JP2011074276A - Water-based ink composition for ballpoint pen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based ink composition for a ballpoint pen suppressing occurrence of thin spots or writing impossibility due to clogging at the pen tip in writing. <P>SOLUTION: This water-based ink composition for a ballpoint pen comprises at least a colorant, water, and a thickening polymer, which is a polysaccharide whose molecular weight is about 1×10<SP>7</SP>to 1×10<SP>9</SP>or an acrylic acid-methacrylic acid copolymer having a molecular weight of ≥5×10<SP>5</SP>, present in ink in a particle state, and an inorganic particle such as silica and alumina whose average particle diameter is smaller than that of the polymer particle. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a water-based ink composition for a ballpoint pen that is suitably used for a ballpoint pen using a so-called ballpoint pen tip in which a ball is partially held from the tip of a ball holder as a writing member. More specifically, the present invention relates to a water-based ink composition for ballpoint pens that suppresses the occurrence of blurring or inability to write due to clogging at the writing tip.

A ballpoint pen is a ball that serves as a writing member in a through-hole that serves as an ink passage accommodated in an ink tank. The ink is transferred by bringing the ball into contact to form handwriting.
In recent years, ink used for ballpoint pens has a relatively high viscosity in a low shear rate region such as in an ink tank, but relatively high in a high shear rate region such as around a rotating ball as a writing member. An ink having shear thinning that has a low viscosity is known, and an ink composition using a polysaccharide as the ink having shear thinning is disclosed (Patent Documents 1 and 2).

JP 59-74175 JP 2005-307165 A

  The particle diameter in the state in which the polysaccharide of Patent Document 1 is present in the ink is approximately 10 μm or more, and even if it is relatively small, it exceeds 5 μm. Therefore, a water-based ballpoint pen with a small diameter ball and a ballpoint pen tip with a small clearance between the ball and the ball holding portion or a ballpoint tip with a small clearance between the ball and the ball holding portion even when the ball is relatively large is filled. In practical use, the shear-thinning agent is clogged in the ball-point pen tip and ink ejection is hindered, resulting in blurring or inability to write. Patent Document 2 discloses an ink in which a polysaccharide is present in a state of particles having an average particle diameter of less than 5 μm in the ink. However, since the polysaccharide has adhesiveness, the aggregation of particles over time. The writing stability over a long period of time cannot be maintained.

The present invention relates to at least a colorant, water, a polysaccharide having a molecular weight of about 1 × 10 ⁷ to 1 × 10 ⁹ present in the form of particles in the ink, or an alkyl acid having a molecular weight of about 5 × 10 ⁵ or more. The gist of the present invention is a water-based ink composition for ballpoint pens comprising a thickening polymer that is an alkyl methacrylate copolymer and inorganic particles having an average particle diameter smaller than that of the thickening polymer particles.

Viscosity polymer particles having a molecular weight of about 1 × 10 ⁷ to 1 × 10 ⁹ or an alkyl acid-alkyl methacrylate copolymer having a molecular weight of about 5 × 10 ⁵ or more are prepared as an ink. When they are in a static state, they adhere to each other due to their intermolecular forces and tackiness, and are in an aggregated state, but the ink is obtained by adding inorganic particles having an average particle size smaller than this thickening polymer particle. To prevent the adhesion of thickening polysaccharides by adsorbing inorganic particles on the surface of thickening polymer particles before they become bonded, and forming a layer of inorganic particles at the grain boundaries of thickening polysaccharides. Then, aggregation of the thickening polysaccharide particles when the ink is in a static state can be prevented. Therefore, it is presumed that writing blur due to clogging with a small-diameter ball can be prevented.

The thickening polymer present in the form of particles in the ink is a polysaccharide having a molecular weight of about 1 × 10 ⁷ to 1 × 10 ⁹ or an alkyl acid-alkyl methacrylate copolymer having a molecular weight of about 5 × 10 ⁵ or more. Coalescence is mentioned.
In the case of polysaccharides, thickening polysaccharides with a molecular weight of less than about 1 × 10 ⁷ exist as a three-dimensional network structure, but the network structure is relatively weak and easily broken by heat and shear for long-term storage. In this case, the thickening polysaccharide having a large molecular weight of 1 × 10 ⁷ to 1 × 10 ⁹ has a long molecular chain and is strongly entangled with each other, and exists in a particle state. Because it is not broken by heat and shear. As an example of a thickening polysaccharide having a molecular weight of about 1 × 10 ⁷ to 1 × 10 ⁹ , Zeta Seagum (Hakuto Co., Ltd.) or Arcacy Gum (Hakuto Co., Ltd.) can be used.
Zetasea gum and Arcacia gum are derived from natural products, so it is difficult to determine their molar ratio as one, but Zetasea gum is composed of 2 glucose, 1 glucuronic acid, and 3 rhamnose as constituent monosaccharides. Alkathy gum is a natural high molecular polysaccharide composed of 2 glucose, 1 glucuronic acid, 1 fucose and 1 rhamnose, and in the molecular chain Since there are many hydrophilic hydroxyl groups and the cohesive force due to hydrogen bonding between the molecular chains is stronger, the affinity with other substances is inferior and the entangled molecules are difficult to loosen. Therefore, when water and polysaccharides are added and dissolved by stirring, it is preferable to stir or heat with high shearing force so that the entangled molecules are easily loosened. In this way, a granular gel can be obtained by thoroughly loosening a polysaccharide having a large molecular weight of about 1 × 10 ⁷ to 1 × 10 ⁹ , a long molecular chain, and a tightly entangled molecule. Examples of the alkyl acid-alkyl methacrylate copolymer having a molecular weight of about 5 × 10 ⁵ or more include Pemulene TR-1, TR-2, Carbopol 941, and 1342 Carbopol (above, BF Good). Rich Chemical Co.).

