JP2017082218A - Aqueous brilliant ink composition for ball point pen - Google Patents

Abstract

An ink that can be used by filling a ballpoint pen refill to form a handwriting with a radiant feeling, has good handwriting dryness, does not cause the handwriting to show through the paper, and has a handwriting with sufficient radiance. An object of the present invention is to provide a water-based glittering ink composition for ballpoint pens which can be written on attached paper, does not squeak at the time of writing, and does not fade over time at low temperatures. The present invention provides a water-based glittering ink composition for ballpoint pens that contains at least a glittering pigment containing a metal, water, xanthan gum, and welan gum. [Selection] Figure 1

Description

  The present invention relates to a water-based glittering ink composition for ballpoint pens that forms a brilliant handwriting and a ballpoint pen using the water-based glittering ink composition for ballpoint pens.

Conventionally, ink for water-based ballpoint pens that uses a polysaccharide as an agent for imparting shear thinning to an ink composition that has a relatively large particle size and a flat pigment, and that forms a handwriting with a high lustrous feel and has a glittering feel. It has been known. The water-based ballpoint pen ink, which has a shear thinning viscosity that decreases in viscosity due to the shearing force caused by the rotation of the ball during writing, has a high viscosity when left standing, thereby suppressing the precipitation of glittering pigment and ink leakage from the pen tip. At the time of writing, the ink viscosity is lowered by the shearing force of the rotating ball, so that the ink can be smoothly ejected. Inks using polysaccharides as shear thinning agents have little viscosity drop when left standing due to metal ions, can disperse and stabilize glitter pigments for a long time, and are widely used in glitter ink compositions. Yes. In addition, among known polysaccharides used as thickeners to improve the dispersibility of metal powder pigments, there is a problem that they cannot be used by increasing or decreasing the viscosity over time. .
In particular, xanthan gum is known to impart a high shear thinning index to the ink composition only when contained in a small amount, and welan gum is stable over time in a high-temperature environment, and when used as a pigment ink. It is known that it is excellent in stability (Patent Document 1, Patent Document 2).
Furthermore, it is also known to suppress a viscosity change by combining a natural polysaccharide such as xanthan gum or welan gum with a water-soluble soybean polysaccharide as a binder component (Patent Document 3).

JP 2001-192597 A JP 2003-012973 A Japanese Patent Laid-Open No. 11-130998

However, polysaccharides exhibit shear thinning due to entanglement, but polysaccharides with a large molecular weight do not pass through narrow spaces such as paper fibers due to their large structure, and ink whose viscosity has once decreased is applied to the paper. In order to obtain a sufficient glitter feeling by ejecting a pigment with a relatively large particle size such as a glittering pigment, the penetrability of the handwriting to the paper does not occur. When the amount of discharge was increased by adjusting the ballpoint pen tip, the glitter pigment worked like a lid on the handwriting, and the handwriting was more difficult to dry.
In addition, because the main solvent is water and the polysaccharides are highly hydrophilic, when the oil on the hand adheres to the paper surface during writing, the oil is a component of the oil on the surface. Because the ink is repelled and the glitter pigment is not uniformly scattered on the handwriting, the pigment does not get onto the handwriting and the pigment is separated into a part with no glitter and a part with glitter. The feeling was reduced, or the handwriting was not formed on the hand grease, and the line skipped.
Furthermore, in order to discharge the glitter pigment from the ballpoint pen tip, it is necessary to increase the ball house inner diameter of the ballpoint pen tip, increase the caulking inner diameter of the tip of the ballpoint pen tip, or increase the ball movement amount. Due to the force, the position of the ball was not stabilized, and the phenomenon that the ball collided with the metal inner wall in the chip and made a metal sound (sound) was likely to occur.
It is known that xanthan gum or welan gum alone forms a double helix structure in an aqueous solution.
Since xanthan gum and welan gum alone have a three-dimensional network structure with relatively large and non-uniform pore sizes in the ink, the water and solvent in the network just below the flat pigments are adsorbed by the pigment and handwritten. The drying speed was different between the part with and without the glitter pigment, and the dry state was uneven, slowing the overall handwriting drying property.
This is because, in the case of xanthan gum alone, the side chain of xanthan gum is long, so that after forming a double helix structure in an aqueous solution, the xanthan gum tends to be in a super-associated state due to the entanglement between the side chains of xanthan gum. In addition, welan gum has a short side chain and a carboxyl group in the main chain. In the case of welan gum alone, when a double helix structure is formed in an aqueous solution, the carboxyl group of the main chain of welan gum is oriented outward of the double helix, but the solubility of the hydrophilic group is lower than that of xanthan gum. This is because the molecular spread is small.
Furthermore, welan gum aqueous solution has high temporal stability at high temperatures in pigment dispersions, but has lower solubility in mixed solvents containing solvents and activators other than water compared to xanthan gum, etc. In water-based inks for ballpoint pens, in which an organic solvent and a surfactant are essential, welan gum is precipitated due to the materials used in combination, and the solution tends to become unstable at low temperatures and over time.

  The present invention is an ink composition that can be used by filling in a ballpoint pen refill and can form a handwriting with a radiant feeling.It has good handwriting dryness, there is no back-through of the handwriting on the paper, and a handwriting with sufficient radiance. An object of the present invention is to provide a water-based glittering ink composition for ballpoint pens that can be written on paper with hand grease, does not squeak at the time of writing, and does not fade over time at low temperatures.

The aqueous glittering ink composition for ballpoint pens of the present invention is
(1) A water-based glittering ink composition for ballpoint pens containing at least a glittering pigment containing a metal, water, xanthan gum, and welan gum.

According to the configuration of (1) above,
As a result of intensive studies by the present inventors, by using the xanthan gum and welan gum together with the glitter pigment containing metal, the metal of the glitter pigment containing metal, and xanthan gum and welan gum interact, By forming a three-dimensional network structure with a relatively small diameter and uniform pore size, it is possible to suppress the penetrating of the handwriting to the paper, and also to write on the paper with hand grease, making a noise during writing Thus, a glittering ink composition capable of drying the handwriting very quickly was obtained.
This is because xanthan gum and welan gum form a double helix structure in an aqueous solution, the side chains of xanthan gum are oriented outwards of the double helix at appropriate intervals, and the double side carboxyl groups of xanthan gum double Maintains the hydrophilicity of the helix structure to maintain good solubility of the double helix, suppresses the formation of a super-association state of the double helix and maintains good solubility, and further contains a metal This is because a three-dimensional network structure having a relatively small diameter and a uniform pore diameter is formed by the interaction between the glitter pigment and the carboxyl group of the side chain of the double helix.
The structure of the above (1) is based on the above knowledge obtained by the present inventors, and the combination of a bright pigment containing metal, xanthan gum, and a polysaccharide containing welan gum has good handwriting dryness, There is no see-through of the handwriting on the paper, it is possible to write on paper with hand-brightness with a handwriting with sufficient radiance, no noise at the time of writing, and no fading at low temperatures over time.

  (2) In some embodiments, in the configuration of (1), when a: the content of xanthan gum in the ink [wt%] and b: the content of the welan gum in the ink [wt%], a / b = 0.35 or more and 4.0 or less, and a + b which is the content of xanthan gum and welan gum in the ink is 0.3% by weight or more and 0.7% by weight or less.

  According to the configuration of (2) above, when the content of xanthan gum in the ink is a [wt%] and the content of the welan gum in the ink is b [wt%], a / b = 0.35 or more. The handwriting can be dried more quickly by setting a + b, which is 4.0 or less, and the content of xanthan gum and welan gum in the ink to 0.3 wt% or more and 0.7 wt% or less.

  (3) In some embodiments, in the configuration of (1) or (2) above, a polyglycerol fatty acid ester having an HLB value of 8 or more and 18 or less is contained.

  According to the configuration of (3) above, the addition of a polyglycerin fatty acid ester having an HLB value of 8 or more and 18 or less maintains the solubility of welan gum, and blurring due to poor ink follow-up at low temperatures or over time. Can be prevented.

  (4) In some embodiments, 3-methyl-3-methoxy-1-butanol is contained in the above configurations (1) to (2).

  According to the configuration of (4) above, by adding 3-methyl-3-methoxy-1-butanol, the alkyl group of 3-methyl-3-methoxy-1-butanol is adsorbed on the surface of the paper, Since the solvent is easily and easily desorbed, the structure of xanthan gum and welan gum rapidly collapses into a thin film, so that the drying property of the handwriting can be made faster.

  According to an embodiment of the present invention, in an ink composition that can be used by being filled in a ballpoint pen refill to form a lustrous handwriting, the handwriting dryness is good, the handwriting does not show through the paper, and sufficient radiance is achieved. It is possible to provide a water-based glittering ink composition for ballpoint pens which can be written on paper with hand-feeling with a feeling of handwriting, does not squeak at the time of writing, and does not fade at low temperatures over time.

It is a longitudinal cross-sectional view which shows the ball-point pen refill used for a ball-point pen. It is an expanded sectional view which shows the I section in FIG. It is a longitudinal cross-sectional view of the 1st ball-point pen tip. FIG. 4 is a cross-sectional view taken along line II-II ′ in FIG. 3. FIG. 4 is a cross-sectional view taken along the line III-III ′ of FIG. 3. It is a longitudinal cross-sectional view of the 2nd ball-point pen tip. FIG. 7 is a cross-sectional view taken along the line II-II ′ of FIG. 6. FIG. 7 is a cross-sectional view taken along the line III-III ′ of FIG. 6. It is a longitudinal cross-sectional view of the 3rd ball-point pen tip. FIG. 10 is a cross-sectional view taken along the line II-II ′ of FIG. 9. FIG. 10 is a cross-sectional view taken along the line III-III ′ of FIG. 9.

