: An aqueous ink composition for ball point pen contains at least carbon black or an organic pigment, water, polysaccharides, 2-methylpentane-2,4-diol, alumina particles, and styrene-acrylic acid resin emulsion having a solid content acid value of 1 or more and less than 100.SELECTED DRAWING: Figure 1

Description

The present invention relates to a water-based ink composition for a ballpoint pen containing at least carbon black and / or an organic pigment as a coloring component, water as a liquid medium, and a polysaccharide as a shear thinning agent.

In recent years, a water-based ink composition for a ballpoint pen has been known in which a polysaccharide is added to water as a main medium to impart shear thinning, which reduces the viscosity due to the shearing force of the rotation of the ball during writing. Since the ink composition for a ballpoint pen having this shear-reducing viscosity has a high viscosity when not writing, it suppresses the precipitation of the pigment over time and the leakage of the ink composition from the pen tip, and the shearing of the rotating ball during writing. Since the viscosity of the ink composition decreases during writing due to the force, the ink composition can be ejected smoothly. In the case of such a water-based ink composition for a ballpoint pen, since the main solvent is water and the hydrophilicity of the polysaccharide is high, sebum adhering to the hand (hereinafter referred to as "hand fat") adheres. When trying to write on the surface of the paper, since the component of the hand grease is an oil component, the ink composition may be repelled, resulting in a line skipping phenomenon in which the writing line is not partially formed. In addition, polysaccharides form an apparently large mesh-like network due to the entanglement of chemical structures, and because of the large structure, they do not pass through narrow spaces such as paper fibers, and ink whose viscosity has once decreased penetrates into paper. Since it quickly returns to its original state and becomes highly viscous, the handwriting does not show through to the paper, but on the other hand, it may be difficult for the handwriting to dry with a ballpoint pen having a large amount of ink composition such as a ballpoint pen having a large ball diameter.
In addition, in ink compositions to which a high boiling point organic solvent such as glycerin or ethylene glycol is added to suppress drying of the pen tip, the hydrophilicity of these relatively hard-to-volatile solvents slows down the drying of handwriting. In addition, there is a problem that the ink composition is more easily repelled on the paper surface contaminated with handwriting, and the line skipping of the handwriting tends to occur.
When a solvent or additive that is hydrophobic but soluble in water is added, the dryness of the handwriting and the writing property on the surface to which the hand oil is attached are improved, but the dissolution stability of the polysaccharide is lowered and the pigment is pigmented. There was a concern that the dispersibility and shear thinning of the solvent would become unstable, pigment aggregation would occur over time, and the writing quality would deteriorate.

For example, as a means for speeding up the drying property of handwriting, polyhydric alcohols and / or glycol ethers having 4 or more carbon atoms and having a specific gravity of less than 1.00 (25 ° C.) that are solubilized in water in an ink composition. (Patent Document 1) is known.
Further, as a means for preventing the line skipping phenomenon due to hand grease, a crosslinked poly N-vinylcarboxylic acid amide and an alkylbenzene sulfonate are used in combination in the ink composition to reduce the frictional resistance between the ball and the ball seat. There is known an example (Patent Document 2) in which the ball can be easily rotated so that the ball can rotate satisfactorily without slipping even on a paper surface contaminated with hand grease to form a handwriting.

Japanese Unexamined Patent Publication No. 2006-193688 Japanese Unexamined Patent Publication No. 2003-073605

Although the ink composition according to the invention described in Patent Document 1 has good initial handwriting drying property, the dispersibility of the pigment is unstable, so that the ink composition on the surface to which hand grease adheres due to a change in the ejection amount due to writing or the like The stability of writing deteriorated, and the line skipping phenomenon sometimes occurred. In the initial stage, the ink composition according to the invention described in Patent Document 2 can write well on the surface to which hand grease is attached, but if writing is continued, it is difficult to reduce the frictional resistance of the seat until the end of the ink, in particular. On a surface with a lot of hand grease, the performance to prevent the line skipping phenomenon was likely to be insufficient.

The present invention relates to carbon black and / or organic pigments, water, polysaccharides, 2-methylpentane-2,4-diol, alumina particles and styrene-acrylic acid having a solid acid value of 1 or more and less than 100. The first gist is a water-based ink composition for ballpoint pens containing at least a resin emulsion, and the second is a water-based ink composition for ballpoint pens containing alumina particles having a center particle size of 0.15 μm or more and less than 0.4 μm. It is a summary.

In the present invention, since the dispersibility of the pigment is stable while having excellent handwriting drying property, the amount of ink ejected by writing is stable until the end of the ink, and this and the frictional resistance of the seat are also reduced until the end of the ink. Therefore, it was possible to obtain a water-based ink composition for a ballpoint pen that can continue to form a stable writing line even on a surface with a large amount of hand grease.

It is a vertical sectional view which shows the writing tool which concerns on one Embodiment. It is a vertical cross-sectional view which shows the refill used for the writing tool shown in FIG. It is an enlarged sectional view which shows the part I in FIG. It is a vertical sectional view of the ballpoint pen tip for a test. FIG. 4 is a cross-sectional view taken along the line II-II'of FIG.

The carbon black and / or organic pigment used in the water-based ink composition for a ballpoint pen of the present invention is used to give a coloring effect to a handwriting to make it visible and to form a water-resistant handwriting. Specific examples of pigments include carbon black, azo pigments as organic pigments, nitroso pigments, nitro pigments, basic dye pigments, acid dye pigments, built-in dye pigments, medium dye pigments, and natural dyes. Examples include system pigments. Specific examples include Mitsubishi carbon black # 10B, # 20B, # 14, # 25, # 30, # 33, # 40, # 44, # 45, and # 45. # 45L, # 50, # 55, # 95, # 260, # 900, # 1000, # 2200B, # 2300, # 2350, # 2400B, # 2650, # 2700 , # 4000B, CF9, MA8, MA11, MA77, MA100, MA220, MA230, MA600 and MCF88 (all 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, manufactured by Colombian Carbon Japan Co., Ltd.), C.I. I. Pigment Black 7, etc. Specific examples of organic pigments include C.I. I. Pigment Red 170, C.I. I. Pigment 213, C.I. I. Pigment Orange 38, C.I. I. Pigment Blue 15, C.I. I. Pigment Violet 23, Aniline Black (CI 50440), Cyanin Black, Naftor Yellow S (CI 10316), Hansa Yellow 10G (CI 11710), Hansa Yellow 5G (CI 11660), Hansa Yellow 3G (CI11670), Hansaello G (CI11680), Hansaero GR (CI11730), Hansaero A (CI11735), Hansaero RN (CI11740), Hansa Brilliant Yellow 5GX (CI 11741), Hansa Yellow R (CI 12710), Pigment Yellow L (CI 12720), Benzidine Yellow (CI 21090), Benzidine Yellow G (CI 21095) ), Benzidine Yellow GR (CI 21100), Benzidine Yellow GG (CI 21105), Permanent Yellow NCG (CI 20040), Balkan Fast Yellow 5G (CI 21220), Balkan Fast Yellow R (CI 21135), tertazine rake (CI 19140), quinoline ero rake (CI 47005), aniline ero 6GL (CI 60520), permanent ero FGL, permanent ero H10G , Permanent Yellow HR, Anslapyrimidine Yellow (CI68420), Sudan I (CI12055), Permanent Orange (CI12075), Resole Fast Orange (CI12125), Permanent Orange GTR (CI12305), Hansa Yellow 3R (CI11725), Balkan Fast Orange GG (CI21165), Benzidine Orange G (CI21110), Persian Orange (CI15510) , Indanthrone Brilliant Orange GK (CI 59305), Indanthrone Brilliant Orange RK (CI 59105), Indanthrone Brilliant Orange GR (CI 71105), Permanent Brown FG (CI) .12480), Parabrown (CI12071), Permanent Red 4R (CI12120), Parared (CI12070), Fire Red (CI12085), Parachlor Orthoaniline Red (.12480) CI12090), Resole Fast Scarlet, Brilliant Fast Scarlet (CI12315), Brilliant Carmin BS, Permanent Red F2R (C.I. I. 12310), Permanent Red F4R (CI 12335), Permanent Red FRL (CI 12440), Permanent Red FRLL (CI 12460), Permanent Red F4RH (CI 12420), Fast Scarlet VD , Balkan Fast Rubin B (CI 12320), Balkan Fast Pink G (CI 12330), Light Fast Red Toner B (CI 12450), Light Fast Red Toner R (CI 12455) , Permanent Carmine FB (CI12490), Pyrazolone Red (CI12120), Resole Red (CI15630), Lake Red C (CI15585), Lake Red D (CI) .15500), Anthocin B (CI18030), Brilliant Scarlet G (CI15800), Risolrubin GK (CI15825), Permanent Red F5R (CI15865), Brilliant Carmine 6B (.15500) CI 15850), Pigment Scarlet 3B (CI 16105), Bordeaux 5B (CI 12170), Truisin Maroon (CI 12350), Permanent Bordeaux F2R (CI 12385), Helio Bordeaux BL (CI 14830), Bordeaux 10B (CI 15880), Bon Maroon Light (CI 15825), Bon Maroon Medium (CI 15880), Eosin Lake (CI 45380) ), Rhodamin Lake B (CI 45170), Rhodamin Lake Y (CI 45160), Alizarin Lake (CI 58000), Thioing Digo Red B (C.I. 73300), Thio Indigo Maroon (C.I. 73300) CI 73385), Permanent Red FGR (CI 12370), PV Carmine HR, Watching Red, Monolite Fast Red YS (CI 59300), Permanent Red BL, Fast Violet B, Methyl Violet Lake (CI 42535), Dioxazine Violet, Alkaline Blue Lake (CI 42750A, CI 42770A), Peacock Blue Lake (CI 42090), Peacock Blue Lake (CI 42025) , Victoria Blue Lake (CI 44045), Phtalocyanin Blue (CI 74160), Fast Sky Blue (CI 7) 4180), Indanthrone Blue RS (C.I. I. 69800), Indanthrone Blue BC (CI 69825), Indigo (CI 73000), Pigment Green B (CI 10066), Naphthol Green B (CI 10020), Green Gold ( CI 12775), acid green lake, malachite green lake (CI 42000), phthalocyanine green and the like can be mentioned, and these are dispersed in a liquid medium and used. The amount of these carbon blacks or organic pigments added is preferably 3.0% by weight or more and 15.0% by weight or less with respect to 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 see, and if it is more than 15.0% by weight, the writing taste may be slightly heavy. These carbon blacks and organic pigments may be used alone or in combination of two or more.