  The colorant used in the ink composition of the present invention imparts a coloring effect to the handwriting and makes it visible, and includes pigments and dyes. Specific examples of pigments include organic pigments such as azo pigments, nitroso pigments, nitro pigments, basic dye pigments, acidic dye pigments, built dye pigments, mordant dye pigments, and natural dye pigments. Pigment, ocher, barium yellow, ultramarine, bitumen, cadmium red, barium sulfate, titanium oxide, petal, iron black, carbon black and other inorganic pigments, aluminum powder, gold powder, silver powder, copper powder, tin powder, brass powder, etc. Metal powder pigments, fluorescent pigments, mica pigments, and the like. Specific examples include aniline black (CI 50440), cyanine black, naphthol yellow S (CI 10316), Hansa Yellow 10G (CI 11710), Hansa Yellow 5G (CI 11660), Hansa Yellow. 3G (C.I. 11670), Hansa Yellow G (C.I. 11680), Hansa Yellow GR (C.I. 11730), Hansa Yellow A (C.I. 11735), Hansa Yellow RN (C.I. 11740), Hansa Yellow R (C.I. 12710), Pigment Yellow L (C.I. 12720), Benzidine Yellow (C.I. 21090), Benzidine Yellow G (C.I. 21095), Benzidine Yellow GR (C.I. 21100) ), Permanent Aero NCG (C.I. 20040), Balkan Fastoe -5G (C.I. 21220), Vulcan Fast Yellow R (C.I. 21135), Tartrazine Lake (C.I. 19140), Quinoline Yellow Lake (C.I. 47005), Anslagen Yellow 6GL (C Permanent Yellow FGL, Permanent Yellow H10G, Permanent Yellow HR, Anthrapyrimidine Yellow (CI. 68420), Sudan I (C.I. 12055), Permanent Orange (C.I. 12075), Resol Fast Orange (C.I. 12125), Permanent Orange GTR (C.I. 12305), Hansa Yellow 3R (C.I. 11725), Vulcan Fast Orange GG (C.I. 21165), Benzidine Orange G (C.I 21110), Persian ole Di (C.I.15510), Indanthrene brilliant orange GK (C.I.59305), Indanthrene brilliant orange RK (C.I.59105), Indanthrene brilliant orange GR (C.I.71105) Permanent Brown FG (C.I. 12480), Para Brown (C.I. 12071), Permanent Red 4R (C.I. 12120), Para Red (C.I. 12070), Fire Red (C.I. 12085) ), Parachlor ortho aniline red (C.I. 12090), resol fast scarlet, brilliant fast scarlet (C.I. 12315), brilliant carmine BS, permanent red F2R (C.I. 12310), permanent red F4R (C I.1 2335), permanent red FRL (C.I. I. 12440), Permanent Red FRLL (C.I. 12460), Permanent Red F4RH (C.I. 12420), Fast Scarlet VD, Vulcan Fast Rubin B (C.I. 12320), Vulcan Fast Pink G (C.I. 12330), Light Fast Red Toner B (C.I. 12450), Light Fast Red Toner R (C.I. 12455), Permanent Carmine FB (C.I. 12490), Pyrazolone Red (C.I. 12120), Resol Red (C.I. 15630), Lake Red C (C.I. 15585), Lake Red D (C.I. 15500), Anthosine B (C.I. 18030), Brilliant Scarlet G (C.I. 15800), Risol rubin GK (C.I.158) 5), Permanent Red F5R (C.I. 15865), Brilliant Carmine 6B (C.I. 15850), Pigment Scarlet 3B (C.I. 16105), Bordeaux 5B (C.I. 12170), Toluidine Maroon (C Perm. Bordeaux F2R (C.I. 12385), Helio Bordeaux BL (C.I. 14830), Bordeaux 10B (C.I. 15880), Bon Maroon Light (C.I. 15825), Bonn Maroon Medium (C.I. 15880), Eosin Lake (C.I. 45380), Rhodamine Lake B (C.I. 45170), Rhodamine Lake Y (C.I. 45160), Alizarin Lake (C.I. 58000) ), Thioindigo red B (C.I. 73300), thioindigo Rune (C.I. 73385), Permanent Red FGR (C.I. 12370), PV Carmine HR, Watching Red, Monolite Fast Red YS (C.I. 59300), Permanent Red BL, Fast Violet B, Methyl Violet Lake (C.I. 42535), Dioxazine Violet, Alkaline Blue Lake (C.I. 42750A, C.I. 42770A), Peacock Blue Lake (C.I. 42090), Peacock Blue Lake (C.I. 42025), Victoria Blue Lake (C.I. 44045), Phthalocyanine Blue (C.I. 74160), Fast Sky Blue (C.I. 74180), Indanthrene Blue RS (C.I. 69800), Indance Ren Blue BC (C.I.6 9825), Indigo (C.I. I. 73000), Pigment Green B (C.I. 10006), Naphthol Green B (C.I. 10020), Green Gold (C.I. 12775), Acid Green Lake, Malachite Green Lake (C.I. 42000), Examples thereof include phthalocyanine green, which are used by dispersing them in a liquid medium.