  The glitter pigment is used to form a beautiful handwriting with a glitter feeling by being contained in the ink. The glittering pigment containing a metal that can be used is not particularly limited as long as it is conventionally known. For example, metal powder such as aluminum powder and bronze powder, metal-coated glass flake, metal A vapor deposition film etc. are mentioned.

Examples of the metal powder include aluminum powder, brass powder, stainless steel powder, tin powder, zinc powder, bronze powder, nickel powder, copper powder, gold powder, and silver powder, and mixed powders and alloy powders of these metals. As an aluminum powder pigment, Super Fine No. 22000, ibid. 18000, Fine No. 900, 800 (above, manufactured by Daiwa Metal Powder Industry Co., Ltd.), AA12, AA8, No. 900, no. 1800 (above, manufactured by Fukuda Metal Foil Powder Co., Ltd.), aluminum powder 1000, 2700 (above, manufactured by Nakatsuka Metal Foil Powder Co., Ltd.), and the like. In addition, aluminum powder is crushed and polished in a ball mill containing a high-boiling petroleum solvent (mineral spirit, etc.) and an anti-friction agent such as stearic acid, resulting in very thin scaly aluminum particles. The paste has a low risk of ignition and explosion, has good storage stability, and is easy to handle in use. As the aluminum paste, Super Fine No. 22000WN, ibid. 1800WN (Yamato Metal Powder Industry Co., Ltd.), WB0230, WXM0630, Friend Color D45BL, Friend Color D462BL, Friend Color D851BL, Friend Color D451RE, Friend Color D462RE, Friend Color D111RE, Friend Color D45YE, Friend Color D462YE, Friend Color D851YE (above, Toyo Aluminum Co., Ltd.) etc. are mentioned.
Examples of the copper and copper alloy powder pigment include Pale Gold E5, 2L5, Rich Gold L7, 3L7, ECopper (manufactured by Fukuda Metal Foil Powder Co., Ltd.). You may use metal powder individually or in mixture of 2 or more types.

  Other bright pigments containing metals that can be used include Metashine MT1030GP, Metashine MT2080GP, Metashine 2025PS, Metashine 1030PS, Metashine 2080PS, Metashine 5090PS, Metashine 5230PS, Metashine 5230PS, Metashine 5480PS ( As described above, manufactured by Nippon Sheet Glass Co., Ltd.), LG neo R-GOLD # 35, LG neo B-GOLD # 35, LG neo S-GOLD # 35, LG neo R-GOLD # 100, LG neo B-GOLD # 100, LG neo S-GOLD # 100, Elgie neo RED # 100, Elgie neo BLUE # 100, Elgie neo GREEN # 100, Elgie ne VIOLET # 100, Elgie neo BLACK # 100, Elgie neo Copper # 100, Elgie neo PINK # 100, Elgie neo YELLOW # 100, Elgie neo R-GOLD # 150, Elgie neo B-GOLD # 150, Elgie neo S-GOLD # 150, Elgie neo RED # 150, Elgie neo BLUE # 150, Elgie neo GREEN # 150, Elgie neo VIOLET # 150, Elgie neo BLACK # 150, Elgie neo COPPER # 150, Elgie neo PINK # 150, Elgie neo YELLOW # 150, Elgie neo R-GOLD # 200, Elgie neo B-GOLD # 200, Elgi neo S-GOLD # 200, Elgi neo RED # 200, Elgi neo BLUE # 200, Elgi neo GREEN # 200, Elgi neo VIOLET # 200, Elgi neo BLACK # 200, Elgi neo COPPER # 200, Elgi neo PINK # 200, Elgi neo YELLOW # 200, Elgi neo R-GOLD # 325, Elgi neo B-GOLD # 325, Elgi neo S-GOLD # 325, Elgi neo RED # 325, Elgie neo BLUE # 325, Elgie neo GREEN # 325, Elgie E ET # 325, Elgie neo BLACK # 325, Elgie neo Copper # 325, Elgie n eo PINK # 325, LG neo YELLOW # 325, LG neo R-GOLD # 500, LG neo B-GOLD # 500, LG neo S-GOLD # 500 (above, manufactured by Oike Imaging Co., Ltd.), Diamond Piece LG Gold No . 55, Diamond Piece DG Gold No. 55, Diamond Piece Green No. 55, Diamond Piece Blue No. 55, Diamond Piece Red No. 55, Diamond Piece Maroon No. 55, Diamond Piece Ocean Green No. 55, Diamond Piece Sky Blue No. 55, Diamond Piece Black No. 55, diamond piece Pink No. 55, Diamond Piece Violet No. 55, Diamond Piece Emerald No. 55, Diamond Piece Copper No. 55, Diamond Piece LG Gold H25, Diamond Piece DG Gold H25, Diamond Piece Green H25, Diamond Piece Blue H25, Diamond Piece Red H25, Diamond Piece Maroon H25, Diamond Piece Ocean Green H25, Diamond Piece Sky Blue H25, Diamond Piece Black H25 , Diamond Piece Pink H25, Diamond Piece Violet H25, Diamond Piece Emerald H25, Diamond Piece Copper H25, Diamond Piece LG Gold H55, Diamond Piece DG Gold H55, Diamond Piece Green H55, Diamond Diamond Piece Red H55, Diamond Piece Red H55, Diamond Piece Maroon H55, Diamond Piece Ocean Green H55, Diamond Piece Sky Blue H55, Diamond Piece Black H55, Diamond Piece Pink H55, Diamond Piece Violet H55, Diamond Piece Emerald H55, Diamond Piece Copper H55 , Diamond piece LG Gold CO-40UC, diamond piece DG Gold CO-40UC, diamond piece Green CO-40UC, diamond piece Blue CO-40UC, diamond piece Red CO-40UC, diamond piece Pink CO-4 UC, diamond piece Lavender CO-40UC (or, Dia Kogyo Co., Ltd.) and the like. The metallic pigments may be used alone or in combination of two or more.

  Among the glitter pigments containing these metals, it is particularly preferable to include the LNG neo series because both the clear color tone and the strength of the handwriting glitter are compatible. The content of the glittering pigment containing a metal in the ink composition is 0.5% by weight or more and 20.0% by weight or less, more preferably 2.0% by weight or more and 10.0% by weight with respect to the total amount of the ink composition. When it is below, a high glitter feeling can be obtained on the handwriting, and clogging of the nib due to sedimentation of the glitter pigment containing metal hardly occurs. A particle size of 20 μm or more and 100 μm or less is preferable because it can impart sufficient glitter to the handwriting and hardly clog the pen tip.