Water-dispersion type pigments dispersed using a commercially available surfactant are preferably used because they improve handleability and productivity. Specific examples of the water-dispersion type pigments include Fuji SP Black 8031, 8041, 8119, 8167, 8276, 8381, 8406, Fuji SP Red 5096, 5111, 5193, 5220, and Fuji SP Borderux. 5500, Fuji SP Blue 6062, 6474, 6133, 6134, 6401, 6555, Fuji SP Green 7051, Fuji SP Yellow 4060, 4360, 4361, 4178, 4443, Fuji SP Biolet 9011, , FUJI SP Pink 9524, 9527, FUJI SP Orange 534, 636, FUJI SP Pink 9249, FUJI SP Brown 3074, FUJI SP RED 5543, 5657, 5565, 5544 Black CN, Emacol Blue FBB, FB, KR, Emacol Green LXB, Emacol Violet BL, Emacol Brown3101, Emacol Carmmine FB, Emacol RedBS, Emacol Orange FB, Emacol RedBS, Emacol Orange R , GG, F5G, F7G, 10GN, 10G, Sandye Super Black K, C, Sandye Super Gray B, Sandye Super BrownSB, FRL, RR, SandySerGerSup Blue HRL, GLL, HB, FBL-H, FBL-160, FBB, Sandye Super Violet BL H / C, BL, Sandye Super Borderax FR, Sandye SuperPinSimpR , Sandye superCarmmine FB, Sandye SuperRed FFG, RR, BS, 1315, Sandye Super Orange FL, R, BO, Sandye Gold Yellow 5GR, R, 3R, Sandye Ywllow GG, F3R, IRC, FGN, GN, GRS, GSR-130 GSN-130, GSN, 10GN (manufactured by Sanyo Dye Co., Ltd.), Rio Fast Black Fx 8012, 8313, 8169, Rio Fast Red Fx 8209, 8172, Rio Fast Red S Fx 8315, 8316, Rio Fast Blue Fx 8170, Rio Fast Blue FX 8170, Rio Fast Blue S Fx 8312, Rio Fast Green S Fx 8314, EM green G, (above, Toyo Ink Co., Ltd.), NK 2104, 2105, 2106, 2107, 2108, 2117, 2127, 2137, 2167, 2101P, 2102P, 2103P, 2104P, 2105P, 2106P, 2107P, 2108P. 2117P, 2127P, 2137P, 2167P, 2405E, 2404E, 2407E, 2408E, 2167E, NKW-3002, 3003, 3004, 3005, 3007, 3077, 3008, 3402, 3404, 3405, 3407, 3408, 3477, 3602, 3603, 3604, 3605, 3607, 3677, 3608, 3702, 3703, 3704, 3705. , 3777, 3708, 6013, 6038, 6559 (manufactured by Nippon Fluorescent Co., Ltd.), Victoria Yellow G-11, G-20, Victoria Orange G-16, G-21, Victoria Red G -19, G-22, Victoria Pink G-17, G-23, Victoria Green G-18, G-24, Victoria Blue G-15, G-25 (all manufactured by Gokoku Dye Co., Ltd.), Polx series such as Polux PC5T1020, Polux Black PC8T135, Poluk Red IT1030 (all manufactured by Sumika Color Co., Ltd.), etc. Can be mentioned.

Inorganic pigments such as ocher, barium yellow, ultramarine, dark blue, cadmium red, barium sulfate, titanium oxide, petals, iron black, etc. and metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, tin powder, brass powder, etc. Fluorescent pigments and mica-based pigments can also be used in combination. Dyes can also be used together. As a specific example, any of acid dyes, direct dyes, basic dyes and the like can be used. To give an 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 Conch (51), Kayaras Spragley VGN (71), Kayaras Direct Brilliant Yellow G (CI Direct Yellow 4) ), Direct Fast Yellow 5GL (26), Eisen Primula Hero GCLH (44), Direct Fast Yellow R (50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX (same) 4), Direct Fast Scarlet 4BS (23), Eisen Direct Roudulin BH (31), Direct Scarlet B (37), Kayaku Direct Scarlet 3B (39), Eisen Primula Pink 2BLH (75), Sumi Light Red F3B (80), Eisen Primula Red 4BH (81), Kayaras Splarbin BL (83), Kayaras Light Red F5G (225), Kayaras Light Red F5B (226), Kayaras Light Rose FR (227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (15), Sumilite Supra Blue BRR Conch (71), Divogen Turquoise Blue S (86) , Water Blue # 3 (86), Kayaras Star Kois Blue GL (86), Kayaras Splat Blue FF2GL (106), Kayaras Splatter Coise Blue FBL (199), Acid Blue Black 10B (CI Acid Black 1), Nigrosin (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (26), Suminol Fast Black BR Conch (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conch (52), Sumilan Black WA (52), Lanil Black BG Extra Conc (107), Kayanol Milling Black TLB (109), Sminol Milling Black B (109), Kayanol Milling Black TLR ( 110), Eisen Opal Black New Conch (119), Water Black 187-L (154), Kayaqua 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), Daiwata Tragin (23), Kayaktor Tragin (23) , Suminol Fast Yellow R (25), Diasid Light Yellow 2GP (29), Suminol Milling Yellow O (38), Suminol Milling Yellow 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% (141), Kayanol Yellow NG (135), Kayanol Milling Yellow 5GW (127), Kayanol Milling Yellow 6GW (142), Sumitomo Fast Scarlet A (CI Acid Red 8) ), Kayaku Silk Scarlet (9), Solar Rubin Extra (14), Daiwa New Coxin (18), Eisen Bonso RH (26), Daiwa Red No. 2 (27), Suminol Leveling Brilliant Red S3B (35), Kayacil rubinol 3GS (37), Eisen erythrosin (51), Kayaqua acid rodamine FB (52), Suminol leveling rubinol 3GP (57), Diaside alizarin rubinol F3G 200% (82), Eisen Eosin GH (87), Water Pink # 2 (92), Eisen Acid Floxin PB (92), Rose Bengal (94), Kayanol Milling Scarlet FGW (111), Kayanol Milling Rubin 3BW (129), Sminool Milling Brilliant Red 3BN Conch (131), Sminol Milling Brilliant Red BS (138), Eisen Opal Pink BH (186), Sminol Milling Brilliant Red B Conch (249) ), Kayaqua Acid Brilliant Red 3BL (254), Kayaqua Acid Brilliant Red BL (265), Kayanor 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 (1), Patent Blue AF (7), Water Blue # 9 (9), Daiwa Blue 1 (9), Spranol Blue B (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 Arizarin Saffylol SE (43) , Suminol Leveling Sky Blue R Extra Conch (62), Mitsui Nylon Fast Sky Blue B (78), Sumitomo Brilliant Indocyanine 6Bh / c (83), Sandrancyanine N-6B 350% (90), Water Blue # 115 (90), Orient Solve Blue OBB (93), Sumitomo Brilliant Blue 5G (103), Kayanol Milling Ultra Sky SE (112), Kayanol Milling Cyanine 5R (113), Eisen Opal Blue 2GLH (158), Daiwa Guinea Green B (C.I. I. Acid dyes such as Acid Green 3), Acid Brilliant Milling Green B (9), Daiwa Green # 70 (16), Kayanol Cyanine Green G (25), Suminol Milling Green G (27), Eisenkachi Ron Yellow 3GLH (CI Basic Yellow 11), Eisenka Chiron Brilliant Yellow 5GLH (13), Sumi Acrylic Yellow E-3RD (15), Maxiron Yellow 2RL (19), Astrazon Yellow 7GLL (13) 21), Kayakrill Golden Yellow GL-ED (28), Astrazon Yellow 5GL (51), Eisencatilon Orange GLH (CI Basic Orange 21), Eisencatilon Brown 3GLH (30), Rhodamine 6GCP (CI Basic Red 1), Eisen Astrafloxin (12), Sumiacrylic Brilliant Red E-2B (15), Astrazon Red GTL (18), Eisencatylon Brilliant Pink BGH (27) , Maxiron Red GRL (46), Eisen Methyl Violet (CI Basic Violet 1), Eisen Crystal Violet (3), Eisen Rhodamine B (10), Astrazon Blue G (CI Basic Blue) 1), Astrazon Blue BG (3), Methylene Blue (9), Maxiron Blue GRL (41), Eisencatylon Blue BRLH (54), Eisen Diamond Green GH (CI Basic Green 1) , Eisenmalakite Green (4), Bismarck Brown G (CI Basic Brown 1) and other basic dyes. These pigments and dyes may be used alone or in combination of two or more.