Commercially available water-dispersed pigments are preferably used because of their increased handleability and productivity. Specific examples of water-dispersed pigments include Fuji SP Black 8031, 8119, 8167, 8276, 8381, 8406, Fuji SP Red 5096, 5111, 5193, 5220, Fuji SP Bordeaux 5500, Fuji. SP Blue 6062, 6133, 6134, 6401, Fuji SP Green 7051, Fuji SP Yellow 4060, 4178, Fuji SP Violet 9011, FujiSP Pink 9524, 9527, Fuji SP OrangeF 34 5543, 5544 (above, manufactured by Fuji Dye Co., Ltd.), Emacol Black CN, Emacol Blue FBB, FB, KR, Emacol Green LXB, Emacol Violet BL, Emacol Brown 3101, Emacol Carmine FB, Emacol RedBS, Emacol Orange R, Emacol Yellow FD, G7 G1, G5 10GN, 10G, Sandy Super Black K, C, Sandy Super Gray B, Sandy Super Brown SB, FRL, RR, Sandy Super G Green L5G, GXB, SandL Super H -H, FBL-160, FBB, Sandye Super Violet BL H / C, BL Sandy Super Bordeaux FR, Sandy Super Pink FBL, F5B, Sandy Super Rubin FR, Sandy super Carminine FB, Sandy Super Red FFG, Sandy Super Carbine FB, Sandy Super Red FF, Sandy Super Red 5GR, R, 3R, Sandye Ywllow GG, F3R, IRC, FGN, GN, GRS, GSR-130, GSN-130, GSN, 10GN (above, Sanyo Dye) Manufactured), Rio Fast Black Fx 8012, 8313, 8169, Rio Fast Red Fx 8209, 8172, Rio Fast Red SF 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) 2102, 2103, 2104, 2105, 2106, 2106, 2108, 2108, 2117, 2127, 2137, 2167, 2101P, 2102P, 2103P, 2104P, 2105P, 2105P, 2106P 2107P, 2108P, 2117P, 2117P, 2127P, 2137P, 2167P, NKW-3002, 3003, 3004, 3005, 3007, 3077, 3008, 3402, 3404, 3405, 3407, 3408, 3477, 3602, 3603, 3604, 3605, 3607, 3777, 3608, 3702, 3703, 3704, 3705, 3777, 3708 6013, 6038, 6559 (manufactured by Nippon Fluorescence Co., Ltd.), Cosmo Color S1000F Series (manufactured by Toyo Soda Co., Ltd.), Victoria Yellow G-11, G-20, Victoria Orange G-16, G-21, Victoria Red G-19, G-22, Victoria Pink G-17, G-23, Victoria Green G-18, G-24, Victoria Blue G-15, G-25 (and above) , Gokoku Color Co., Ltd.), Pollux PC5T1020, Pollux Black PC8T135, Polook Thread IT 030, etc. Pollux series of (manufactured by Sumika Color Co., Ltd.), and the like.
As specific examples of the dye, any of acid dyes, direct dyes, basic dyes and the like can be used. For example, Japanol Fast Black D Conch (CI Direct Black 17), Water Black 100L (19), Water Black L-200 (19), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black EX (38), Direct Fast Black Conk (51), Kayala Spragley VGN (71), Kayalas Direct Brilliant Yellow G (CI Direct Yellow 4) ), Direct Fast Yellow 5GL (26), Eisen Primula Yellow GCLH (44), Direct Fast Yellow R (50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet G X (4), Direct Fast Scarlet 4BS (23), Eisen Direct Rhodulin BH (31), Direct Scarlet B (37), Kayak Direct Scarlet 3B (39), Eisen Primula Pink 2BLH (75) ), Sumilite Red F3B (80), Eisen Primula Red 4BH (81), Kayara Spral Bin BL (83), Kayara Light Red F5G (225), Kayara Light Red F5B (226), Caillas Light Rose FR (same as 227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (same as 15), Sumilite Splash Blue BRR Conch (same as 71), Dibogen Turquoise Blue S 86), Water Blue # 3 (same as above) 6), direct dyes such as Kayala Star Coyze Blue GL (86), Kayala Supra Blue FF2GL (106), Kayara Supra Turquoise Blue FBL (199), Acid Blue Black 10B (CI Acid Black) 1), Nigrosine (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (26), Suminol Fast Black BR Conk (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conk (52), Sumilan Black WA (52), Ranil Black BG Extra Conk (107), Kyanol Milling Black TLB (109), Suminol Milling Black B (109), Kaya NORMILLING BLACK TLR ( 110), Eisen Opal Black New Conque (119), Water Black 187-L (154), Kayaku Acid Brilliant Flavin FF (C.I. I. Acid Yellow 7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Daiwa Tarrazine (23), Kayaktor Torazin (23) , Suminol Fast Yellow R (25), Diacid Light Yellow 2GP (29), Suminoll Milling O O (38), Suminol Milling MR MR (42), Water Yellow # 6 (42), Kayanol Yellow NFG (49), Suminol Milling Yellow 3G (72), Suminol Fast Yellow G (61), Suminol Milling Yellow G (78), Kayanol Yellow N5G (110), Suminol Milling Yellow 4G 200% (same 141), Kayanor Yellow NG (same 135), Kayano Lumiling Yellow 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 Conk (62), Mitsui Nylon Fast Sky Blue B (78), Sumitomo Brilliant Indocyanine 6Bh / c (83), Sandlancyanine N-6B 350% (90), Water Blue # 115 (90), Orient Soluble Blue OBB The same 93), Sumitomo brilliant blue 5G (the 103), Kaya Nord milling Ultra Sky SE (the 112), Kaya Nord milling cyanine 5R (the 113), Aizen Opal Blue 2GLH (the 158), Daiwa Guinea green B (C. I. Acid Green 3), Acid Brilliant Milling Green B (same 9), Daiwa Green # 70 (same 16), Cyanol Cyanine Green G (same 25), Suminol Milling Green G (same 27), etc. Ron Yellow 3GLH (CI Basic Yellow 11), Eisen Cachiron Brilliant Yellow 5GLH (13), Sumiacryl Yellow E-3RD (15), Maxilon Yellow 2RL (19), Astrazone Yellow 7GLL (same) 21), Kayacrill Golden Yellow GL-ED (same 28), Astrazone Yellow 5GL (same 51), Eisen Cachiron Orange GLH (CI Basic Orange 21), Eisen Katyron Brown 3GLH (same 30), Rhodamine 6 GCP (C.I. Cred 1), Eisen Astrafloxin (12), Sumiacryl Brilliant Red E-2B (15), Astrazone Red GTL (18), Eisen Cathlon Brilliant Pink BGH (27), Maxilon Red GRL (same) 46), Eisenmethyl Violet (CI Basic Violet 1), Eisen Crystal Violet (Same 3), Eisen Rhodamine B (Same 10), Astrazone Blue G (CI Basic Blue 1), Astrazone Blue BG (Same 3), methylene blue (same 9), maxilon blue GRL (same 41), Eisen Cachiron blue BRLH (same 54), Eisen Diamond Green GH (CI Basic Green 1), Eisen Malachite Green (same 4) ), Bismarck Blau G include basic dye (C.I. Basic Brown 1) and the like. The above pigments and dyes can be used alone or in combination.

Water is used as the main ink agent.
Furthermore, conventionally known high-boiling organic solvents can be used for various purposes as inks, for example, prevention of ink freezing at low temperatures and prevention of ink drying at the nib. Specific examples of the high-boiling organic solvent include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, hexylene glycol, 1,3-butylene glycol, thiodiethylene glycol, glycerin, benzyl glycol, and benzyl diglycol. , Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, ethylene glycol monobutyl ether ,ethylene glycol Glycols such as nohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether Alcohol solvents such as ethers, benzyl alcohol, α-methylbenzyl alcohol, lauryl alcohol, tridecyl alcohol, isododecyl alcohol, isotridecyl alcohol, propylene glycol methyl ether acetate, propylene glycol diacetate, 2-pyrrolidone, N- Methyl-2-pyrrolidone, etc. Is mentioned. These high boiling point organic solvents can be used alone or in combination. The amount used is preferably 10 to 60% by weight based on the total amount of the ink composition. These organic solvents can be used alone.