A colorant other than the glittering pigment containing a metal can be used in combination with a conventionally known colorant for color matching.
As the dye, any of acid dyes, direct dyes, basic dyes and the like used in conventional water-based inks can be used. For example, Japan Fast Black D Conch (CI Direct Black 17), Water Black 100L (CI Direct Black 19), Water Black L-200 (CI Direct Black 19), Direct Fast Black B (CI Direct Black 22), Direct Fast Black AB (CI Direct Black 32), Direct Deep Black EX (CI Direct Black 38), Direct Fast Black Conc (CI Direct Black 51), Caillas Spragley VGN (CI Direct Black 71), Caillas Direct Brilliant Yellow G (CI Direct Yellow 4), Direct Fast Yellow 5GL (CI Direct Air) -26), Eisen Primula Yellow GCLH (CI Direct Yellow 44), Direct Fast Yellow R (CI Direct Yellow 50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX (CI Direct Red 4), Direct Fast Scarlet 4BS (CI Direct Red 23), Eisen Direct Rhodurin BH (CI Direct Red 31), Direct Scarlet B (CI Direct) Red 37), Kayak Direct Scarlet 3B (CI Direct Red 39), Eisen Primula Pink 2BLH (CI Direct Red 75), Sumilite Red F3B (CI Direct Red 80), Eisenprim Red 4BH (C.I. Direct Red 81), Cayalas Spralbin BL (C.I. Direct Red 83), Cayalas Light Red F5G (C.I. Direct Red 225), Cayalas Light Red F5B (C.I. I. Direct Red 226), Cayalas Light Rose FR (C.I. Direct Red 227), Direct Sky Blue 6B (C.I. Direct Blue 1), Direct Sky Blue 5B (C.I. Direct Blue 15), Sumilite Spula Blue BRR Conch (CI Direct Blue 71), Dibogen Turquoise Blue S (CI Direct Blue 86), Water Blue # 3 (CI Direct Blue 86), Kayara Star Coyze Blue GL (CI Direct Blue 86), Kayara Sp La Blue FF2GL (C.I. I. Direct Blue 106), Caillas Splatter Turquoise Blue FBL (CI Direct Blue 199) and other direct dyes, Acid Blue Black 10B (CI Acid Black 1), Nigrosine (CI Acid Black 2) , Suminol Milling Black 8BX (CI Acid Black 24), Kayanol Milling Black VLG (CI Acid Black 26), Suminol Fast Black BR Conch (CI Acid Black 31), Mitsui Nylon Black GL (CI Acid Black 52), Eisen Opal Black WH Extra Conch (CI Acid Black 52), Sumilan Black WA (CI Acid Black 52), Ranil Black BG Extra Conc (CI . Acid Black 107), Cyanol Milling Black TLB (CI Acid Black 109), Suminol Milling Black B (CI Acid Black 109), Cyanol Milling Black TLR (CI Acid Black 110), Eisen Opal Black New Conk (CI Acid Black 119), Water Black 187-L (CI Acid Black 154), Kayaqua Acid Brilliant Flavin FF (CI Acid Yellow 7: 1), Kayasil Yellow GG (C.I. I. Acid Yellow 17), Xylene Light Yellow 2G 140% (CI Acid Yellow 17), Suminol Leveling Yellow NR (CI Acid Yellow 19), Daiwa Tarrazine (CI Acid Yellow 23), Kayaktor Thrazine ( CI Acid Yellow 23), Suminol Fast Yellow R (CI Acid Yellow 25), Diacid Light Yellow 2GP (CI Acid Yellow 29), Suminol Milling Yellow O (CI Acid Yellow) 38), Suminol Milling Yellow MR (CI Acid Yellow 42), Water Yellow # 6 (CI Acid Yellow 42), Kayanol Yellow NFG (CI Acid Yellow 49), Suminol Milling Yellow 3G (CI Acid Yellow 72), Suminol Fast Yellow G (CI Acid Yellow 61), Suminol Milling Yellow G (CI Acid Yellow 78), Kayanol Yellow N5G (C.I. Acid Yellow 110), Suminoll Milling Yellow 4G 200% (CI Acid Yellow 1) 41), Kayanolero NG (C.I. I. Acid Yellow 135), Cyanol Milling Yellow 5 GW (CI Acid Yellow 127), Cyanol Milling Yellow 6 GW (CI Acid Yellow 142), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (CI Acid Red 9), Solar Rubin Extra (CI Acid Red 14), Daiwa New Coxin (CI Acid Red 18), Eisenbonso RH (CI Acid Red) 26), Daiwa Red No. 2 (CI Acid Red 27), Suminol Leveling Brilliant Red S3B (CI Acid Red 35), Kayasil Rubinol 3GS (CI Acid Red 37), Eisen Erythrosin (CI Acid Red 51), Kayakashi Drodamine FB (CI Acid Red 52), Suminol Leveling Rubinol 3GP (CI Acid Red 57), Diacid Alizarin Rubinol F3G 200% (CI Acid Red 82), Eisen Eosin GH (C I. Acid Red 87), Water Pink # 2 (C.I. Acid Red 92), Eisen Acid Phloxin PB (C.I. Acid Red 92), Rose Bengal (C.I. Acid Red 94), Kayanol Milling Scarlet FGW (CI Acid Red 111), Cyanol Milling Rubin 3BW (CI Acid Red 129), Sminool Milling Brilliant Red 3BN Conch (CI Acid Red 131), Suminol Milling Brilliant Red BS CI Acid Red 138), Eisen Opal Pink BH (CI Acid Red 186), Suminol Milling Brilliant Red B Conch (CI Acid Red 249), Kayaku Acid Brilliant Red 3BL (C.I. Acid Red 254), Kayaku Acid Brilliant Brilliant Red BL (CI Acid Red 265), Kayanol Milling Red GW (CI Acid Red 276), Mitsui Acid Violet 6BN (CI Acid Violet 15) Mitsui Acid Violet BN (C.I. Acid Violet 17), Sumitomo Patent Pure Blue VX (C.I. Acid Blue 1), Water Blue # 106 (C.I. Acid Blue 1), Patent Blue AF (C.I.) I. A Cid Blue 7), Water Blue # 9 (C.I. I. Acid Blue 9), Daiwa Blue No. 1 (CI Acid Blue 9), Supranol Blue B (CI Acid Blue 15), Orient Soluble Blue OBC (CI Acid Blue 22), Suminol Leveling Blue 4GL (C.I. Acid Blue 23), Mitsui Nylon Fast Blue G (C.I. Acid Blue 25), Kayasil Blue AGG (C.I. Acid Blue 40), Kayasil Blue BR (C.I. Acid Blue 41) ), Mitsui Alizarin Saphirol SE (CI Acid Blue 43), Suminol Leveling Sky Blue R Extra Conch (CI Acid Blue 62), Mitsui Nylon Fast Sky Blue B (CI Acid Blue 78) , Sumitomo Brilliant Indocyanine 6Bh / c ( CI Acid Blue 83), Sandlancyanine N-6B 350% (CI Acid Blue 90), Water Blue # 115 (CI Acid Blue 90), Orient Soluble Blue OBB (CI Acid) Blue 93), Sumitomo Brilliant Blue 5G (C.I. Acid Blue 103), Cyanol Milling Ultra Sky SE (C.I. Acid Blue 112), Cyanol Milling Cyanine 5R (C.I. Acid Blue 113), Eisen Opal Blue 2GLH (C.I. Acid Blue 158), Daiwa Guinea Green B (C.I. Acid Green 3), Acid Brilliant Milling Green B (C.I. Acid Green 9), Daiwa Green # 70 (C.I. Acid green 16), Kayanorushi Acid dyes such as Nin Green G (C.I. Acid Green 25), Suminol Milling Green G (C.I. Acid Green 27), Eisen Katylon Yellow 3GLH (C.I.Basic Yellow 11), Eisen Katyrone Brilliant Yellow 5GLH (CI Basic Yellow 13), Sumiacryl Yellow E-3RD (CI Basic Yellow 15), Maxilon Yellow 2RL (CI Basic Yellow 19), Astrazone Yellow 7GLL (C.I. I. Basic Yellow 21), Kayacrill Golden Yellow GL-ED (C.I. Basic Yellow 28), Astrazone Yellow 5GL (C.I.Basic Yellow 51), Eisen Catillon Orange GLH (C.I.Basic Orange) 21) Eye Zenkachiron Brown 3GLH (C.I. I. Basic Orange 30), Rhodamine 6GCP (CI Basic Red 1), Eisen Astrafloxin (CI Basic Orange 12), Sumiacryl Brilliant Red E-2B (CI Basic Orange 15), Astrazone Red GTL (CI Basic Orange 18), Eisen Catillon Brilliant Pink BGH (CI Basic Orange 27), Maxilon Red GRL (CI Basic Orange 46), Eisen Methyl Violet (CI Basic Orange) Violet 1), Eisen Crystal Violet (CI Basic Violet 3), Eisen Rhodamine B (CI Basic Violet 10), Astrazone Blue G (CI Basic Blue 1), Astra Zombie BG (C.I. Basic Blue 3), Methylene Blue (C.I.Basic Blue 9), Maxilon Blue GRL (C.I.Basic Blue 41), Eisen Catillon Blue BRLH (C.I.Basic Blue 54) And basic dyes such as Eisen Diamond Green GH (CI Basic Green 1), Eisen Malachite Green (CI Basic Green 4), Bismarck Brown G (CI Basic Brown 1), and the like.
The dyes may be used alone or in combination of two or more. The content of the dye in the ink composition is preferably 0.1% by weight or more and 30.0% by weight or less based on the total amount of the ink composition. If the amount is less than 0.1% by weight, the dyeing is not sufficient. If the amount is more than 30.0% by weight, the solid content increases, so that the ink follow-up property is deteriorated and blurring tends to occur.