2-Methylpentane-2,4-diol is used to obtain a handwriting without line skipping phenomenon without the ink being repelled by the hand grease component while having excellent handwriting drying property. The amount of 2-methylpentane-2,4-diol used is preferably 5.0% by weight or more and 30.0% by weight or less based on the total amount of the ink composition.

A ballpoint pen containing alumina particles causes line skipping because the frictional force between the ball seat and the ball remains smaller than the frictional force between the paper surface contaminated with the hand grease component and the ball even when writing over a long distance. do not do. In particular, alumina particles having a central particle size of 0.15 μm or more and less than 0.4 μm are preferable because they can more stably maintain a state in which the frictional force between the ball seat and the ball is small. For the central particle size of alumina, a dispersion prepared by adding alumina to ethanol and dispersing it with ultrasonic waves for 20 minutes was used with Nanotrac Wave2-EX150 (dynamic light scattering type particle size distribution measuring device manufactured by Microtrac Bell Co., Ltd.). Was measured. The central particle size is the diameter at which the large powder and the small powder are equal in quantity when the powder is divided into two from a certain particle size, and the median diameter, median diameter, and d50. It is also called a value. As the alumina particles, high-purity alumina AKP-53 (center particle size 0.17 μm), AKP-50 (center particle size 0.20 μm), and AKP-30 (center particle size 0.30 μm) manufactured by Sumitomo Chemical Co., Ltd. ), AKP-20 (center particle size 0.46 μm), AKP-3000 (center particle size 0.70 μm), AA-03 (center particle size 0.44 μm), AA-04 (center particle size 0) .50 μm), AA-05 (center particle size 0.53 μm), AA-07 (center particle size 0.83 μm), WA # 30000 (center particle size 0.35 μm) manufactured by Fujimi Incorporated Co., Ltd., WA # 20000 (center particle size 0.45 μm), WA # 10000 (center particle size 0.60 μm), WA # 8000 (center particle size 1.2 μm), WA # 6000 (center particle size 2.0 μm), Harzok Japan Alumina powder AP005 (center particle size 0.05 μm), AP01 (center particle size 0.1 μm), AP03 (center particle size 0.3 μm), AP1 (center particle size 1 μm) manufactured by Co., Ltd. can be mentioned. These aluminas may be used alone or in combination of two or more. The amount of alumina particles used is preferably 0.001% by weight or more and 10% by weight or less with respect to the total amount of the ink composition.

A styrene-acrylic acid resin emulsion having a solid acid value of 1 or more and less than 100 is used to impart hand-fat writing stability over long-distance writing. As a specific example that can be used as a styrene-acrylic acid resin emulsion having a solid content acid value of 1 or more and less than 100, John Krill 7100 manufactured by BASF Japan Co., Ltd. (solid content acid value 51, solid content 48%, average particle size 0. 10 μm), 390 (solid acid value 54, solid content 46%, average particle size 0.09 μm), PDX7326 (solid acid value 38, solid content 38.5%, average particle size 0.10 μm), same PDX7370 (solid content acid value 87, solid content 42%, average particle size 0.08 μm), PDX7341 (solid content acid value 51, solid content 49%, average particle size 0.10 μm), 8380 (solid content acid value) 19, solid content 41%, average particle size 0.09 μm), 8300 (solid content acid value 60, solid content 43.5%, average particle size 0.09 μm), 74J (solid content acid value 51, solid content) 45%, average particle size 0.08 μm), 8383 (solid acid value 23, solid content 40%, average particle size 0.09 μm), PDX7323 (solid acid value 87, solid content 42%, average particle size) 0.08 μm), PDX7734 (solid acid value 89, solid content 41.4%, average particle size 0.09 μm), PDX7775 (solid acid value 55, solid content 45%, average particle size 0.08 μm) , 7741 (solid content acid value 52, solid content 49%, average particle size 0.10 μm), PDX7677 (solid content acid value 70, solid content 46%, average particle size 0.01 μm), 7600 (solid content). Acid value 60, solid content 47%, average particle size 0.09 μm), 775 (solid content acid value 55, solid content 45%, average particle size 0.08 μm), 537J (solid content acid value 40, solid content) 46%, average particle size 0.07 μm), 352J (solid content acid value 51, solid content 45%, average particle size 0.10 μm), 352D (solid content acid value 51, solid content 45%, average particle size) 0.10 μm), PDX7145 (solid acid value 32, solid content 50%, average particle size 0.16 μm), 538J (solid acid value 61, solid content 45%, average particle size 0.10 μm), same 8311 (solid content acid value 26, solid content 42%, average particle size 0.09 μm), PDX7667 (solid content acid value 82, solid content 45%, average particle size 0.09 μm), PDX7700 (solid content acid value) 60, solid content 48%, average particle size 0.10 μm), 7641 (solid content acid value 60, solid content 52%, average particle size 0.10 μm), 780 (solid content acid value 46, solid content 48%) , Average particle size 0.10 μm), 7610 (solid content acid value 50, solid content 52%, average particle size 0.13 μm), PDX764 3 (solid content acid value 64, solid content 51.5%, average particle size 0.14 μm), PDX7690 (solid content acid value 85, solid content 42.5%, average particle size 0.10 μm), PDX7511 (solid content acid value 85, solid content 0.10 μm) Solid content acid value 54, solid content 45.0%, average particle size 0.09 μm), PDX7164 (solid content acid value 4, solid content 47.0%, average particle size 0.17 μm), PDX7430 (solid content) Acid value 20, solid content 38.0%, average particle size 0.12 μm), PDX7440 (solid content acid value 1, solid content 48.5%, average particle size 0.25 μm), PDX7480 (solid content acid value) 18, solid content 44.0%, average particle size 0.10 μm), PDX7357 (solid acid value 59, solid content 49.5%), PDX7616A (solid acid value 38, solid content 44%), same PDX7732 (solid content acid value 87, solid content 41.4%, average particle size 0.10 μm), PDX7787 (solid content acid value 87, solid content 41.4%, average particle size 0.10 μm), PDX7356 (solid content acid value 87, solid content 41.4%, average particle size 0.10 μm) Solid content acid value 78, solid content 45.5%), PDX7615 (solid content acid value 51, solid content 50.5%, average particle size 0.12 μm), PDX7158 (solid content acid value 54, solid content 41) %), PDX7199 (solid content acid value 31, solid content 49.5%, average particle size 0.27 μm), PDX7538 (solid content acid value 62, solid content 45.5%, average particle size 0.08 μm) , PDX7780 (solid content acid value 46, solid content 48%, average particle size 0.10 μm) and the like. These styrene-acrylic acid resin emulsions having a solid acid value of 1 or more and less than 100 may be used alone or in combination of two or more.