It is necessary that the average particle diameter of the inorganic particles is smaller than the average particle diameter of the thickening polymer.
Examples of inorganic particles include magnesium hydroxide, alumina, boron carbide, silicon carbide, molybdenum oxide, calcium carbonate and silica, aluminum silicate, silicon nitride, sericite, talc, mica, graphite, kaolin clay, bentonite, Nε -Lauroyl lysine, boron nitride, mica, N-lauroyl-β-alanine calcium, calcium carbonate, magnesium carbonate, magnesium sulfate, lead chromate, barium chromate, calcium silicide, calcium silicate, potassium silicofluoride, oxidation Silver, zirconium oxide, sodium oxide, palladium oxide, zinc oxide, cobalt oxide, lithium tungsten oxide, titanium oxide, magnesium oxide, barium oxide, molybdenum oxide, molybdenum barium oxide, lithium tungsten oxide, sodium hypochlorite , Potassium tetraborate, sodium tetraborate, potassium nitrate, strontium nitrate, magnesium nitrate hexahydrate, lithium hydroxide monohydrate, calcium hydride, lithium hydride, sulfamic acid, nickel sulfamate, potassium selenate , Zirconium carbide, tungsten carbide, titanium carbide, calcium tungstate, zirconium carbonate, sodium carbonate decahydrate, strontium carbonate, sodium thiosulfate, sodium thiosulfate pentahydrate, magnesium thiosulfate, calcium nitride, zirconium nitride, nitride Titanium, magnesium nitride, sodium disulfite, molybdenum disilicide, titanium diboride, lithium nickelate, potassium disulfate, potassium fluoride, calcium fluoride, potassium hydrogen fluoride, sodium fluoride, barium fluoride Magnesium fluoride, lithium fluoride, calcium boride, molybdate, calcium molybdate, cobalt molybdate, titanium iodide, zinc sulfide, silicon sulfide, iron sulfide, sodium sulfide, palladium sulfide, aluminum sulfate, potassium aluminum sulfate Examples thereof include dodecahydrate, potassium sulfate, calcium sulfate, potassium hydrogen sulfate, lead sulfate, barium sulfate, lithium sulfate monohydrate and the like. As long as the effects of the present invention are not impaired, potassium titanate whisker, calcium carbonate whisker, titanium dioxide whisker, magnesium sulfate whisker, calcium sulfate whisker, aluminum sulfate whisker and the like can be used as the fibrous material. The inorganic particles have various shapes such as a spherical shape, a needle shape, an indefinite shape, and a plate shape. The average minor axis A of the inorganic particles and the average major axis B of the inorganic particles have a relationship of B / A> 5. Furthermore, it is preferable that the average major axis B and the average middle diameter C of the inorganic particles satisfy the relationship B / C <4. This is because when B / A ≦ 5, the inorganic particles adsorbed on the thickening polymer become thicker, the apparent size of the thickening high molecular weight after the inorganic particles are adsorbed increases, and the fluidity of the ink is affected. It is because it may come out. Here, the dimension of the inorganic particles is such that the length of the axis where the particle has the maximum outer diameter is the major axis B which is the particle diameter, the length where the outer diameter is the maximum on the axis perpendicular to the axis is the medium diameter C, and the major axis The length which becomes the maximum outer diameter on the axis orthogonal to each of B and the medium diameter C is the short diameter A, and can be measured with an electron microscope. These inorganic particles can be used alone or in combination. The amount used is preferably 0.1 to 5% by weight based on the total amount of ink. If it is less than 0.1%, the adsorption of inorganic particles is small and the effect of preventing aggregation is not sufficient, and if it is 5% or more, the amount of inorganic particles increases and the handwriting may be somewhat different from the desired color. Because there is,

  Furthermore, wetting agents such as urea, ethylene urea and thiourea, antiseptics such as benzothiazoline and omadin, rust inhibitors such as benzotriazole, and styrene-acrylic copolymers for fixing pigments to the writing surface And alkali salts thereof, emulsions such as vinyl acetate, acrylic and styrene-acrylic resins, pH adjusters such as sodium hydroxide, 2,2-aminomethyl-1,3-propanediol, diethanolamine, silicone emulsions Various additives such as defoaming agents such as alumina, extender pigments such as alumina, aluminum silicate, calcium carbonate, and resin spheres can be used as necessary.

  In producing the ink composition of the present invention, various conventionally known methods can be employed. For example, after adding water and polysaccharides to a stirrer such as a Henschel mixer with high shearing force and stirring and dissolving, add the pigment and other remaining components dispersed by a dispersing machine such as a ball mill, bead mill, and roll mill, and further mix and stir. Can be easily obtained. You may perform the removal of the foam by a defoamer, filtration of the coarse thing by a filter, etc. as needed. Furthermore, it is preferable to perform an aging process in which heat is applied after adjusting the ink in order to make the polysaccharide sufficiently soluble.

  Hereinafter, the present invention will be described in detail with reference to examples. In the examples, “parts” simply means “parts by weight”.

Example 1
Ion-exchanged water 50.97 parts Propylene glycol 6.00 parts Glycerin 14.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J734 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 1.00 parts FUJI SP BLACK 8970 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
25.00 parts Sodium salt 20% aqueous solution of oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts Diethanolamine (pH adjuster) 0.20 parts Zeta Seagum (Thickening polysaccharide) , Hakuto Co., Ltd. 0.22 parts Inorganic particles (plate-like silica, average major axis 0.6 μm, average middle diameter 0.6 μm, average minor axis less than 0.1 μm) 0.10 parts Among the above components, ion exchange, ethylene Glycol and zeta sea gum were put into a Henschel mixer and stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 2.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered, defoamed with the defoamer, and after leaving to stand in 70 degreeC environment for 24 hours, the black water-based ink for ball-point pens was obtained.

(Example 2)
Ion-exchanged water 46.85 parts Ethylene glycol 10.00 parts Glycerin 10.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill 450 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 2.00 parts FUJI SP RED 5653 (pigment dispersion, manufactured by Fuji Color Co., Ltd.) 25.00 parts Oxyethylene alkyl ether Phosphoric acid (Phosphanol RS710, manufactured by Toho Chemical Co., Ltd.) 20% sodium salt aqueous solution) 5.00 parts Diethanolamine (pH adjuster) 0.20 parts Zeta Seagum (thickening polysaccharide, Hakuto Co., Ltd.) 0 .25 parts Inorganic particles (plate-like silica, average major axis 1.0 μm, average medium diameter 0.9 μm, average minor axis less than 0.1 μm) 0.10 parts Among the above components, ion exchange, ethylene glycol and zeta sea gum, Henschel mixer The mixture was stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 3.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Thereafter, filtration was carried out, defoaming was carried out with a defoaming machine, and then the mixture was left standing at 70 ° C. for 24 hours, and then a red ballpoint pen aqueous ink was obtained.