Examples of pigments include azo pigments, nitroso pigments, nitro pigments, basic dye pigments, acidic dye pigments, built dye pigments, mordant dye pigments, and natural dye pigments used in conventional water-based inks. Organic pigments such as ocher, barium yellow, bitumen, cadmium red, barium sulfate, titanium oxide, petals, iron black, carbon black and the like. Specifically, aniline black (C.I. 50440), cyanine black, naphthol yellow S (C.I. 10316), Hansa Yellow 10G (C.I. 11710), Hansa Yellow 5G (C.I. 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 Yellow NCG (CI. 20040), Vulcan Fast Yellow 5 (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.I. 60520), 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 orange ( 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), Para Chlorortoaniline 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. 1233 5), 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 include phthalocyanine green.
In addition, the use of an aqueous ink base dispersed in an aqueous medium is advantageous for the production of pigment inks. Specifically, Fuji SP Black 8031, Fuji SP Black 8119, Fuji SP Black 8167, Fuji SP Black 8276, Fuji SP Black8381, Fuji SP Black 8406, Fuji SP Red 896, Fuji SP Red 896, Fu5 SP , Fuji SP Blue 6062, Fuji SP Blue 6133, Fuji SP Blue 6134, Fuji SP Blue 6401, Fuji SP Green 7051, Fuji SP Yellow 4060, Fuji SP 4190 SP Yellow 4601 SP Yellow 6190 SP 9527, Fuji SP Orange 534, Fuji SP Brown 3074, Fuji SP RED 5543, FUJI SP RED 5544 (above, manufactured by Fuji Dye Co., Ltd.), Emacol Black CN, Emol Blue FBB, Emol Blue B LXB, Emacol Violet BL, Emacol Brown 3101, Emacol Carmine FB, Emacol Red BS, Emacol Orange R, Emacol Yellow FD, Emacol Yellow IRN, Ecol Yellow E36 macol Yellow F5G, Emacol Yellow F7G, Emacol Yellow 10GN, Emacol Yellow 10G, Sandye Super Black K, Sandye Super Black C, Sandye Super Grey B, Sandye Super Brown SB, Sandye Super Brown FRL, Sandye Super Brown RR, SandyeSuper Green L5G, Sandy Super Green GXB, Sandy Super Navy Blue HRL, Sandy Super Navy Blue GLL, Sandy Super Navy Blue HB, Sandy Super Navy S Blue F er Navy Blue FBL-160, Sandye Super Navy Blue FBB, Sandye Super Violet BL H / C, Sandye Super Violet BL BL, Sandye Super Bordeaux FR, Sandye Super Pink FBL, Super Pink F5B, Sandye Super Rubine FR, Sandye super Carmmine FB , Sandy Super Red FFG, Sandy Super Red RR, Sandy Super Red BS, Sandy Super Orange FL, Sandy Super Orange R, Sandy Super Orange BO, SandY G e Gold Yellow R, Sandye Gold Yellow 3R, Sandye Ywllow GG, Sandye Ywllow F3R, Sandye Ywllow IRC, Sandye Ywllow FGN, Sandye Ywllow GN, Sandye Ywllow GRS, Sandye Ywllow GSR-130, Sandye Ywllow GSN-130, Sandye Ywllow GSN, Sandye Ywllow 10GN (above, manufactured by Sanyo Dye Co., Ltd.), Rio Fast BlackFx 8012, Rio Fast BlackFx 8313, Rio Fast BlackFx 8169, Rio Fast Red Fx8109, RioFast 8x8, Rio Fast Red 8x8 315, Rio Fast Red S Fx 8316, Rio Fast Blue Fx 8170, Rio Fast Blue FX 8170, Rio Fast Blue S Fx 8312, Rio Fast Green S 101 2102, NKW-2103, NKW-2104, NKW-2105, NKW-2106, NKW-2107, NKW-2108, NKW-2117, NKW-2127, NKW-2137, NKW-2167, NKW-2101P, NKW-2102P, NKW-2103P, NKW-2104P, NKW-2105P, NKW-2106P, NKW-2107P, NKW-2108P, NKW-2117P, NKW-2127P, NKW-2 137P, NKW-2167P, NKW-3002, NKW-3003, NKW-3004, NKW-3005, NKW-3007, NKW-3077, NKW-3008, NKW-3402, NKW-3404, NKW-3405, NKW-3407, NKW-3408, NKW-3477, NKW-3602, NKW-3603, NKW-3604, NKW-3605, NKW-3607, NKW-3377, NKW-3608, NKW-3702, NKW-3703, NKW-3704, NKW- 3705, NKW-3777, NKW-3708, NKW-6013, NKW-6038, NKW-6559 (above, Nippon Fluorescence Co., Ltd.), Cosmo Color S1000F Series (Toyo Soda Co., Ltd.), Victoria Yellow G-11, the same 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 Examples include G-15, G-25 (above, manufactured by Mikuni Dye Co., Ltd.), Pollux PC5T1020, Pollux Black PC8T135, Polook Thread IT1030, and other Pollux series (above, manufactured by Sumika Color Co., Ltd.).
You may use a pigment individually or in mixture of 2 or more types. The content of the pigment in the ink composition is preferably 0.1% by weight or more and 10.0% by weight or less based on the total amount of the ink composition. If the amount is less than 0.1% by weight, the dyeing is not sufficient. If the amount is more than 10.0% by weight, a lot of pigment adheres to the glittering pigment containing metal and the glittering feeling is lost.

The xanthan gum and welan gum used in the present invention are used in combination to form a three-dimensional network structure having a relatively small diameter and a uniform pore diameter. This three-dimensional network structure was retained in the three-dimensional network structure having a relatively small diameter and a uniform pore diameter while being able to suppress the back-through of the handwriting to the paper by staying on the surface of the paper after writing. The ink water and solvent are uniformly adsorbed on the paper surface, and the amount of water and solvent adsorbed on the flat pigment is very small so that the handwriting is dried very quickly and uniformly. This three-dimensional network structure having a relatively small diameter and a uniform pore diameter has many portions that are retained even in a flow state in which shearing occurs due to the rotation of the ball in the ball-point pen tip. There is higher cushioning performance than a three-dimensional network structure with holes. For this reason, it is presumed that the effect of suppressing the squeal that the ball collides with the metal inner wall in the chip is high.
Xanthan gum is a structure consisting of a main chain of glucose repeating structure and a side chain having one glucuronic acid between mannose. Specifically, Kelzan, S, T, ST, ASX, ASX, AR, HP, G, Ketrol CG, CG-T, CG-SFT (above, Sanki Co., Ltd.) Manufactured), San Ace, S, C, C-S, B-S, NF, G, G-ES, NXG-S, NXG-C, Bistop D-3000-DF, The same D-3000-DF-C (manufactured by Saneigen FSI Co., Ltd.), and the like.
Welan gum has a structure composed of a main chain having a repeating structure composed of glucose, glucuronic acid and rhamnose, and a side chain of rhamnose or mannose. Specific examples include K1A96, BG3810 (manufactured by Sanki Co., Ltd.), and the like.
In particular, when the content of xanthan gum in the ink is a [wt%] and the content of the welan gum in the ink is b [wt%], a / b = 0.35 or more and 4.0 or less, and The content of a + b, which is the content of xanthan gum and welan gum, in the ink composition is more preferably 0.3 wt% or more and 0.7 wt% or less based on the total amount of the ink composition.
Among the xanthan gums, Kelzan, Kelzan AR, Kelzan S, Kelzan T, and Kelzan ST are preferable because they have particularly fast drying properties when used in combination with welan gum.

Specific examples of polyglycerol fatty acid esters having an HLB value of 8 to 18 used in the present invention include hexaglyceryl monolaurate (HLB value: 14.5), hexaglyceryl monomyristate (HLB value: 11.0), Hexaglyceryl monostearate (HLB value: 9.0), hexaglyceryl monooleate (HLB value: 9.0), decaglyceryl monolaurate (HLB value: 15.5), decaglyceryl monomyristate (HLB value: 14.0), decaglyceryl monostearate (HLB value: 12.0), decaglyceryl monostearate (HLB value: 15.0), decaglyceryl monoisostearate (HLB value: 12.0), monooleic acid Decaglyceryl (HLB value: 12.0), decaglyceryl monolinoleate (HLB value: 1) .0), decaglyceryl distearate (HLB value: 9.5), diisostearate decaglyceryl (HLB value: 10.0), and the like.
Among polyglycerin fatty acid esters having an HLB value of 8 or more and 18 or less, those having a fatty acid residue of myristic acid or lauric acid are preferred, and in particular, hexaglyceryl monolaurate and hexaglyceryl monomyristate are ink viscosity at lower temperatures and over time. It was preferable because it was easy to obtain the effect of preventing ink bleeding due to the rise.
Polyglycerin fatty acid esters having an HLB value of 8 or more and 18 or less may be used alone or in admixture of two or more. The content of the polyglycerol fatty acid ester having an HLB value of 8 or more and 18 or less in the ink composition is preferably 0.5% by weight or more and 10.0% by weight or less with respect to the total amount of the ink composition. When the amount is less than 0.5% by weight, the ink leakage due to a decrease in ink viscosity at high temperature and the effect of preventing ink bleeding due to an increase in ink viscosity due to poor solubility of the thickener at low temperature are not improved. If it is more than 0% by weight, the blur of the handwriting becomes large.

When 3-methyl-3-methoxy-1-butanol is used in combination with water as a main solvent, a handwritten paper in which a three-dimensional structure having a relatively small and uniform pore diameter of a polysaccharide in ink is written on paper. Therefore, it is used for the purpose of speeding up the handwriting dryness by making the mixed solvent easy to desorb.
3-Methyl-3-methoxy-1-butanol is excellent in solubility of polysaccharides, and since the release of the polysaccharides from the network structure to the paper surface is fast, the solvent penetrates to the back of the paper surface even though the handwriting dryness is fast. Does not slip through the paper. In particular, welan gum is poorly soluble in water-soluble organic solvents among polysaccharides, and depending on the amount and type of the solvent, the ink tends to come out due to poor dissolution at low temperatures, and scumming is likely to occur. -Methoxy-1-butanol is optimal for improving the solubility of welan gum.
The content of 3-methyl-3-methoxy-1-butanol in the ink composition is preferably 5.0% by weight or more and 30.0% by weight or less based on the total amount of the ink composition. If it is less than 5.0% by weight, the nib drying property may not be sufficient, and even if it is added in an amount of 30.0% by weight or more, the improvement of the handwriting drying property is not seen and is meaningless. 10.0% by weight or more and 20.0% by weight or less is particularly preferable because it is difficult to see through and the handwriting is dried quickly.

  Water is used as the main solvent. The main solvent in this invention refers to the solvent which occupies 50.0 weight% or more in the solvent in the ink composition whole quantity.

Conventionally known water-soluble organic solvents other than 3-methyl-3-methoxy-1-butanol can also be used as long as they do not inhibit the solubility of welan gum. Specifically, 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 monohexyl ether Glycol ethers such as 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, benzyl Alcohol solvents such as 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- Examples include pyrrolidone and the like.
Among the water-soluble organic solvents that can be used, glycerin has relatively good solubility for welan gum, but since it easily penetrates into the paper surface, it is easy to see through, and the addition amount needs attention.
The water-soluble organic solvents may be used alone or in combination of two or more. The content of the water-soluble organic solvent in the ink composition is preferably 0.05% by weight or more and 15.0% by weight or less based on the total amount of the ink composition.