Water is used as the main solvent for ink. In the present invention, the main solvent means a solvent that accounts for 50% by weight or more of the total amount of the solvent in the total amount of the ink composition. It is preferable to use ion-exchanged water or purified water.
Further, conventionally known organic solvents can be used in combination for various qualities of ink, for example, prevention of ink freezing at low temperature, prevention of ink drying at a pen tip, and the like. Specific examples of the organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, thiodiethylene glycol, glycerin, benzyl glycol, and benzyl. Glycos such as 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, ethylene glycol monoisopropyl ether, Sulfolane, 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, Propropylene Glycol Monobutyl Ether, Propylene Glycol Monophenyl Ether , Tripropylene glycol monobutyl ether, glycol ethers such as tripropylene glycol monophenyl ether, isopropyl alcohol, 3-methyl-3-methoxy-1-butanol, benzyl alcohol, α-methylbenzyl alcohol, lauryl alcohol, tridecyl alcohol, Examples thereof include alcohol solvents such as isododecyl alcohol and isotridecyl alcohol, propylene glycol methyl ether acetate, propylene glycol diacetate, 2-pyrrolidone, N-methyl-2-pyrrolidone, sulfolane, and γ butyrolactone. These organic solvents may be used alone or in combination of two or more. The amount of these organic solvents used is preferably 0.05% by weight or more and 30.0% by weight or less with respect to the total amount of the ink composition. The reason is unknown, but in particular, when 2-methylpentane-2,4-diol is used in combination with water and a polysaccharide alcohol of 2.5% by weight or more and 20.0% by weight or less based on the total amount of the ink composition. It dries faster, evenly and evenly to make the three-dimensional network structure of the polysaccharide more uniform.

The water-based ink composition for ballpoint pens has a high viscosity when left standing to suppress ink leakage from the pen tip, and when writing, the viscosity of the polysaccharide is reduced by the shearing force of the rotating ball, and the ink is discharged smoothly. It is used for the purpose of obtaining shear thinning for making the ink. Specific examples include xanthan gum, succinoglycan, welan gum, daiyutan gum, alcacylan, alcasea gum, zeta seagum, gellan gum, guar gum, psyllium seed gum, tamarind seed gum, tragant gum, galactomannan, cellulose, cellulose fiber, cellulose oxide, caraginan, gati gum. , Karaya gum, fermented cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose and salts thereof. In particular, xanthan gum is preferable because 2-methylpentane-2,4-diol and a styrene-acrylic acid resin emulsion having a solid acid value of 1 or more and less than 100 can maintain hand-fat writing stability for a long period of time. Xanthan gum is a polysaccharide consisting of glucose, mannose, and glucuronic acid that is separated and purified from the culture solution of xanthomonadaceae. To give specific examples, Kelzan, S, T, ST, ASX, ASXT, AR, HP, G, Ketrol CG, CG-T, CG-SFT (above, Sansho shares) (Manufactured by the company), San Ace, S, C, CS, BS, NF, G, ES, NXG-S, NXG-C, Bistop D-3000-DF , D-3000-DF-C (all manufactured by Sanei Gen FFI Co., Ltd.), Echo Gum, 630, F, T, GM, RD, SF, 521, LAX- There are T, Monato Gum GS, HP, HS, KT, Minute GR, MA, Salt (all manufactured by DSP Gokyo Food & Chemical Co., Ltd.) and the like. The viscosity, viscoelasticity, and shear thinning of these polysaccharides can be adjusted by heat-treating the polysaccharide or by applying a high pressure to the polysaccharide solution to apply high shear when passing through the nozzle. The amount of the polysaccharide used is preferably 0.05% by weight or more and 5.0% by weight or less with respect to the total amount of the ink composition, but 0.1% by weight or more with respect to the total amount of ink in order to maintain the performance as a ballpoint pen. More preferably, it is 2.0% by weight or less. If it is less than 0.05% by weight with respect to the total amount of the ink composition, the viscosity of the ink when it is left to stand is too low, and the ink tends to leak. On the other hand, if it exceeds 5.0% by weight with respect to the total amount of the ink composition, the viscosity at the time of writing becomes too high, so that the ink ejection from the pen tip tends to be poor and the writing quality tends to be poor. is there.

Phosphoric acid derivatives are generally used to improve the lubricity between the ball and the chip body and to obtain a smooth brush feel. Specific examples of the phosphoric acid derivative include NIKKOL DLP-10, DOP-8NV, DDP-2, DDP-4, DDP-6, DDP-8, DDP-10, TLP-4, and TLP-4. TCP-5, TOP-0V, TDP-2, TDP-6, TDP-8, TDP-10 (Nikko Chemicals, Inc.), Phosphanol RB-410, BH-650, ED- 200, ML-220, ML-240, RS-410, RS-610, RS-710, RL-210, RL-310, RD-720N, LB-400 (Toho Chemicals) Yakuhin Co., Ltd.), Plysurf A212C, A215C, A208F, A208N, M208F, A208B, 219B, DB-01, A210D, AL (Daiichi Kogyo Seiyaku Co., Ltd.). Even if these phosphate derivatives are salted in advance such as sodium salt, potassium salt, lithium salt, and amine salt in the ink, they are made into salts in the ink by using these phosphate derivatives and alkali together at the time of blending the ink. In that case, specific examples of the alkali include sodium hydroxide, lithium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1,3. -Propanediol and the like can be mentioned. The amount of the phosphoric acid derivative used is preferably 0.1% by weight or more and 5.0% by weight or less with respect to the total amount of the ink composition.

Furthermore, a styrene-acrylic copolymer for fixing a wetting agent such as urea, ethylene urea, and thiourea, a preservative such as benzothiazoline and omadin, a rust preventive such as benzotriazole, and a pigment on the writing surface. And its alkali salts, emulsions of vinyl acetate-based, acrylic-based and styrene-acrylic-based resins, and pH adjusters such as sodium hydroxide, 2,2-aminomethyl-1,3-propanediol, triethanolamine, and diethanolamine. , Antifoaming agents such as silicone emulsions, and various additives such as extender pigments such as aluminum silicate, calcium carbonate, and resin spheres can be used as needed.

The water-based ink composition for ballpoint pens of the present invention has a viscosity of 50 mPa · s or more and 30,000 mPa · s or less at a temperature of 25 ° C. and a shear rate of 0.35 / s, and the temperature of the water-based ink composition for ballpoint pens is 25 ° C. and shearing. By adjusting the viscosity at a speed of 35 / s to 50 mPa · s or more and 3000 mPa · s or less, the writing taste, the uniformity of the stroke, the density of the stroke, the control of the so-called ink stick that the ink is applied to the paper surface as a ball, and the suppression of bleeding. , Ink ejection stability, strike-through control of brush strokes on paper, brush stroke suppression, writing performance during drying, ink dripping suppression, ink leakage from the gap between the ball and tip when the ballpoint pen is not used, writing tip It is preferable because the writing performance and storage stability such as suppression of backflow of ink, suppression of sedimentation of pigments, and suppression of separation when the ink is left facing upward are ensured.

In producing the ink composition of the present invention, various conventionally known methods can be adopted. For example, water, a solvent and polysaccharides are put into a stirrer such as a Henschel mixer, a propeller stirrer, a homogenizer, a turbo mixer, or a high-pressure homogenizer having a high shearing force, and the mixture is stirred and dispersed. , A colorant dispersed by a disperser such as a high-pressure homogenizer, a ball mill, a bead mill, or a roll mill, and other remaining components are added, and the mixture is further mixed and stirred. Further, in these preparation steps, the generated heat of dispersion can be used as it is for stirring, heat is applied, or cooled and stirred. If necessary, the defoaming machine may be used to remove bubbles, or the filter may be used to filter coarse matter. Further, an aging step may be performed after adjusting the ink in order to sufficiently disperse the polysaccharide. These various mixing steps, dispersion steps, filtration steps, heating steps or cooling steps may be carried out individually, or two or more kinds of steps may be carried out in parallel.