(Example 3)
Ion-exchanged water 48.00 parts Propylene glycol 10.00 parts Glycerin 10.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J775 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts FUJI SP BLUE 6474 (pigment dispersion, manufactured by Fuji Color Co., Ltd.) 20.00 parts Oxyethylene oleyl ether Sodium salt 20% aqueous solution of phosphoric acid (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 5.00 parts Triethanolamine (pH adjuster) 1.00 parts Zeta Seagum (thickening polysaccharide, Hakuto Co., Ltd.) 0.30 parts Inorganic particles (plate-like silica, average major axis 2.0 μm, average median diameter 0.2 μm, average minor axis less than 0.1 μm) 0.10 parts In the above components, ion exchange, ethylene glycol and zeta sea gum, Henschel The mixture was put into a mixer and stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 5.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Thereafter, filtration was carried out, defoaming was carried out with a defoaming machine, and the mixture was left standing in an environment at 70 ° C. for 24 hours.

Example 4
Ion-exchanged water 42.85 parts Propylene glycol 10.00 parts Glycerin 10.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J775 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts NKW2167E (colored resin dispersion, manufactured by Nippon Fluorescence Co., Ltd.) 25.00 parts Oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Co., Ltd.) 20% aqueous sodium salt solution 5.00 parts Triethanolamine (pH adjuster) 1.00 parts Zeta Seagum (thickening polysaccharide, Hakuto Co., Ltd.) 0. 25 parts inorganic particles (plate-like silica, average major axis 0.6 μm, average median diameter 0.6 μm, average minor axis less than 0.1 μm) 0.30 parts Among the above components, ion exchange, ethylene glycol and zeta sea gum are added to the Henschel mixer. The mixture was stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 5.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered and defoamed with the defoaming machine and obtained the water-based ink for purple ball-point pens.

(Example 5)
Ion-exchanged water 22.90 parts Propylene glycol 12.00 parts Glycerin 15.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.1 part Jonkrill J734 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts FUJI SP BLACK 8970 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
25.00 parts Sodium salt 20% aqueous solution of oxyethylene oleyl ether phosphoric acid (Phosphanol RB410, manufactured by Toho Chemical Co., Ltd.) 5.00 parts Diethanolamine (pH adjuster) 0.20 parts Viscosity adjuster solution A 14 0.000 part inorganic particles (plate-like silica, average major axis 0.3 μm, average median diameter 0.3 μm, average minor axis less than 0.03 μm) 0.30 parts These blends are placed in a Henschel mixer and heated to 50 ° C. After mixing and stirring at 1300 rpm for 60 minutes, the mixture was cooled and taken out. The average particle size of this Arca gum was 1.0 μm. Then, it filtered, defoamed with the vacuum degassing machine, and after leaving to stand in 70 degreeC environment for 24 hours, the black water-based ink for ball-point pens was obtained.

(Viscosity modifier solution A)
Ion-exchanged water 73.50 parts Ethylene glycol 25.00 parts Proxel GXL (preservative, Avicia Co., Ltd.) 0.50 parts Alkasy gum (thickening polysaccharide, manufactured by Hakuto Co., Ltd.) 1.00 parts The mixture was put into a Henschel mixer, heated to 70 ° C., stirred and dissolved at 2800 rpm for 60 minutes, cooled, and taken out to obtain a viscosity modifier solution A. The average particle size of this Arca gum was 1.0 μm.

(Example 6)
Ion-exchanged water 28.10 parts Propylene glycol 10.00 parts Glycerin 10.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J775 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts FUJI SP BLUE 6474 (pigment dispersion, manufactured by Fuji Color Co., Ltd.) 20.0 parts sodium oleylsarcosine 20% aqueous solution of salt (lubricant, sarcosinate OH, manufactured by Nikko Chemicals Co., Ltd.) 5.00 parts Triethanolamine (pH adjuster) 1.20 parts Viscosity adjuster solution A 20.00 parts Inorganic particles (plate-like alumina) Average major axis 0.3 μm, average middle diameter 0.3 μm, average minor axis less than 0.03 μm)
0.10 parts Of these formulations, except for Johncrill J775, put into a Henschel mixer, heat to 70 ° C., stir at 2800 rpm for 60 minutes, cool, add Joncryl J775, stir at 1300 rpm for 10 minutes and take out. It was. The average particle size of this Arca gum was 1.0 μm. Then, it filtered, defoamed with the vacuum degassing machine, and after leaving to stand in 70 degreeC environment for 24 hours, the blue water-based ink for ball-point pens was obtained.

(Example 7)
Ion-exchanged water 28.10 parts Propylene glycol 10.00 parts Glycerin 10.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J775 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts FUJI SP BLUE 6474 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
20.00 parts 20% aqueous solution of oleyl sarcosine sodium salt (lubricant, sarcosineate OH, manufactured by Nikko Chemicals Co., Ltd.) 5.00 parts triethanolamine (pH adjuster) 1.20 parts Viscosity adjuster solution A 20. 00 parts Inorganic particles (plate-like calcium carbonate, average major axis 0.6 μm, average medium diameter 0.6 μm, average minor axis less than 0.1 μm) 0.10 parts Of these blends, except for John Krill J775, Henschel mixer The mixture was heated to 70 ° C., stirred at 2800 rpm for 60 minutes, cooled, added Joncrill J775, and taken out after stirring at 1300 rpm for 10 minutes. The average particle size of this Arca gum was 1.0 μm. Then, it filtered, defoamed with the vacuum degassing machine, and after leaving to stand in 70 degreeC environment for 24 hours, the blue water-based ink for ball-point pens was obtained.

(Example 8)
Water 27.80 parts Glycerin 21.00 parts Ethylene glycol 4.00 parts Benzotriazole 1.00 parts Proxel GXL (s) (preservative, Avicia Co., Ltd.) 0.20 parts NKW-2167E-P (colored resin dispersion) 40.00 parts 20% aqueous solution of sodium salt of oleyl sarcosine (lubricant, sarcosinate OH, manufactured by Nikko Chemicals Co., Ltd.) 5.00 parts Jonkrill 61j (water-soluble styrene-acrylic copolymer) Union, Johnson Polymer Co., Ltd.
0.50 parts Pemulene TR-1 (thickening polymer, acrylic acid-alkyl methacrylate copolymer, manufactured by BFGoodrich) 0.40 parts inorganic particles (plate-like silica, average major axis 0.6 μm, average middle diameter 0) 0.1 μm, average minor axis less than 0.1 μm) 0.10 parts In the above components, Pemulen TR-1 and water were mixed and stirred with a propeller stirrer for 30 minutes to prepare an aqueous solution of Pemulen TR-1. The average particle size of Pemulen TR-1 was 2.0 μm. The remaining components were added to this and further stirred for 1 hour. Thereafter, the pH was adjusted to 7.0 with triethanolamine, followed by filtration and defoaming with a defoamer to obtain an aqueous ink for purple ballpoint pen.