  Various resins can be used in combination as a binder for fixing the ink coloring material on the paper surface. Specifically, shellac, styrene-maleic acid copolymer, styrene-acrylic acid copolymer and salts of styrene-acrylic acid copolymer, alkali metal salt, amine salt, ammonium salt, α-methylstyrene -Water-soluble resins such as alkali metal salts, amine salts, and ammonium salts of acrylic acid copolymers can be used. In addition, water-insoluble resins such as acrylic resins, vinyl acetate resins, and styrene-butadiene copolymers can also be used. The water-insoluble resin is used in the form of an aqueous emulsion. Among these, acrylic resins and further acrylic emulsions are preferable because they improve the fixability of the metallic pigments on the paper surface and the storage stability of the ink.

In addition to the above components, various additives conventionally used in water-based inks for writing instruments can be used as necessary.
For example, sugar alcohols such as sorbit and xylit to prevent ink evaporation, urea, ethylene urea and their derivatives are used, polyethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, Alkaline metal salts and amine salts such as oleic acid, acylamino acids, acylglutamic acid, taurine, methyltaurine, phosphate esters, castor oil, hydrogenated castor oil, polyoxyethylene hydrogenated castor oil, water-soluble lubricating oil, particulate alumina, sulfide A lubricant such as molybdenum can be used. Among them, N-coconut oil fatty acid acyl-L-glutamic acid, N-lauroyl-L-glutamic acid, N-stearoyl-L-glutamic acid, N-coconut oil fatty acid acyl-sodium L-glutamate, N-lauroyl-L-glutamic acid sodium, N-myristoyl-L-glutamate potassium, N-myristoyl-L-glutamate sodium, N-acyl-L-glutamate sodium, N-stearoyl-L-glutamate sodium, N-coconut oil fatty acid acyl-L-glutamate triethanolamine solution Lauroyl-L-glutamic acid triethanolamine solution, N-coconut oil fatty acid acyl-potassium L-glutamic acid potassium hydroxide solution, N-coconut oil fatty acid acyl-sodium L-glutamate sodium hydroxide solution are more preferred.

  Furthermore, anionic, nonionic and cationic surfactants, silicone surfactants, surface tension regulators such as fluorine surfactants, rust preventives such as benzotriazole and ethylenediaminetetraacetic acid, silicones, fluorine -Type antifoaming agents, ascorbic acid or salts thereof and derivatives thereof, tocopherol or salts thereof and derivatives thereof, hydroquinone, hydroquinone derivatives, hydrooxysulfonic acid and salts thereof, etc., sodium hydroxide as a pH adjuster Alkalizing agents such as alkanolamines, amines, ammonium, etc. Antiseptic / antifungal agents such as sodium dehydroacetate, 1,2-benzisothiazin-3-one, 2-pyridinethiol-1-oxide sodium salt it can. Among the antiseptic / antifungal agents, 1,2-benzoisothiazolin-3-one and 2-pyridinethiol-1-oxide / sodium salt have a synergistic effect by combining them, so that the antiseptic / antifungal effect can be achieved with less content It is known that 1,2-benzisothiazin-3-one and 2-pyridinethiol-1-oxide sodium salt are used in combination. These may be used alone or in admixture of two or more.

  Various methods known in the art can be employed as the ink production method. For example, it can be produced using an apparatus such as a ball mill, a bead mill, a roll mill, a Henschel mixer, a propeller stirrer, a homogenizer, a kneader. Since it is important to dissolve xanthan gum and welan gum well, it is desirable that they are sufficiently dissolved in water or a solution containing water as a good solvent. Filtration and centrifugation may be performed to remove coarse particles and gas. Heating, cooling, pressurization, decompression, or inert gas replacement may be performed during production. The power may be electricity or pressurized air. Further, an aging process may be performed after adjusting the ink in order to make the dispersibility of xanthan gum and welan gum sufficient. These may be used alone or in combination of two or more.

  A ballpoint pen that uses the water-based ink composition described above in an ink storage tube will be described. A ballpoint pen tip, which is the tip of a ballpoint pen, holds a ball as a writing member and the ball in a state of partially protruding from the tip opening of an ink passage hole penetrating the ball holder. A ballpoint pen refill is mounted directly or via a connecting member. The ball holder is formed on a cylindrical member made of metal such as stainless steel or white and white using a cutting blade such as a drill or a broach with an inward protruding portion serving as a rear movement restricting portion of the ball together with a through hole serving as an ink passage hole. The diameter of the through hole and the number and width of the radial grooves formed between the inward protruding portions can be adjusted as appropriate according to the physical properties of the ink. Moreover, the pipe material in which the through hole was previously formed can also be used. When pipe material is used, the outer wall portion of the pipe material is pressed and deformed by a pin to form a concave portion, thereby forming a convex portion on the inner wall portion corresponding to the portion, and the convex portion is inside. It becomes a direction protrusion part.

  In addition, a coil spring is placed behind the ball, and the ball is pressed against the inner edge of the tip opening of the ball holder to seal the ink passage when not in use and bleed out ink from the tip of the ballpoint pen tip. In addition, it is possible to prevent the ink from moving when the impact is caused by dropping or the pen tip is left facing upward. As a material of the coil spring, a metal material such as a stainless steel wire such as SUS304, a hard steel wire, and a piano wire, or a resin such as polycarbonate or polyetheretherketone can be used. In order to prevent corrosion and elution into ink, the surface can be subjected to surface coating treatment such as nickel plating. The load with which the coil spring presses the ball is preferably 0.01 N or more and 1.50 N or less.

  As the ball, a cemented carbide using tungsten carbide as a main component and using cobalt, nickel, chromium, or the like as a binder phase, or a ceramic sintered body mainly containing silicon carbide, zirconia, alumina, or the like is used. Further, both cemented carbide and ceramic sintered body can have a Vickers hardness (HV) of 1000 or more and 2000 or less, and the ball surface roughness arithmetic average height (Ra: JIS B 0601) is 1.0 nm. A film having a thickness of 20.0 nm or less can be used. As a ball diameter, a small-diameter ball of 0.1 mm to 0.5 mm, a medium-diameter ball larger than 0.5 mm and 0.7 mm or less, and a large-diameter ball exceeding 0.7 mm can be used. Among these, when the ball diameter is 0.7 mm or more, a sufficient handwriting width is obtained, and a change in the hue of the handwriting depending on the viewing angle is easily obtained. The ink discharge amount is preferably 0.004 g / m or more and 0.010 g / m or less. Furthermore, it is more preferable to set it to 0.005 g / m or more and 0.009 g / m or less because the handwriting is easy to dry while maintaining the glitter.

  The ball holder that can be used with the ballpoint pen tip can be made of a copper alloy such as stainless steel, brass, or white, and stainless steel is preferred from the viewpoint of durability and corrosion resistance. Stainless steel SUS430 is used. In addition, the Vickers hardness (HV) is preferably 150 or more and 300 or less in order to suppress deformation of the tip of the ballpoint pen tip while having good workability. In addition, it can be made of a highly wear-resistant resin such as polyoxymethylene resin, and a conventionally known material such as another synthetic resin can also be used.

  The ink storage tube may be an extruded or injection-molded pipe made of a copper alloy such as aluminum, stainless steel or brass, or a synthetic resin such as polypropylene resin, polybutylene terephthalate resin or polyether ketone resin having transparency. The inner diameter of the storage tube is a diameter that prevents ink from flowing out of the storage tube when the ballpoint pen is stored upside down or sideways or when a strong impact is applied to the ballpoint pen, but does not hinder ink movement when writing. The diameter is preferably 0.5 mm or more and 15.0 mm or less, and may be a straight line such as a pipe or a combination of different inner diameters in multiple stages. In addition, in order to prevent that the solvent permeates over time, the solid content ratio in the ink increases, and as a result, the ink is thickened and the assumed fluidity and writing taste cannot be obtained. The wall thickness of the ink containing tube is desirably 0.2 mm or more. In addition, when the surface roughness of the inner wall surface is smooth, the ink remains on the inner wall surface when the ink moves by writing, and the pipe clearness is improved. Further, by applying a fluorine-based surfactant, silicone or the like to the inner wall surface, the contact angle between the ink and the inner wall surface of the receiving tube can be reduced, and the pipe clearability can be further improved.

  The ball-point pen tip and the ink storage tube are connected to form a ball-point pen, but a chip holder that is a connection relay member may be interposed between the ball-point pen tip and the ink storage tube. The material of the chip holder is formed by extrusion or injection molding of a copper alloy such as aluminum, stainless steel or brass, or a synthetic resin such as polypropylene resin, polybutylene terephthalate resin or polyether ketone resin. If the through-hole formed in the chip holder is large, even a composition having a pigment having a relatively large particle size like the ink composition of the present invention can be sufficiently distributed, but if it is too large, the cap It is desirable that the minimum inner diameter of the through hole be 0.5 mm or more and 2.5 mm or less because the ink easily moves when the ballpoint pen is subjected to an impact due to the fitting or dropping of the ink.