In addition, an ink backflow prevention body is placed at the interface position of the ink in the ink storage tube to prevent unintended movement of the ink to the opposite side of the pen tip and ink leakage from the rear opening of the ink storage tube due to the movement. be able to. When the ink backflow preventive body is a liquid composition, a non-volatile and / or refractory liquid can be used. Specifically, vaseline, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, Examples thereof include polyether-modified silicone oil and fatty acid-modified silicone oil. These non-volatile and / or non-volatile liquids may be used alone or in combination of two or more. The non-volatile and / or refractory liquid is preferably thickened to a suitable viscosity by adding a gelling agent, and as such a gelling agent, silica having a hydrophobic treatment on the surface and methyl on the surface are used. Chemicalized silica, aluminum silicate, swelling mica, clay thickeners such as bentonite and montmorillonite treated with hydrophobicity, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, trivendilidene Examples thereof include sorbitol, fatty acid amide, amide-modified polyethylene wax, hydrogenated castor oil, dextrin-based compounds such as fatty acid dextrin, and cellulose-based compounds. Among them, fatty acid metal soap, fatty acid dextrin, and amide-modified polyethylene wax can be preferably used because they have excellent solvent resistance of the gel. In addition, fine particles such as alcohol-based solvent, glycol-based solvent, surfactant, resin, and metal oxide can be added to adjust gel strength and viscosity, prevent backflow prevention body from coloring, and prevent backflow. .. Further, in the ink backflow prevention composition, an individual such as a synthetic resin columnar object called a float or the like is arranged to narrow the space where the apparent backflow prevention body composition is arranged to resist an external force. The impact resistance may be improved by making it difficult to move.

Hereinafter, some embodiments of a ballpoint pen using the water-based ink composition for a ballpoint pen of the present invention will be described with reference to the accompanying drawings. However, the dimensions, materials, shapes, relative arrangements, etc. of the components described as embodiments or shown in the drawings are not intended to limit the scope of the present invention to this, but are merely explanatory examples. Absent.

FIG. 1 is a vertical sectional view showing a writing tool according to an embodiment. FIG. 2 is a vertical cross-sectional view showing a refill portion of the writing instrument shown in FIG.
As shown in FIG. 2, the refill 200 includes a ballpoint pen tip 1 as a writing section and an ink containing tube 6 as an ink containing section in which the ink 7 supplied to the ballpoint pen tip 1 (writing section) is stored. ..

In the exemplary embodiment shown in FIGS. 1 and 2, the writing instrument 100 includes a refill 200 and an exterior body 300.

In the embodiment shown in FIG. 1, the exterior body 300 is composed of a shaft cylinder 18, and the front shaft 19 and the rear shaft 20 of the shaft cylinder 18 are detachably fixed by screwing. A crown 21 is attached to and fixed to the rear portion of the rear axle 20 by uneven screwing while being inserted into the inner hole of the rear axle 20, and the portion exposed from the rear end of the rear axle 20 is attached to the outer surface of the rear axle 20. It is arranged so as to cover the base surface of the clip 25. Further, the crown 21 has a tubular shape, and the groove formed inside the crown 21 serves as a cam groove of the debit cam mechanism to regulate the sliding position of the rotor 23 to be installed, and by pushing the knock 22. As the rotor 23 rotates, the forward / backward movement position of the ballpoint pen refill 200 connected to the rotor 23 is defined.
A ballpoint pen refill 200 is arranged in the barrel 18 so as to be movable back and forth. An elastic member 24 made of a coil spring or the like is arranged in front of the ballpoint pen refill 200, and urges the ballpoint pen refill 200 toward the rear. The rear end of the ballpoint pen refill 200 is in contact with the tip of the rotor 23. That is, the ballpoint pen refill 200 is a haunting writing instrument that appears and disappears from the tip opening of the barrel 18 by the pressing operation of the knock 22.

As shown in FIG. 2, the refill 200 is provided via a ballpoint pen tip 1 having a ball 2 which is a writing member and a ball holder 3 which rotatably holds the ball 2 and a tip holder 5 having a through hole 4 formed therein. It has an ink storage tube 6 connected to the ballpoint pen tip 1. The ball holder 3 holds the ball 2 in a state of partially protruding from the tip opening of the ink through hole formed as a through inner hole.
Further, the ink composition 7 is housed in the ink storage tube 6, and an ink backflow preventive body 8 that is incompatible with the ink 7 is arranged in contact with the rear end interface of the ink composition 7. A ballpoint pen body that does not use the exterior body 30 can also be formed by arranging a tail plug or the like for preventing leakage of the ink composition 7 at the rear end of the ink storage tube 6 of the refill 20.

FIG. 3 is a diagram showing the configuration of the ballpoint pen tip 1 of the ballpoint pen refill 200 according to the embodiment, and is an enlarged vertical sectional view of part I of FIG. The coil spring 9 is omitted.
In the embodiment shown in FIG. 3, the ball holder 3 has a through hole formed as an ink passage in a metal cylindrical material by a drill or the like, and the through hole is formed in the ball house portion 11 from the tip side where the ball protrudes. It has a middle hole 12 and a rear hole 13. An inwardly projecting portion 14 is formed between the ball house portion 11 and the rear hole 13. The tip opening 15 of the ball house portion 11 has been reduced in diameter by caulking, and the diameter-reduced tip opening 15 and the inwardly protruding portion 14 move in the front-back and left-right directions of the ball 2. It defines the range to be obtained. By arranging a plurality of inward protrusions 14 at equal intervals in an annular shape, a radial groove 16 is formed between the adjacent inward protrusions, and the ink is formed from the rear hole 13 through the inner hole 12. It serves as a passage for the ink composition that supplies the composition 7 into the ball house portion 11. The radial groove 16 is formed by cutting after processing the ball house portion 11, the middle hole 12, and the rear hole 13. In this example, the radial groove 16 penetrates the inwardly projecting portion 14 in the axial direction and communicates with the rear hole 13 to secure the supply of the ink composition 7 to the ballhouse portion 11. However, it may be connected to the inner hole 12 in a state where the inwardly protruding portion 14 does not penetrate in the axial direction.

By arranging the coil spring 9 behind the ball 2 and pressing the ball 2 against the inner edge of the tip opening of the ball holder 3, the through holes of the ink composition are sealed when not in use, and the through hole of the ink composition is sealed from the tip of the ballpoint pen tip. It is possible to prevent the ink from oozing out, and to prevent the impact of dropping and the movement of the ink when the pen tip is left facing upward. The load with which the coil spring 9 presses the ball 2 is preferably 0.01 N or more and 1.50 N or less. As a means for pressing the ball 2, a method of directly pressing the ball 2 with a coil spring 9 having a straight portion formed as in this embodiment may be used, or a spherical or cylindrical shape is formed between the coil spring 9 and the ball 2. It may be pressed through another member of. Further, the elastic force of an elastic member such as a resin may be used.

In the above, the haunting type ballpoint pen has been described as an example of the ballpoint pen, but a cap type ballpoint pen may also be used. Alternatively, the ballpoint pen according to some embodiments may be a ballpoint pen configured to assist the ejection of the ink composition during writing by the pressure of a compressed gas or the like.

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

(Preparation of ink composition)
Ink compositions of Examples 1 to 180 and Comparative Examples 1 to 15 having the compositions shown in Tables 2 to 21 below were prepared.
Specifically, the following materials were used as the materials of each composition shown in Tables 2 to 21.

<Carbon black>
CB-1: FUJI SP BLACK 8041 (black pigment dispersion, carbon black, manufactured by Fuji Dye Co., Ltd.)
CB-2: FUJI SP BLACK 8031 (black pigment dispersion, carbon black, manufactured by Fuji Dye Co., Ltd.)