Example 9
Water 27.80 parts Glycerin 21.00 parts Ethylene glycol 4.00 parts Benzotriazole 1.00 parts Proxel GXL (s) (preservative, Avicia Co., Ltd.) 0.20 parts NKW-2167E-P (colored resin dispersion) 40.00 parts 20% aqueous solution of sodium salt of oleyl sarcosine (lubricant, sarcosinate OH, manufactured by Nikko Chemicals Co., Ltd.) 5.00 parts Jonkrill 61j (water-soluble styrene-acrylic copolymer) Union, Johnson Polymer Co., Ltd.
0.50 parts Pemulene TR-1 (thickening polymer, acrylic acid-alkyl methacrylate copolymer, BFGoodrich) 0.40 parts inorganic particles (boron nitride), average major axis 0.6 μm, average middle diameter 0 0.10 parts In the above components, pemulene TR-1 and water were mixed and stirred with a propeller stirrer for 30 minutes to prepare an aqueous solution of pemulen TR-1. The average particle size of Pemulen TR-1 was 2.0 μm. The remaining components were added to this and further stirred for 1 hour. Thereafter, the pH was adjusted to 7.0 with triethanolamine, followed by filtration and defoaming with a defoamer to obtain an aqueous ink for purple ballpoint pen.

(Example 10)
Ion-exchanged water 28.10 parts Propylene glycol 10.00 parts Glycerin 10.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J775 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts FUJI SP BLUE 6474 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
20.00 parts 20% aqueous solution of oleyl sarcosine sodium salt (lubricant, sarcosineate OH, manufactured by Nikko Chemicals Co., Ltd.) 5.00 parts triethanolamine (pH adjuster) 1.20 parts Viscosity adjuster solution A 20. 00 parts Inorganic particles (titanium oxide, average major axis 0.6 μm, average median diameter 0.1 μm, average minor axis less than 0.1 μm) 0.10 parts Of these compounds, except for John Crill J775, put into Henschel mixer The mixture was heated to 70 ° C., stirred at 2800 rpm for 60 minutes, cooled, added Joncrill J775, and taken out after stirring at 1300 rpm for 10 minutes. The average particle size of this Arca gum was 1.0 μm. Then, it filtered, defoamed with the vacuum degassing machine, and after leaving to stand in 70 degreeC environment for 24 hours, the blue water-based ink for ball-point pens was obtained.

(Example 11)
Ion-exchanged water 28.10 parts Propylene glycol 10.00 parts Glycerin 10.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J775 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts FUJI SP BLUE 6474 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
20.00 parts 20% aqueous solution of oleyl sarcosine sodium salt (lubricant, sarcosineate OH, manufactured by Nikko Chemicals Co., Ltd.) 5.00 parts triethanolamine (pH adjuster) 1.20 parts Viscosity adjuster solution A 20. 00 parts Inorganic particles (magnesium carbonate, average major axis 0.6 μm, average median diameter 0.03 μm, average minor axis less than 0.1 μm) 0.10 parts Of these compounds, except for John Crill J775, put into Henschel mixer The mixture was heated to 70 ° C., stirred at 2800 rpm for 60 minutes, cooled, added Joncrill J775, and taken out after stirring at 1300 rpm for 10 minutes. The average particle size of this Arca gum was 1.0 μm. Then, it filtered, defoamed with the vacuum degassing machine, and after leaving to stand in 70 degreeC environment for 24 hours, the blue water-based ink for ball-point pens was obtained.

(Example 12)
Ion-exchanged water 28.10 parts Propylene glycol 10.00 parts Glycerin 10.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J775 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts FUJI SP BLUE 6474 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
20.00 parts 20% aqueous solution of oleyl sarcosine sodium salt (lubricant, sarcosineate OH, manufactured by Nikko Chemicals Co., Ltd.) 5.00 parts triethanolamine (pH adjuster) 1.20 parts Viscosity adjuster solution A 20. 00 parts Inorganic particles (boron carbide, average major axis 0.3 μm, average median diameter 0.2 μm, average minor axis less than 0.1 μm) 0.10 parts Of these compounds, except for John Crill J775, put into Henschel mixer The mixture was heated to 70 ° C., stirred at 2800 rpm for 60 minutes, cooled, added Joncrill J775, and taken out after stirring at 1300 rpm for 10 minutes. The average particle size of this Arca gum was 1.0 μm. Then, it filtered, defoamed with the vacuum degassing machine, and after leaving to stand in 70 degreeC environment for 24 hours, the blue water-based ink for ball-point pens was obtained.

(Example 13)
Ion-exchanged water 50.97 parts Propylene glycol 6.00 parts Glycerin 14.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J734 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 1.00 parts FUJI SP BLACK 8970 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
25.00 parts Sodium salt 20% aqueous solution of oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts Diethanolamine (pH adjuster) 0.20 parts Zeta Seagum (Thickening polysaccharide) , Hakuto Co., Ltd. 0.22 parts Inorganic particles (molybdenum oxide, average major axis 0.6 μm, average middle diameter 2.0 μm, average minor axis less than 0.1 μm) 0.10 parts Among the above components, ion exchange, ethylene glycol And zeta seagum were placed in a Henschel mixer and stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta seagum aqueous solution. The average particle size of the zeta sea gum was 2.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered, defoamed with the defoamer, and after leaving to stand in 70 degreeC environment for 24 hours, the black water-based ink for ball-point pens was obtained.

(Example 14)
Ion-exchanged water 50.97 parts Propylene glycol 6.00 parts Glycerin 14.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J734 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 1.00 parts FUJI SP BLACK 8970 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
25.00 parts Sodium salt 20% aqueous solution of oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts Diethanolamine (pH adjuster) 0.20 parts Zeta Seagum (Thickening polysaccharide) , Hakuto Co., Ltd. 0.22 parts Inorganic particles (aluminum silicate, average major axis 0.6 μm, average middle diameter 0.6 μm, average minor axis less than 0.1 μm) 0.10 parts Among the above components, ion exchange, ethylene glycol And zeta seagum were placed in a Henschel mixer and stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta seagum aqueous solution. The average particle size of the zeta sea gum was 2.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered, defoamed with the defoamer, and after leaving to stand in 70 degreeC environment for 24 hours, the black water-based ink for ball-point pens was obtained.