Further, an ink backflow prevention composition that suppresses backward movement and leakage of ink can be used in the ink containing tube.
The ink backflow prevention composition comprises a non-volatile liquid or a hardly volatile liquid. Specifically, petroleum jelly, 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 include polyether-modified silicone oil and fatty acid-modified silicone oil. These non-volatile liquids or hardly volatile liquids may be used alone or in admixture of two or more.
The non-volatile liquid and / or the hardly volatile liquid is preferably thickened to a suitable viscosity by adding a gelling agent. Swelling mica, hydrophobic thickeners such as bentonite and montmorillonite, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, fatty acid amide, amide modified polyethylene Examples thereof include dextrin compounds such as wax, hydrogenated castor oil, and fatty acid dextrin, and cellulose compounds. Of these, fatty acid metal soaps, fatty acid dextrins, and amide-modified polyethylene waxes are preferably used because of their excellent solvent resistance. In addition, by adding fine particles such as alcohol solvents, glycol solvents, surfactants, resins, metal oxides, etc., the functions required for ink backflow prevention compositions (gelation, coloring prevention, backflow prevention) can be improved. it can. Further, the anti-backflow composition may further include a float as a backflow preventer to improve impact resistance.

  Formulation examples of the ink composition will be described in more detail based on examples and comparative examples.

The viscosity values in the examples and comparative examples were measured using a rheometer of a modular compact rheometer MCR302 (manufactured by Anton Paar), the measurement temperature was 25 ° C., and the geometry was a shear rate measured using a 1 ° / φ50 mm cone plate. .35 (1 / s) and a shear rate of 1.32 (1 / s). In addition, when the shear rate is between 3 (1 / s) and 500 (1 / s), the shear stress and the shear rate change based on the power law. The power law flow equation is defined by S = AD ⁿ (where S is the shear stress, D is the shear rate, and n is the shear thinning index). From this equation, the viscosity at a certain shear rate can be obtained by obtaining S / D. From the above, A and n are described.

Example 1
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.25% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.25% by weight
LG neo SILVER # 200 (Metallic pigment, manufactured by Oike Industry Co., Ltd.) 4.0% by weight
Daiwa Red No. 106WB (red dye, manufactured by Daiwa Kasei Co., Ltd.) 2.0% by weight
Water Yellow 6C (Yellow dye, manufactured by Orient Chemical Co., Ltd.)
1.0% by weight
Daiwa Blue No. 1 (blue dye, manufactured by Daiwa Kasei Co., Ltd.) 3.0% by weight
Water Black 256L (14% aqueous solution of black dye, 1.0% by weight manufactured by Orient Chemical Co., Ltd.)
Joncryl PDX 7430 (acrylic emulsion, manufactured by BASF Corporation) 3.0% by weight
3-Methyl-3-methoxy-1-butanol 12.0% by weight
Glycerin 10.0% by weight
NIKKOL Hexaglyn1-L (hexaglyceryl monolaurate, manufactured by Nikko Chemicals Co., Ltd.) 1.5% by weight
Amisoft CS-11 (N-coconut oil fatty acid acyl-L-glutamate sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 1.0% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
1.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.2% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.2% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Ion-exchanged water 56.88% by weight
10% NaOH 0.9% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 9500 mPa · s when the shear rate is 0.35 (1 / s), 3800 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 4717.2 and n = 0.221 according to the flow formula of

Example 2
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.2% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.3% by weight
LG neo GREEN # 325 (Metallic luster pigment, manufactured by Oike Industry Co., Ltd.) 4.0% by weight
Water Yellow 6C (Yellow dye, manufactured by Orient Chemical Co., Ltd.)
3.0% by weight
Water Yellow 2 (Yellow dye, manufactured by Orient Chemical Industry Co., Ltd.) 1.0% by weight
Water blue 119 (blue dye, manufactured by Orient Chemical Industry Co., Ltd.)
1.0% by weight
Daiwa Blue No. 1 (blue dye, manufactured by Daiwa Kasei Co., Ltd.) 3.0% by weight
Joncryl PDX 7430 (acrylic emulsion, manufactured by BASF Corporation) 2.5% by weight
3-methyl-3-methoxy-1-butanol 10.0% by weight
Glycerin 10.0% by weight
NIKKOL Hexaglyn1-M (hexaglyceryl monomyristate, manufactured by Nikko Chemicals Co., Ltd.) 1.3% by weight
Amisoft CS-11 (N-coconut oil fatty acid acyl-L-glutamate sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 1.0% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
1.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.3% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.2% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Ion-exchanged water 58.48% by weight
10% NaOH 0.9% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 10100 mPa · s when the shear rate is 0.35 (1 / s), 3950 mPa · s when the shear rate is 1.32 (1 / s), and the power law. According to the flow formula of A = 4779.4, n = 0.209.

Example 3
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.4% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.1% by weight
Elgie neo B. GOLD # 325 (a bright pigment containing metal, manufactured by Oike Industry Co., Ltd.) 6.0% by weight
Water Yellow 6C (Yellow dye, manufactured by Orient Chemical Co., Ltd.)
3.0% by weight
Water Yellow 2 (Yellow dye, manufactured by Orient Chemical Industry Co., Ltd.) 2.0% by weight
Joncryl PDX 7667 (acrylic emulsion, manufactured by BASF Corporation) 5.0% by weight
3-Methyl-3-methoxy-1-butanol 12.0% by weight
Glycerin 10.0% by weight
NIKKOL Hexaglyn1-M (hexaglyceryl monomyristate, manufactured by Nikko Chemicals Co., Ltd.) 1.5% by weight
Amisoft MK-11 (potassium N-myristoyl-L-glutamate, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 1.0% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.3% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.5% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Ion-exchanged water 55.98% by weight
10% NaOH 0.9% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 8500 mPa · s when the shear rate is 0.35 (1 / s), 3550 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 4551.2 and n = 0.195 according to the flow formula of

Example 4
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.15% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.35% by weight
LG neo BLUE # 200 (a bright pigment containing metal, manufactured by Oike Industry Co., Ltd.) 4.0% by weight
Water blue 119 (blue dye, manufactured by Orient Chemical Industry Co., Ltd.)
1.0% by weight
Water Blue 105 (Blue dye, manufactured by Orient Chemical Industry Co., Ltd.)
1.0% by weight
Daiwa Blue No. 1 (blue dye, manufactured by Daiwa Kasei Co., Ltd.) 3.0% by weight
Joncryl PDX 7430 (acrylic emulsion, manufactured by BASF Corporation) 6.0% by weight
3-methyl-3-methoxy-1-butanol 13.0% by weight
Glycerin 5.0% by weight
NIKKOL Decaglyn1-L (decaglyceryl monolaurate, manufactured by Nikko Chemicals Co., Ltd.) 1.0% by weight
Amisoft LS-11 (N-lauroyl-L-glutamate sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 1.0% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
1.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.2% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.2% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Ion-exchanged water 60.38% by weight
10% NaOH 0.9% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution, and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.4. The viscosity of the ink is 12000 mPa · s when the shear rate is 0.35 (1 / s), 4300 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 4798.8 and n = 0.228 according to the flow formula of

Example 5
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.2% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.3% by weight
LG neo Pink # 325 (Metallic pigment, manufactured by Oike Kogyo Co., Ltd.) 5.0% by weight
Water Red 1 (Red dye, manufactured by Orient Chemical Co., Ltd.)
2.0% by weight
Daiwa Red No. 104WB (red dye, manufactured by Daiwa Kasei Co., Ltd.)
1.0% by weight
Daiwa Blue No. 1 (blue dye, manufactured by Daiwa Kasei Co., Ltd.) 3.0% by weight
Joncryl 352D (acrylic emulsion, manufactured by BASF Corporation)
5.0% by weight
3-Methyl-3-methoxy-1-butanol 15.0% by weight
Glycerin 10.0% by weight
NIKKOL Hexaglyn1-M (hexaglyceryl monomyristate, manufactured by Nikko Chemicals Co., Ltd.) 1.5% by weight
Amisoft LS-11 (N-lauroyl-L-glutamate sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 1.0% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
1.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.3% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.1% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Ion-exchanged water 53.88% by weight
10% NaOH 0.9% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 11000 mPa · s when the shear rate is 0.35 (1 / s), 4250 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 4810.6 and n = 0.208 according to the flow formula of

Example 6
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.1% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.2% by weight
LG neo Silver # 200 (Metallic pigment, manufactured by Oike Industry Co., Ltd.) 2.0% by weight
Water black 256L (14% aqueous solution of black dye, manufactured by Orient Chemical Co., Ltd.) 1.0% by weight
Joncryl 352D (acrylic emulsion, manufactured by BASF Corporation)
3.0% by weight
3-Methyl-3-methoxy-1-butanol 12.0% by weight
Glycerin 10.0% by weight
NIKKOL Hexaglyn1-L (hexaglyceryl monolaurate, manufactured by Nikko Chemicals Co., Ltd.) 1.5% by weight
Amisoft CS-11 (N-coconut oil fatty acid acyl-L-glutamate sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 1.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.3% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.3% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Ion exchange water 66.28% by weight
10% NaOH 0.5% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution, and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.0. The viscosity of the ink is 6500 mPa · s when the shear rate is 0.35 (1 / s), 3360 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 4519.5 and n = 0.186 according to the flow equation.