<Organic pigment>
OP-1: FUJI SP RED 5657 (red pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-2: FUJI SP RED 5563 (red pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-3: FUJI SP BLUE 6474 (blue pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-4: FUJI SP BLUE 6062 (blue pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-5: FUJI SP VIOLET 9011 (purple pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-6: FUJI SP RED 5543 (red pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-7: FUJI SP BLUE 6555 (blue pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-8: FUJI SP YELLOW 4360 (yellow pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-9: FUJI SP YELLOW 4443 (yellow pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-10: FUJI SP ORANGE 636 (orange pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-11: FUJI SP PINK 9429 (pink pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-12: FUJI SP VIOLET 9602 (purple pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-13: FUJI SP BLUE 6401 (blue pigment dispersion, organic pigment, manufactured by Fuji Dye Co., Ltd.)
OP-14: NKW 2404E (orange pigment dispersion, organic pigment, manufactured by Nippon Fluorescent Chemical Co., Ltd.)
OP-15: NKW 2405E (yellow pigment dispersion, organic pigment, manufactured by Nippon Fluorescent Chemical Co., Ltd.)
OP-16: NKW 2407E (pink pigment dispersion, organic pigment, manufactured by Nippon Fluorescent Chemical Co., Ltd.)
OP-17: NKW 2408E (blue pigment dispersion, organic pigment, manufactured by Nippon Fluorescent Chemical Co., Ltd.)
OP-18: NKW 2167E (purple pigment dispersion, organic pigment, manufactured by Nippon Fluorescent Chemical Co., Ltd.)

<Main solvent>
MS: Ion-exchanged water <organic solvent>
SOL-1: 2-methylpentane-2,4-diol SOL-2: ethylene glycol SOL-3: glycerin SOL-4: 3-methyl-3-methoxy-1-butanol SOL-5: 1,5-pentanediol SOL-6: Diethylene glycol monomethyl ether SOL-7: 1,2-butylene glycol SOL-8: Isopropyl glycol SOL-9: Sulfolane SOL-10: Diethylene glycol

<Lubricant>
LU-1: Phosphanol RB-410 (polyoxyethylene alkyl ether phosphoric acid (alkyl group C18, number of moles of ethylene oxide added 4), manufactured by Toho Chemical Industry Co., Ltd.) was adjusted to pH 8.3 by adding NaOH. 20 wt% phospanol RB-410 aqueous solution LU-2: phosphanol RS-710 (polyoxyethylene alkyl ether phosphoric acid (alkyl group C13, number of moles of ethylene oxide added 10), manufactured by Toho Chemical Industry Co., Ltd.) 20 wt% phospanol RS-710 aqueous solution adjusted to pH 8.3 by adding NaOH LU-3: Phosphanol RL-310 (polyoxyethylene alkyl ether phosphoric acid (alkyl group C18, number of moles of ethylene oxide added 3) ), 20 wt% phosphanol RL-310 aqueous solution LU-4: phosphanol ML-240 (polyoxyethylene alkyl ether phosphoric acid (polyoxyethylene alkyl ether phosphoric acid)) adjusted to pH 8.3 by adding NaOH to Toho Kagaku Kogyo Co., Ltd. 20 wt% phospanol ML-240 aqueous solution LU-5: phosphanol LB-, which was adjusted to pH 8.3 by adding NaOH to alkyl group C12, ethylene oxide added moles 4), manufactured by Toho Chemical Industry Co., Ltd. 20 wt% Phosphanol LB-400 adjusted to pH 8.3 by adding NaOH to 400 (polyoxyethylene alkyl ether phosphoric acid (alkyl group C18, number of moles of ethylene oxide added 4), manufactured by Toho Chemical Industry Co., Ltd.) Aqueous solution LU-6: 20 wt% plysurf A208N adjusted to pH 8.3 by adding NaOH to plysurf A208N (polyoxyethylene oleyl ether phosphate (alkyl groups C12, C13), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Aqueous solution LU-7: 20 wt% plysurf A215C aqueous solution LU which was adjusted to pH 8.3 by adding NaOH to plysurf A215C (polyoxyethylene oleyl ether phosphoric acid (alkyl group C13), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). -8: 20 wt% plysurf A208F aqueous solution LU-9 adjusted to pH 8.3 by adding NaOH to plysurf A208F (polyoxyethylene oleyl ether phosphoric acid (alkyl group C8), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) : Phosphanol ML-200 (polyoxyethylene alkyl ether phosphoric acid (alkyl group C12, number of moles of ethylene oxide added 0), manufactured by Toho Chemical Industry Co., Ltd.) with NaOH added 20 wt% phospanol ML-200 aqueous solution adjusted to pH 8.3 LU-10: Prysurf A219B (polyoxyethylene oleyl ether phosphoric acid (alkyl group C12), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) with NaOH. In addition, a 20 wt% plysurf A219B aqueous solution adjusted to pH 8.3

<Activator>
ACT-1: Neoperex G-25 (sodium alkylbenzene sulfonate, manufactured by Kao Corporation)

<Rust inhibitor>
RI-1: 20 wt% ethylene glycol solution of benzotriazole

<Alumina>
AO-1: AKP-50 (center particle size 0.20 μm alumina manufactured by Sumitomo Chemical Co., Ltd.)
AO-2: 0.67 wt% glycerin dispersion of AKP-50 (center particle size 0.20 μm alumina manufactured by Sumitomo Chemical Co., Ltd.) AO-3: AKP-53 (center particle size 0.18 μm alumina manufactured by Sumitomo Chemical Co., Ltd.)
AO-4: AKP-30 (center particle size 0.27 μm alumina manufactured by Sumitomo Chemical Co., Ltd.)
AO-5: AP03 (center particle size 0.3 μm, manufactured by Harzok Japan Co., Ltd.)
AO-6: AP005 (center particle size 0.05 μm, manufactured by Harzok Japan Co., Ltd.)
AO-7: AP01 (center particle size 0.1 μm, manufactured by Harzok Japan Co., Ltd.)
AO-8: AKP-20 (center particle size 0.46 μm alumina, manufactured by Sumitomo Chemical Co., Ltd.)
AO-9: 0.67 wt% glycerin dispersion of AKP-20 (center particle size 0.46 μm alumina, manufactured by Sumitomo Chemical Co., Ltd.) AO-10: AA-05 (center particle size 0.53 μm polyhedral spherical alumina, Sumitomo Chemical Co., Ltd.) Made by Chemical Co., Ltd.)
AO-11: WA # 8000 (center particle size 1.2 μm plate-like alumina, manufactured by Fujimi Incorporated Co., Ltd.)
AO-12: WA # 6000 (center particle size 2.0 μm plate-like alumina, manufactured by Fujimi Incorporated Co., Ltd.)

<Antifungal agent>
AM-1: Proxel GXL (S) (antifungal agent, manufactured by Lonza Japan Co., Ltd.)
AM-2: Proxel GXL (antifungal agent, manufactured by Lonza Japan Co., Ltd.)
AM-3: Courtside S (antifungal agent, manufactured by Takeda Pharmaceutical Company Limited)
AM-4: San-Ai Bucksodium Omagine (antifungal agent, manufactured by San-Ai Oil Co., Ltd.)
AM-5: Soda benzoate (preservative)

<Styrene-acrylic acid resin emulsion>
AC-1: John Krill 734 (styrene-acrylic acid resin emulsion, average particle size 0.08 μm, acid value 87, manufactured by BASF Japan Ltd.)
AC-2: John Krill PDX7323 (styrene-acrylic acid resin emulsion, average particle size 0.08 μm, acid value 87, manufactured by BASF Japan Ltd.)
AC-3: John Krill PDX7734 (Emulsion of styrene acrylic copolymer, average particle size 0.09 μm, acid value 89, manufactured by BASF Japan Ltd.)
AC-4: John Krill PDX7775 (Emulsion of styrene acrylic copolymer, average particle size 0.08 μm, acid value 55, manufactured by BASF Japan Ltd.)
AC-5: John Krill PDX7741 (Emulsion of styrene acrylic copolymer, average particle size 0.10 μm, acid value 52, manufactured by BASF Japan Ltd.)
AC-6: John Krill PDX7667 (Emulsion of styrene acrylic copolymer, average particle size 0.09 μm, acid value 82, manufactured by BASF Japan Ltd.)
AC-7: John Krill 352D (Emulsion of styrene acrylic copolymer, average particle size 0.10 μm, acid value 51, manufactured by BASF Japan Ltd.)
AC-8: John Krill 780 (styrene-acrylic acid resin emulsion, average particle size 0.10 μm, acid value 46, manufactured by BASF Japan Ltd.)
AC-9: John Krill PDX7362 (styrene-acrylic acid resin emulsion, average particle size 0.25 μm, acid value 38, manufactured by BASF Japan Ltd.)
AC-10: John Krill PDX7145 (styrene-acrylic acid resin emulsion, average particle size 0.16 μm, acid value 56, manufactured by BASF Japan Ltd.)
AC-11: John Krill PDX7440 (Styrene-acrylic acid resin emulsion, average particle size 0.25 μm, acid value 1, manufactured by BASF Japan Ltd.)
AC-12: John Krill 74J (styrene-acrylic acid resin emulsion, average particle size 0.08 μm, acid value 51, manufactured by BASF Japan Ltd.)
AC-13: John Krill 711 (styrene-acrylic acid resin emulsion, average particle size 0.09 μm, acid value 100, manufactured by BASF Japan Ltd.)
AC-14: John Krill 450 (styrene-acrylic acid resin emulsion, average particle size 0.16 μm, acid value 100, manufactured by BASF Japan Ltd.)
AC-15: John Krill PDX7630A (styrene-acrylic acid resin emulsion, average particle size 0.16 μm, acid value 200, manufactured by BASF Japan Ltd.)