(Example 15)
Ion-exchanged water 50.97 parts Propylene glycol 6.00 parts Glycerin 14.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J734 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 1.00 parts FUJI SP BLACK 8970 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
25.00 parts Sodium salt 20% aqueous solution of oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts Diethanolamine (pH adjuster) 0.20 parts Zeta Seagum (Thickening polysaccharide) , Hakuto Co., Ltd. 0.22 parts Inorganic particles (magnesium hydroxide, average major axis 0.6 μm, average middle diameter 0.5 μm, average minor axis less than 0.1 μm) 0.10 parts Among the above components, ion exchange, ethylene Glycol and zeta sea gum were put into a Henschel mixer and stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 2.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered, defoamed with the defoamer, and after leaving to stand in 70 degreeC environment for 24 hours, the black water-based ink for ball-point pens was obtained.

(Example 16)
Ion-exchanged water 50.97 parts Propylene glycol 6.00 parts Glycerin 14.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J734 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 1.00 parts FUJI SP BLACK 8970 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
25.00 parts Sodium salt 20% aqueous solution of oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts Diethanolamine (pH adjuster) 0.20 parts Zeta Seagum (Thickening polysaccharide) , Hakuto Co., Ltd. 0.22 parts Inorganic particles (aluminum sulfate, average major axis 0.6 μm, average middle diameter 0.5 μm, average minor axis less than 0.1 μm) 0.10 parts Among the above components, ion exchange, ethylene glycol And zeta seagum were placed in a Henschel mixer and stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta seagum aqueous solution. The average particle size of the zeta sea gum was 2.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered, defoamed with the defoamer, and after leaving to stand in 70 degreeC environment for 24 hours, the black water-based ink for ball-point pens was obtained.

(Example 17)
Water 27.80 parts Glycerin 21.00 parts Ethylene glycol 4.00 parts Benzotriazole 1.00 parts Proxel GXL (s) (preservative, Avicia Co., Ltd.) 0.20 parts NKW-2167E-P (colored resin dispersion) 40.00 parts 20% aqueous solution of sodium salt of oleyl sarcosine (lubricant, sarcosinate OH, manufactured by Nikko Chemicals Co., Ltd.) 5.00 parts Jonkrill 61j (water-soluble styrene-acrylic copolymer) Union, Johnson Polymer Co., Ltd.
0.50 parts Pemulene TR-1 (thickening polymer, acrylic acid-alkyl methacrylate copolymer, BFGoodrich) 0.40 parts inorganic particles (silica, average major axis 0.6 μm, average medium diameter 0.6 μm) , Average minor axis 0.2μm)
0.10 parts In the above components, Pemulen TR-1 and water were mixed and stirred with a propeller stirrer for 30 minutes to prepare an aqueous solution of Pemulen TR-1. The average particle size of Pemulen TR-1 was 2.0 μm. The remaining components were added to this and further stirred for 1 hour. Thereafter, the pH was adjusted to 7.0 with triethanolamine, followed by filtration and defoaming with a defoamer to obtain an aqueous ink for purple ballpoint pen.

(Example 18)
Ion-exchanged water 50.97 parts Propylene glycol 6.00 parts Glycerin 14.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J734 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 1.00 parts FUJI SP BLACK 8970 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
25.00 parts Sodium salt 20% aqueous solution of oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts Diethanolamine (pH adjuster) 0.20 parts Zeta Seagum (Thickening polysaccharide) , Hakuto Co., Ltd. 0.22 parts Inorganic particles (alumina, average major axis 1.0 μm, average middle diameter 1.0 μm, average minor axis less than 1.0 μm) 0.10 parts Among the above components, ion exchange, ethylene glycol and The zeta sea gum was placed in a Henschel mixer and stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 2.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered, defoamed with the defoamer, and after leaving to stand in 70 degreeC environment for 24 hours, the black water-based ink for ball-point pens was obtained.

(Comparative Example 1)
Water 27.80 parts Glycerin 21.00 parts Ethylene glycol 4.00 parts Benzotriazole 1.00 parts Proxel GXL (s) (preservative, Avicia Co., Ltd.) 0.20 parts NKW-2167E-P (colored resin dispersion) 40.00 parts 20% aqueous solution of sodium salt of oleyl sarcosine (lubricant, sarcosinate OH, manufactured by Nikko Chemicals Co., Ltd.) 5.00 parts Jonkrill 61j (water-soluble styrene-acrylic copolymer) Union, Johnson Polymer Co., Ltd.
0.50 parts Pemulene TR-1 (thickening polymer, acrylic acid-alkyl methacrylate copolymer, manufactured by BFGoodrich) 0.40 parts inorganic particles (plate-like silica, average major axis 5.0 μm, average medium diameter 4) 0.0 μm, average minor axis less than 0.1 μm) 0.10 parts In the above components, Pemulen TR-1 and water were mixed and stirred with a propeller stirrer for 30 minutes to prepare an aqueous solution of Pemulen TR-1. The average particle size of Pemulen TR-1 was 2.0 μm. The remaining components were added to this and further stirred for 1 hour. Thereafter, the pH was adjusted to 7.0 with triethanolamine, followed by filtration and defoaming with a defoamer to obtain an aqueous ink for purple ballpoint pen.

(Comparative Example 2)
Ion-exchanged water 48.00 parts Propylene glycol 10.00 parts Glycerin 10.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J775 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts FUJI SP BLUE 6474 (pigment dispersion, manufactured by Fuji Color Co., Ltd.) 20.00 parts Oxyethylene oleyl ether Sodium salt 20% aqueous solution of phosphoric acid (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 5.00 parts Triethanolamine (pH adjuster) 1.00 parts Zeta Seagum (thickening polysaccharide, Hakuto Co., Ltd.) 0.30 parts Inorganic particles (alumina, average major axis 5.0 μm, average median diameter 5.0 μm, average minor axis less than 5.0 μm) 0.10 parts Among the above components, ion exchange, ethylene glycol and zeta sea gum in a Henschel mixer The mixture was stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 5.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Thereafter, filtration was carried out, defoaming was performed with a defoaming machine, and then the mixture was left standing at 70 ° C. for 24 hours, and then a blue water-based ink for a ballpoint pen was obtained.

(Comparative Example 3)
In Example 1, the same black water-based ink for ballpoint pens as in Example 1 was obtained except that inorganic particles were not added and the amount of water was increased accordingly. The average particle size of the zeta sea gum was 2.0 μm.

(Comparative Example 4)
In Example 1, the same black water-based ink for ballpoint pens as in Example 1 was obtained except that the inorganic particles were changed to an average major axis of 5.2 μm, an average medium diameter of 5.0 μm, and an average minor axis of 5 μm. The average particle size of the zeta sea gum was 2.0 μm.