Example 7
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.3% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.4% by weight
LG neo Yellow # 325 (Metallic pigment, manufactured by Oike Kogyo Co., Ltd.) 4.0% by weight
Water Red 1 (Red dye, manufactured by Orient Chemical Co., Ltd.)
4.0% by weight
Daiwa Red No. 106 (red dye, manufactured by Daiwa Kasei Co., Ltd.) 2.0% by weight
Water Yellow 6C (Yellow dye, manufactured by Orient Chemical Co., Ltd.)
2.0% by weight
Joncryl PDX7430 (acrylic emulsion, manufactured by BASF Corporation)
4.0% by weight
3-Methyl-3-methoxy-1-butanol 15.0% by weight
NIKKOL Hexaglyn1-M (hexaglyceryl monomyristate, manufactured by Nikko Chemicals Co., Ltd.) 1.5% by weight
Amisoft MK-11 (potassium N-myristoyl-L-glutamate, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 1.0% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
3.0% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.3% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.2% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Ion exchange water 59.78% by weight
Triethanolamine 1.2% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 16500 mPa · s when the shear rate is 0.35 (1 / s), 4500 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 5129.5 and n = 0.234 according to the flow formula of

Example 8
A glittering water-based ink composition having a pH of 8.5 was obtained in the same manner as in Example 1 except that 3-methyl-3-methoxy-1-butanol was removed and replaced with ion-exchanged water. The viscosity of the ink is 9300 mPa · s when the shear rate is 0.35 (1 / s), 3750 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 4624.1 and n = 0.215 according to the flow formula of

Example 9
In Example 2, a bright water-based ink composition having a pH of 8.4 was obtained in the same manner except that NIKKOL Hexaglyn1-M was replaced with ion-exchanged water. The viscosity of the ink is 11000 mPa · s when the shear rate is 0.35 (1 / s), 4250 mPa · s when the shear rate is 1.32 (1 / s), and the power law. According to the flow formula of A = 4779.4, n = 0.208.

Example 10
A glittering water-based ink composition having a pH of 8.4 in the same manner as in Example 3 except that 3-methyl-3-methoxy-1-butanol and NIKKOL Hexaglyn1-M were replaced with ion-exchanged water. I got a thing. The viscosity of the ink is 10500 mPa · s when the shear rate is 0.35 (1 / s), 3950 mPa · s when the shear rate is 1.32 (1 / s), and the power law. According to the flow formula of A = 4779.4, n = 0.209.

Example 11
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.2% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.4% by weight
LG neo RED # 325 (Metallic luster pigment, manufactured by Oike Industry Co., Ltd.) 6.0% by weight
Water Red 1 (Red dye, manufactured by Orient Chemical Co., Ltd.)
3.0% by weight
Water Yellow 6C (Yellow dye, manufactured by Orient Chemical Co., Ltd.)
1.0% by weight
Joncryl PDX7430 (acrylic emulsion, manufactured by BASF Corporation)
2.5% by weight
3-methyl-3-methoxy-1-butanol 8.0% by weight
Glycerin 5.0% by weight
Amisoft CS-11 (N-coconut oil fatty acid acyl-L-glutamate sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 0.1% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
1.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.2% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Ion-exchanged water 68.98% by weight
10% NaOH 0.7% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 11500 mPa · s when the shear rate is 0.35 (1 / s), and 4050 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 4785.7 and n = 0.217 in accordance with the flow formula of

Example 12
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.2% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.3% by weight
LNG neo Silver # 325 (Metallic pigment, manufactured by Oike Industry Co., Ltd.) 5.0% by weight
Water Yellow 6C (Yellow dye, manufactured by Orient Chemical Co., Ltd.)
4.0% by weight
Daiwa Blue No. 1 (blue dye, manufactured by Daiwa Kasei Co., Ltd.) 1.0% by weight
Joncryl PDX7667 (acrylic emulsion, manufactured by BASF Corporation)
3.0% by weight
3-Methyl-3-methoxy-1-butanol 2.0% by weight
Glycerin 5.0% by weight
Amisoft MK-11 (potassium N-myristoyl-L-glutamate, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 0.5% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
0.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.2% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Ion exchange water 79.91 wt%
10% NaOH 0.9% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 9000 mPa · s when the shear rate is 0.35 (1 / s), 3650 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 4624.1 and n = 0.215 according to the flow formula of

Example 13
In Example 11, a glittering water-based ink composition having a pH of 8.5 was obtained in the same manner except that the total amount of 3-methyl-3-methoxy-1-butanol was removed and replaced with ion-exchanged water. . The viscosity of the ink is 11300 mPa · s when the shear rate is 0.35 (1 / s), 4030 mPa · s when the shear rate is 1.32 (1 / s), and the power law. According to the flow formula of A = 4779.4, n = 0.209.

Example 14
In Example 12, a glittering water-based ink composition having a pH of 8.5 was obtained in the same manner except that the total amount of 3-methyl-3-methoxy-1-butanol was removed and replaced with ion-exchanged water. . The viscosity of the ink is 9200 mPa · s when the shear rate is 0.35 (1 / s), 3700 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 4655.1 and n = 0.213 in accordance with the flow formula of

Example 15
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.3% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.05% by weight
LG neo PINK # 325 (Metallic pigment, manufactured by Oike Kogyo Co., Ltd.) 4.0% by weight
Daiwa Red No. 104WB (red dye, manufactured by Daiwa Kasei Co., Ltd.)
5.0% by weight
Daiwa Blue No. 1 (blue dye, manufactured by Daiwa Kasei Co., Ltd.) 1.5% by weight
Joncryl PDX7430 (acrylic emulsion, manufactured by BASF Corporation)
2.5% by weight
Glycerin 5.0% by weight
Amisoft CS-11 (N-coconut oil fatty acid acyl-L-glutamate sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 0.5% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
1.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.2% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.2% by weight
Ion exchange water 71.38% by weight
10% NaOH 0.7% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 6000 mPa · s when the shear rate is 0.35 (1 / s), 3500 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 4558.2 and n = 0.169 according to the flow formula of

Example 16
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.1% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.4% by weight
LG neo PINK # 325 (Metallic pigment, manufactured by Oike Kogyo Co., Ltd.) 4.0% by weight
Daiwa Red No. 104WB (red dye, manufactured by Daiwa Kasei Co., Ltd.)
5.0% by weight
Daiwa Blue No. 1 (blue dye, manufactured by Daiwa Kasei Co., Ltd.) 1.5% by weight
Joncryl PDX7430 (acrylic emulsion, manufactured by BASF Corporation)
2.5% by weight
Glycerin 5.0% by weight
Amisoft CS-11 (N-coconut oil fatty acid acyl-L-glutamate sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 0.5% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
1.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.2% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.2% by weight
Ion-exchanged water 76.83% by weight
10% NaOH 0.7% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 13500 mPa · s when the shear rate is 0.35 (1 / s), 4300 mPa · s when the shear rate is 1.32 (1 / s), and the power law A = 4806, n = 0.186 according to the flow formula of

Example 17
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.4% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.4% by weight
LG neo PINK # 325 (Metallic pigment, manufactured by Oike Kogyo Co., Ltd.) 4.0% by weight
Daiwa Red No. 104WB (red dye, manufactured by Daiwa Kasei Co., Ltd.)
5.0% by weight
Daiwa Blue No. 1 (blue dye, manufactured by Daiwa Kasei Co., Ltd.) 1.5% by weight
Joncryl PDX7430 (acrylic emulsion, manufactured by BASF Corporation)
2.5% by weight
Glycerin 5.0% by weight
Amisoft CS-11 (N-coconut oil fatty acid acyl-L-glutamate sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 0.5% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
1.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.2% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.2% by weight
Ion-exchanged water 76.83% by weight
10% NaOH 0.7% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 17500 mPa · s when the shear rate is 0.35 (1 / s), 4800 mPa · s when the shear rate is 1.32 (1 / s), and the power law A = 5311.4 and n = 0.244 according to the flow formula of

Example 18
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.15% by weight
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.65% by weight
LG neo PINK # 325 (Metallic pigment, manufactured by Oike Kogyo Co., Ltd.) 4.0% by weight
Daiwa Red No. 104WB (red dye, manufactured by Daiwa Kasei Co., Ltd.)
5.0% by weight
Daiwa Blue No. 1 (blue dye, manufactured by Daiwa Kasei Co., Ltd.) 1.5% by weight
Joncryl PDX7430 (acrylic emulsion, manufactured by BASF Corporation)
2.5% by weight
Glycerin 5.0% by weight
Amisoft CS-11 (N-coconut oil fatty acid acyl-L-glutamate sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 0.5% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
1.5% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
Sun Eye Buck Sodium Omazine (An antiseptic / antifungal agent containing 2-pyridinethiol-1-oxide / sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.)
0.2% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.02% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) glycerin 0.662% dispersion 1.0% by weight
Potassium hydroquinone sulfonate (oxygen scavenger) 0.2% by weight
Ion-exchanged water 76.25% by weight
10% NaOH 0.7% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Moreover, BG3810 and 15 weight% of ion-exchange water were mixed, and it stirred for 1 hour, and prepared BG3810 aqueous solution. Next, the remaining components were mixed with an aqueous Kelzan AR solution and an aqueous BG3810 solution and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 8.5. The viscosity of the ink is 18500 mPa · s when the shear rate is 0.35 (1 / s), and 5500 mPa · s when the shear rate is 1.32 (1 / s), and the power law. A = 5496.7 and n = 0.253.

Comparative Example 1
BG3810 (Welan gum, manufactured by Sanki Co., Ltd.) 0.3% by weight
LS Silver # 500 (Metallic luster pigment, manufactured by Oike Industry Co., Ltd.) 3.0% by weight
Glycerol 7.0% by weight
Propylene glycol 15.0% by weight
Phosphanol RS710 (phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.)
0.1% by weight
Ion-exchanged water 74.1% by weight
10% NaOH 0.5% by weight
Among the above components, BG3810 and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a BG3810 aqueous solution. Next, the remaining components and the BG3810 aqueous solution were mixed and stirred for 2 hours to obtain a glittering water-based ink composition having a pH of 8.2. The viscosity of the ink is 8500 mPa · s when the shear rate is 0.35 (1 / s), 3500 mPa · s when the shear rate is 1.32 (1 / s), and the power law. According to the flow formula of A = 4544.9, n = 0.21.