<Acrylic resin>
AR-1: John Krill JDX6500 (Acrylic resin aqueous solution, acid value 85, manufactured by BASF Japan Ltd.)
<Resin>
RE-1: GX-205 (crosslinked poly N-vinylacetamide, manufactured by Showa Denko KK)
RE-2: PVA224E (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.)
<Polysaccharide>
PS-1: 6% by weight aqueous solution of Kelzan AR (polysaccharide, xanthan gum dispersion, manufactured by Sansho Co., Ltd.) PS-2: 0.4% by weight aqueous dispersion of Alcacylan (polysaccharide, manufactured by Hakuto Co., Ltd.) < pH adjuster>
PC-1: NaOH
PC-2: Triethanolamine PC-3: Diethanolamine PC-4: Aminomethyl propanol

The ink compositions of each Example and Comparative Example were prepared as follows.
<Examples 1-26, 30-45, 47-180>
The total amount of the 6% by weight aqueous solution of Kelzan AR as a polysaccharide, the total amount of ion-exchanged water as the main solvent, the alumina particles, and the total amount of the organic solvent excluding 2-methylpentane-2,4-diol are homogenized. Stir for 1 hour with a mixer to make an aqueous solution of xanthane gum, then add the total amount of 2-methylpentane-2,4-diol, then add carbon black or organic pigment, and finally the total amount of the remaining formulation. Was added, and the mixture was stirred with a homomixer for 1 hour to obtain an ink composition.

<Examples 27 to 29, 46>
The total amount of the 0.4 wt% aqueous dispersion of Alcacylan as a polysaccharide, the total amount of ion-exchanged water as the main solvent, the alumina particles, and the total amount of the organic solvent excluding 2-methylpentane-2,4-diol. And were stirred with a homomixer for 1 hour to prepare an alkasilan dispersion, then 2-methylpentane-2,4-diol was added, then carbon black or organic pigment was added, and finally the rest. The entire amount of the formulation was added and stirred with a homomixer for 1 hour to obtain an ink composition.

<Comparative Examples 1, 6 to 8>
The total amount of the 6 wt% aqueous solution of Kelzan AR as a polysaccharide, the total amount of ion-exchanged water as the main solvent, and the total amount of the organic solvent excluding 2-methylpentane-2,4-diol were mixed with a homomixer for 1 hour. Stir to make an aqueous solution of xanthane gum, then add 2-methylpentane-2,4-diol, then carbon black or organic pigment, and finally add the entire amount of the remaining formulation to the homomixer. The mixture was stirred for 1 hour to obtain an ink composition.

<Comparative Examples 2, 4, 5, 10 to 15>
The total amount of the 6% by weight aqueous solution of Kelzan AR as a polysaccharide, the total amount of ion-exchanged water as the main solvent, and the total amount of the organic solvent are stirred with a homomixer for 1 hour to prepare an aqueous solution of xanthan gum, and then carbon. Black or organic pigments were added, and finally the entire amount of the remaining formulation was added and stirred with a homomixer for 1 hour to give an ink composition.

<Comparative example 3>
The total amount of the resin, the total amount of ion-exchanged water as the main solvent, and the total amount of the organic solvent are stirred with a homomixer for 1 hour to prepare a resin dispersion, then carbon black or an organic pigment is added, and finally. , The entire amount of the remaining formulation was added, and the mixture was stirred with a homomixer for 1 hour to obtain an ink composition.

<Comparative Example 9>
The total amount of the resin, the total amount of ion-exchanged water as the main solvent, and the total amount of the organic solvent excluding 2-methylpentane-2,4-diol are stirred with a homomixer for 1 hour to prepare a resin dispersion, and then a resin dispersion is prepared. 2-Methylpentane-2,4-diol is added, then carbon black or organic pigment is added, and finally the entire amount of the remaining formulation is added and stirred with a homomixer for 1 hour to prepare the ink composition. Obtained.

(Test ballpoint pen tip)
In order to evaluate the ink compositions according to Examples and Comparative Examples, three types of ballpoint pen tips for testing were prepared. Table 1 shows the measured values of the dimensions of each test ballpoint pen tip, and FIG. 5 is a cross-sectional view taken along the line II-II'of FIGS. 4 and 4 showing the measurement corresponding positions of the respective dimensions.
The test ballpoint pen tip has a tapered pin (not shown) on the inward protrusion 14 (not shown) for the purpose of smoothing the surface of the inward protrusion 14 (see FIG. 3) and improving the rotation of the ball. A second ballpoint pen tip) is driven in or the ball 2 is pressed against the inwardly projecting portion 14 to form a ball seat 17 having substantially the same curvature as the ball 2.
In FIG. 4, the ball 2 in a state where the ball 2 is in contact with the tip opening 15 is shown by a dotted line, and the difference between the deviation between the solid line and the dotted line indicates the amount of movement E of the ball 2 in the front-rear direction. The ball 2 and the coil spring 9 are omitted.
FIG. 5 shows the size of the tip opening 15 from which ink is ejected from the ballpoint pen tip when the ball 2 is seated on the ball receiving seat 17. The cleaner diameter G and the radial groove diameter N mean the radius of curvature of each arrow portion (the radius of the virtual inscribed circle of each arrow portion).
Table 1 shows the dimensional values of each part of the first to third ballpoint pen tips for testing.

The material of the ball 2 used in each test ballpoint pen tip is a cemented carbide PB11 manufactured by Tsubakinakashima Co., Ltd., which contains WC as the main component, and the arithmetic average height Ra of the ball 2 (JIS B 0601). ) Was 3.0 nm. The material of the ball holder 3 was stainless steel (trade name: SF20T, Vickers hardness (HV) 240, manufactured by Shimomura Tokushu Seiko Co., Ltd.).
Further, by arranging a coil spring behind the ball 2 and pressing the ball 2 against the inner edge of the tip opening of the ball holder 3, the ink through hole when not in use is sealed, and the ink from the tip of the ballpoint pen tip is charged. It prevents bleeding, and prevents the impact of dropping and the movement of ink when the pen tip is left facing up. The spring material is SUS304 stainless wire, and the load for pressing the ball 2 is 0.3N.

The tip holder 5 is made of polybutylene terephthalate resin, and the minimum inner diameter of the through hole 4 from the rear of the ballpoint pen tip 1 to the ink storage tube 6 is 0.75 mm.

The ink storage tube 6 uses a pipe formed by extrusion molding of polypropylene resin, and the inner diameter thereof is 4.65 mm in diameter and 0.75 mm in thickness. Then, the amount of ink was 1.0 g, and 0.1 g of the ink backflow prevention composition was filled.

The ink backflow prevention composition was prepared as follows. 50.0% by weight Spectrasin 100 (α-olefin oligomer, substrate, Exxon Mobile Corporation, United States) and 45.3 wt% Lucant HC-100 (ethylene-α-olefin oligomer, substrate, Mitsui Petrochemical) Chemical Co., Ltd.), 3.5% by weight Aerosil R972 (fine particle silica, gelling agent, manufactured by Nippon Aerosil Co., Ltd.) and 1.2% by weight Leopard KL (Dextrin fatty acid ester, manufactured by Chiba Flour Milling Co., Ltd.) Was mixed and stirred with a hot stirrer at 150 ° C. for 2 hours to obtain a backflow preventive body composition. The viscosity of this backflow preventer at a temperature of 25 ° C. and a shear rate of 0.35 / s was 30,000 mPa · s.