(Comparative Example 5)
In Example 7, the same blue water-based ink for ballpoint pens as in Example 7 was obtained except that the inorganic particles were changed to magnesium carbonate (average major axis: 3.0 μm, average middle diameter: 3.0 μm, average minor axis: 3.0 μm). The average particle size of the occasy gum was 1.5 μm.

(Comparative Example 6)
Ion-exchanged water 50.97 parts Propylene glycol 6.00 parts Glycerin 14.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J734 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 1.00 parts FUJI SP BLACK 8970 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
25.00 parts Sodium salt 20% aqueous solution of oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts Diethanolamine (pH adjuster) 0.20 parts Zeta Seagum (Thickening polysaccharide) , Hakuto Co., Ltd. 0.22 parts Inorganic particles (plate-like silica, average major axis 2.0 μm, average median diameter 2 μm, average minor axis less than 0.1 μm) 0.10 parts Among the above components, ion exchange, ethylene glycol and The zeta sea gum was placed in a Henschel mixer and stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 2.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered, defoamed with the defoamer, and after leaving to stand in 70 degreeC environment for 24 hours, the black water-based ink for ball-point pens was obtained.

(Comparative Example 7)
Ion-exchanged water 42.85 parts Propylene glycol 10.00 parts Glycerin 10.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J775 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts NKW2167E (colored resin dispersion, manufactured by Nippon Fluorescence Co., Ltd.) 25.00 parts Oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) Sodium salt 20% aqueous solution 5.00 parts Triethanolamine (pH adjuster) 1.00 parts Zeta Seagum (thickening polysaccharide, Hakuto Co., Ltd.) 0. 25 parts Inorganic particles (calcium fluoride, average major axis 8 μm, average median diameter 7 μm, average minor axis less than 0.1 μm) 0.30 parts Among the above components, ion exchange, ethylene glycol and zeta sea gum are placed in a Henschel mixer at 2800 rpm The mixture was stirred for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 3.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered and defoamed with the defoaming machine and obtained the water-based ink for purple ball-point pens.

(Comparative Example 8)
Ion-exchanged water 32.85 parts Glycerin 20.00 parts Fuji SP Blue 625 (pigment dispersion, Fuji dye) 45.0 parts xanthan gum (thickening polysaccharide, manufactured by Ina Food Industry Co., Ltd.) 0.35 parts Proxel GXL ( s) (preservative, Avicia Co., Ltd.) 0.30 parts Phosphate ester surfactant (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prisurf AL)
0.50 parts Triethanolamine (pH adjuster) 1.00 parts Among the above components, xanthan gum, water and glycerin were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes to prepare a uniformly dissolved Kelzan aqueous solution. This xanthan gum was not particulate. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, after passing once through a fine flow mill with an inverter output of 20 Hz, filtration was performed and defoaming was performed with a defoaming machine to obtain a blue water-based ink for a ballpoint pen.

(Comparative Example 9)
Ion-exchanged water 50.97 parts Propylene glycol 6.00 parts Glycerin 14.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J734 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 1.00 parts FUJI SP BLACK 8970 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
25.00 parts Sodium salt 20% aqueous solution of oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts Diethanolamine (pH adjuster) 0.20 parts Zeta Seagum (Thickening polysaccharide) , Hakuto Co., Ltd. 0.22 parts Inorganic particles (silica, average major axis 0.03 μm, average middle diameter 0.03 μm, average minor axis less than 0.03 μm) 0.01 part Among the above components, ion exchange, ethylene glycol and The zeta sea gum was placed in a Henschel mixer and stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 2.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered, defoamed with the defoamer, and after leaving to stand in 70 degreeC environment for 24 hours, the black water-based ink for ball-point pens was obtained.

(Comparative Example 10)
Ion-exchanged water 50.78 parts Propylene glycol 6.00 parts Glycerin 14.00 parts Benzotriazole 0.40 parts Coatside S (Antidepressant, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.10 parts TSA739 (antifoaming agent, Silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.)
0.10 parts Jonkrill J734 (styrene / acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.) 1.00 parts FUJI SP BLACK 8970 (pigment dispersion, manufactured by Fuji Dye Co., Ltd.)
25.00 parts Sodium salt 20% aqueous solution of oxyethylene oleyl ether phosphate (Phosphanol RB410, manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts Diethanolamine (pH adjuster) 0.20 parts Zeta Seagum (Thickening polysaccharide) , Hakuto Co., Ltd. 0.22 parts Inorganic particles (silica, average major axis 10 μm, average middle diameter 8 μm, average minor axis less than 1.0 μm)
0.20 parts Among the above components, ion exchange, ethylene glycol and zeta sea gum were placed in a Henschel mixer and stirred at 2800 rpm for 60 minutes to prepare a uniformly dissolved zeta sea gum aqueous solution. The average particle size of the zeta sea gum was 2.0 μm. The remaining components were placed in a Henschel mixer and stirred at 1300 rpm for 30 minutes, and then the ink was taken out. Then, it filtered, defoamed with the defoamer, and after leaving to stand in 70 degreeC environment for 24 hours, the black water-based ink for ball-point pens was obtained.

Test Sample Ballpoint Pen The ink compositions obtained in Examples 1 to 18 and Comparative Examples 1 to 10 were refilled with a product code KN123 manufactured by Pentel Co., Ltd. KFRN3 (a ball made of cemented carbide having a diameter of 0.35 mm, a stainless steel ball holder) , Using a synthetic resin chip holder and a transparent plastic hollow pipe for knock type ballpoint pen), 0.5 g of ink and 0.1 g of silicone oil ink follower are filled and defoamed. The test sample ballpoint pen was used.

  Writing distance: Using a self-rotating continuous writing tester (spiral machine, manufactured by Seiki Kogyo Laboratories), the writing distance was measured by continuously writing at a writing speed of 7 cm / sec, a load of 100 g, and an angle of 70 °.

  As described above in detail, the water-based ink composition for ballpoint pens according to the present invention suppresses the occurrence of scumming or inability to write due to clogging at the writing tip, so that it is faded until all the filled ink is consumed. It is useful that the object of being able to write without any problems can be sufficiently achieved.

Claims (1)

At least a colorant, water, a polysaccharide having a molecular weight of about 1 × 10 ⁷ to 1 × 10 ⁹ present in the form of particles in the ink, or an alkyl acid-alkyl methacrylate copolymer having a molecular weight of about 5 × 10 ⁵ or more. A water-based ink composition for ballpoint pens comprising a thickening polymer as a polymer and inorganic particles having an average particle size smaller than that of the thickening polymer particles.