In Examples 1 to 180 and Comparative Examples 1 to 15, a first ballpoint pen tip (denoted as the first tip in the table), a second ballpoint pen tip (denoted as the second tip in the table), and a third ballpoint pen tip (indicated in the table). A test sample ballpoint pen for evaluation was obtained by combining each of them with the third chip). The combinations of the ink compositions of Examples 1 to 180 and Comparative Examples 1 to 15 used in the test sample ballpoint pen for evaluation and the first to third ballpoint pen tips are described in the table (corresponding combinations in the table). Indicated as 〇 in the column of).

Using the ink compositions of Examples 1 to 180 and Comparative Examples 1 to 15 described above and the first to third ballpoint pen tips, the hand-fat writeability test and the handwriting dryness test described below are performed. went.

(Creation of hand-fat paper)
A solution prepared by diluting the hand fat prepared by the artificial hand fat formulation prepared by the following formulation to 30% by weight with acetone (hereinafter referred to as a 30 wt% diluted hand fat solution) is prepared.
This 30 wt% diluted hand fat solution was sprayed uniformly onto the test paper shown in 7.3 of JIS S 6061, dried at room temperature for 2 hours to remove acetone, and contaminated with hand fat. Hand grease paper 1 was prepared. Similarly, a 60% by weight diluted hand-fat solution diluted with acetone to 60% was prepared, and hand-fat paper 2 significantly contaminated with hand-fat was prepared.
(Combined with artificial hand fat)
Squalene 10% by weight
Isopropyl millistate 20% by weight
Olive oil 40% by weight
Cholesterol 2% by weight
Palmitic acid 2% by weight
Oleic acid 13% by weight
Isostearic acid 13% by weight
The above components were stirred and mixed to obtain hand fat.

(Hand-greasy writing test 1 after long-distance writing with hand-fat paper 1)
Tribo manufactured by Trinity Lab Co., Ltd. was used on hand grease paper 1 using a long-distance post-writing hand grease test ball pen that wrote 600 m in a spiral machine writing test (writing speed 7 cm / s, writing angle 70 degrees, writing load 0.98 N). A straight line of 15 cm was written under the writing conditions of −master (Type: TL201Sa) at a writing speed of 7 cm / s, a writing angle of 70 °, and a writing load of 0.98 N). After the writing was completed, the line skipping distance in the straight line was measured and used as the line skipping length (unit: cm, expressed as "hand grease paper 1 line skipping length" in the table). When all the 15 cm straight lines were skipped, writing was repeated until the skipping did not occur. After the writing was completed, the total distance of the line skipping in the straight line written repeatedly was measured and used as the line skipping length. The test results are shown in Tables 2 to 21 (indicated as "hand grease paper 1-line skip length" in the table). The unit of the measurement result shown in the table is [cm].

(Hand-greasy writing test 2 after long-distance writing with hand-fat paper 2)
Tribo manufactured by Trinity Lab Co., Ltd. was used on hand grease paper 2 using a long-distance post-writing hand grease test ball pen that wrote 600 m in a spiral machine writing test (writing speed 7 cm / s, writing angle 70 degrees, writing load 0.98 N). A straight line of 15 cm was written under the writing conditions of −master (Type: TL201Sa) at a writing speed of 7 cm / s, a writing angle of 70 °, and a writing load of 0.98 N). After the writing was completed, the line skipping distance in the straight line was measured and used as the line skipping length (unit: cm, indicated as "hand-fat paper 2-line skipping length" in the table). When all the 15 cm straight lines were skipped, writing was repeated until the skipping did not occur. After the writing was completed, the total distance of the line skipping in the straight line written repeatedly was measured and used as the line skipping length. The test results are shown in Tables 2 to 21 (indicated as "hand grease paper 2-line skip length" in the table). The unit of the measurement result shown in the table is [cm].

(Handwriting drying test)
In an environment with a room temperature of 25 ° C and a humidity of 65%, write the letters "Ei" in a 2 cm x 2 cm box on the test paper shown in 7.3 of JIS S 6061, and eraser (Pentel Co., Ltd.) When the high polymer) was rubbed once with 4.9N), the time until the paper surface became clean was determined. The test results are shown in Tables 2 to 21 (denoted as "handwriting drying time" in the table). The unit of measurement results shown in the table is [seconds].

(Measurement of physical property values)
The following physical property values were measured for Examples 1 to 180 and Comparative Examples 1 to 15 obtained as described above. The measured physical property values and measurement methods are as follows. The measurement results of each physical property value are shown in Tables 2 to 21 below.

<pH>
The pH (denoted as pH in the table) of the ink compositions of each Example and Comparative Example was measured. The pH was measured at a temperature of 25 ° C. using "LAQUA twin" Model: AS 712 manufactured by HORIBA. The pH of the ink composition is preferably 6.0 to 11.0, more preferably 7.0 to 10.0. When the pH of the water-based ink composition is within the above numerical range, discoloration of the ink can be suppressed, the change in the viscosity of the ink over time can be reduced, the dispersion stability of pigments and resins is good, and the ink is dissolved. It is possible to suppress the precipitation of substances and reduce the influence on the ink.
<Viscosity>
Viscosity at a temperature of 25 ° C and a shear rate of 0.35 / s (indicated as viscosity @ 0.35 in the table) and viscosity at a temperature of 25 ° C and a shear rate of 35 / s (viscosity @ in the table) of each example and comparative example. (Notated as 35) was measured. The unit of the measurement result shown in the table is [mPa · s]. The viscosity was measured by using "MCR-302" manufactured by Anton Pearl Co., Ltd., and the measurement conditions were a temperature of 25 ° C. and a 50 mm cone plate (1 ° C.).

Compared with Comparative Examples 1 to 15, the water-based ink compositions for ballpoint pens of Examples 1 to 180 have good handwriting that does not cause line skipping when writing on a paper surface contaminated with a hand grease component even after long-distance writing. Was obtained, and the handwriting drying property was good.
In particular, Examples 1 to 5, 12 to 38, 63 to 94, 97 to 110, 113, 114, 127 to 132, 137, 140, 143, 144, 159, 164, 169, 174 to 180 have central particle sizes. However, by containing alumina particles of 0.15 μm or more and less than 0.40 μm, it had a particularly stable hand grease resistance even after long-distance writing.

On the other hand, in Comparative Examples 1 to 15, since the alumina particles were not blended, the hand grease resistance could not be maintained after long-distance writing. In Comparative Examples 2 and 6 to 8, since the styrene-acrylic acid resin emulsion having a solid acid value of 1 or more and less than 100 was not blended, the hand-fat resistance could not be maintained after long-distance writing. Further, in Comparative Examples 3 and 9, since the added resin was not a polysaccharide, the hand oil resistance could not be maintained after long-distance writing.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and includes a modified form of the above-described embodiments and a combination of these embodiments as appropriate.

In the present specification, expressions such as "same", "equal", and "homogeneous" that indicate that things are in the same state not only represent exactly the same state, but also have tolerances or the degree to which the same function can be obtained. It shall also represent the state in which there is a difference between.
Further, in the present specification, the expression "comprising", "including", or "having" one component is not an exclusive expression excluding the existence of another component.

1 Ball pen tip 2 Ball 3 Ball holder 4 Through hole 5 Chip holder 6 Ink storage tube 7 Ink composition 8 Ink backflow prevention body 9 Coil spring 10 Float 11 Ball house part 12 Middle hole 13 Rear hole 14 Inward protrusion 15 Tip opening Part 16 Radial groove 17 Ball seat 18 Shaft cylinder 19 Front shaft 20 Rear shaft 21 Head crown 22 Knock 23 Rotator 24 Repulsion member 25 Clip 100 Writing tool 200 Refill 300 External body A Ball diameter B Tip opening diameter C Tip opening Gap width D Ball protrusion length E Ball forward / backward movement amount F Ball house diameter G Cleaner diameter H Medium hole diameter I Medium hole length J Rear hole diameter K Radial groove width L Tip outer diameter M Spherical receiving seat outer diameter N Radial Groove diameter O Radial groove depth α Caulking angle β Ball receiving seat opening angle

Claims (2)

At least carbon black and / or organic pigments, water, polysaccharides, 2-methylpentane-2,4-diol, alumina particles, and a styrene-acrylic acid resin emulsion having a solid acid value of 1 or more and less than 100. A water-based ink composition for ballpoint pens containing. The water-based ink composition for a ballpoint pen according to claim 1, wherein the central particle size of the alumina particles is 0.15 μm or more and less than 0.4 μm.

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