Comparative Example 2
Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.9% by weight
LG Green # 325 (Metallic luster pigment, manufactured by Oike Industry Co., Ltd.) 4.0% by weight
Joncryl 1535 (acrylic emulsion, manufactured by BASF Corporation)
10.0% by weight
Glycerol 7.0% by weight
Ethylene glycol 10.0% by weight
Proxel GXL (S) (an antiseptic / antifungal agent containing 1,2-benzisothiazalin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.2% by weight
TSA739 (antifoaming agent, silicone emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.2% by weight
Ion-exchanged water 67.7% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Next, the remaining components and the aqueous Kelzan AR solution were mixed and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 7.5. The viscosity of the ink is 15000 mPa · s when the shear rate is 0.35 (1 / s), 3500 mPa · s when the shear rate is 1.32 (1 / s), and the power law. According to the flow formula of A = 4544.9, n = 0.21.

Comparative Example 3
Kelzan (xanthan gum, manufactured by Sanki Co., Ltd.) 0.7% by weight
Soya Five S-DN (water-soluble soybean polysaccharide, manufactured by Fuji Oil Co., Ltd.)
3.0% by weight
LG Green # 325 (Metallic luster pigment, manufactured by Oike Industry Co., Ltd.) 4.0% by weight
Alpaste WXM0630 (aluminum paste, manufactured by Toyo Aluminum Co., Ltd.) 5.0% by weight
Glycerol 7.0% by weight
Ethylene glycol 10.0% by weight
Proxel GXL (S) (An antiseptic / antifungal agent containing 1,2-benzoisothiazarin-3-one, active ingredient 20%, manufactured by Arch Chemical Japan Co., Ltd.) 0.1% by weight
Benzotriazole (rust inhibitor) 0.1% by weight
Ion-exchanged water 74.1% by weight
Among the above components, Kelzan AR and 15% by weight of ion-exchanged water were mixed and stirred for 1 hour to prepare a Kelzan AR aqueous solution. Further, 15% by weight of ion-exchanged water, Soya Five S-DN and Alpaste WXM0630 were mixed and stirred for 1 hour to prepare a Soya Five S-DN and Alpaste WXM0630 mixed solution. Next, the remaining components, a Kelzan AR aqueous solution, Soya Five S-DN, and Alpaste WXM0630 mixed solution were mixed and stirred for 2 hours to obtain a glittering aqueous ink composition having a pH of 7.5. The viscosity of the ink is 12500 mPa · s when the shear rate is 0.35 (1 / s), 4500 mPa · s when the shear rate is 1.32 (1 / s), and the power law A = 4873.1 and n = 0.206 in accordance with the flow equation.

Ink backflow prevention composition 1
Polybutene HV50 (polybutene, base material, manufactured by Nippon Petrochemical Co., Ltd.)
95.0% by weight
Aerosil R972 (particulate silica, gelling agent, manufactured by Nippon Aerosil Co., Ltd.)
3.0% by weight
Leopard KL (dextrin fatty acid ester, manufactured by Chiba Flour Milling Co., Ltd.)
2.0% by weight
The above components were mixed and stirred with a hot stirrer at 150 ° C. for 2 hours to obtain a backflow preventer 1. This backflow preventer had a viscosity at 25 ° C. of 50000 mPa · S.

Ink backflow prevention composition 2
Lucant HC100 (ethylene olefin, base material, manufactured by Mitsui Petrochemical Co., Ltd.) 94.5% by weight
Aerosil R974 (fine particle silica, gelling agent, manufactured by Nippon Aerosil Co., Ltd.)
4.0% by weight
Leopard KL (dextrin fatty acid ester, manufactured by Chiba Flour Milling Co., Ltd.)
1.5% by weight
The above components were mixed and stirred with a hot stirrer at 150 ° C. for 2 hours to obtain a backflow preventer 2. The backflow preventing body had a viscosity at 25 ° C. of 40000 mPa · S.

  A structure of a ballpoint pen used for a test to be described later will be described with reference to the drawings. FIG. 1 shows a vertical cross-sectional view of a so-called refill ballpoint pen that is assumed to be housed in an exterior body. The ball-point pen tip 1 holds a ball 2 as a writing member so as to be rotatable in a state in which the ball 2 partially protrudes from a front end opening of an ink through hole formed in the ball holder 3. The ballpoint pen tip 1 is connected to the ink containing tube 6 via a tip holder 5 in which a through hole 4 is formed. Ink 7 is accommodated in the ink storage tube 6, and an ink backflow preventing composition 8 that is incompatible with the ink 7 is disposed in contact with the rear end interface of the ink 7. In addition, although illustration and description about the exterior body which accommodates this refill are abbreviate | omitted, well-known exterior bodies, such as an exterior body as described in Unexamined-Japanese-Patent No. 9-58173, can be used, for example. Further, a ball-point pen body that does not use an exterior body can be provided by arranging a tail plug or the like for preventing ink leakage at the rear end of the ink containing tube 6.

  Next, FIG. 2 shows an enlarged vertical sectional view of the I part of the ballpoint pen tip 1 used in FIG. The ball holder 3 forms a through-hole as an ink passage by a drill or the like in the metal columnar material described above, and has a ball house portion 9, a middle hole 10, and a rear hole 11 from the front end side. An inward projecting portion 12 is formed between the ball house portion 9 and the rear hole 11. The diameter of the tip opening 13 of the ball house 9 is reduced by caulking, and the ball 2 moves in the front / rear and left / right directions of the ball 2 by the tip opening 13 reduced in diameter and the inward protrusion 12. It defines the range to obtain. A plurality of inward protruding portions 12 are formed with radial grooves 14 formed by cutting at equal intervals in an annular shape. The radial grooves 14 pass through the inward projecting portion 12 and communicate with the rear hole 11 to ensure ink supply to the ball house portion 9.

First to third ball-point pen tips used in the test were produced based on the above-described example. The first ballpoint pen tip is shown in FIG. 3 and FIG. 4 which is a sectional view taken along the line II-II ′ of FIG. 3 and FIG. 5 which is a sectional view taken along the line III-III ′ of FIG. The first ballpoint pen tip forms a ball receiving seat 15 by driving a tapered pin into the inward protrusion 12 for the purpose of smoothing the surface of the inward protrusion 12 and improving the rotation of the ball. In FIG. 3, the ball 2 in a state where the ball 2 is in contact with the tip opening portion 13 is indicated by a dotted line, and the difference between the deviation between the solid line and the dotted line indicates the movement amount E1 of the ball 2 in the front-rear direction. FIG. 4 shows the size of the tip opening 13 through which ink is ejected from the ballpoint pen tip 1 when the ball 2 is seated on the ball seat 15, and the lattice-shaped range S 1 is between the ball 2 and the ball house 9. The projected area of the tip opening 13 that can be formed is shown. In FIG. 5, the ball 2 is not shown for convenience of explanation, but a dotted line drawn so as to intersect the ball receiving seat 15 and the radial groove 14 is a portion in contact with the ball 2 when it is seated on the ball receiving seat 15. Is shown. That is, the radial grooves 14 located outside the dotted line substantially serve as ink passages for supplying ink into the ball house portion 9, and the projected area of the ink passages is indicated by a grid-like range T1. The value of T1 is the total value of the grid-like ranges of the radial grooves 14 at three locations.
The dimension values and the area values of the first ballpoint pen tip are shown below.
(First ballpoint pen tip)
Ball diameter A1: 1.0 mm
Tip opening diameter B1: 0.980 mm
Tip opening gap width C1: 0.032 mm
Ball protrusion length D1: 0.288mm
Ball longitudinal movement E1: 0.120mm
Ball house diameter F1: 1.085mm
Contact diameter G1: 0.574mm between the ball seat and the ball
Medium hole diameter H1: 0.560mm
Rear hole diameter J1: 1.10mm
Radial groove width K1: 0.30mm
Radial groove radial depth L1: 0.262 mm
Tip opening area S1: 0.110 mm ²
Radial groove total opening area T1: 0.216 mm ²
Caulking angle α1: 80 degrees Ball seat opening angle β1: 110 degrees

The second ballpoint pen tip is shown in FIG. 6 and FIG. 7 which is a sectional view taken along the line II-II ′ of FIG. 6 and FIG. 8 which is a sectional view taken along the line III-III ′ of FIG. The second ballpoint pen tip forms a ball receiving seat 15 by driving a tapered pin into the inward projecting portion 12 in the same manner as the first ballpoint pen tip. Further, the radial groove 14 is formed not to communicate with the rear hole 11 but to stay in the middle of the inward protruding portion 12 in order to suppress the movement of ink in the ballpoint pen tip when an impact is applied to the product. FIG. 6 shows the ball 2 in a state in which the ball 2 is in contact with the tip opening 13 as shown in FIG. 3 of the first ball-point pen tip. The difference between the solid line and the dotted line is the vertical direction of the ball The movement amount E2 is shown. FIG. 7 shows the size of the tip opening 13 through which ink is ejected from the ball-point pen tip 1 when the ball 2 is seated on the ball receiving seat 15 as in FIG. 4 of the first ball-point pen tip. S2 indicates the projected area of the tip opening 13 formed between the ball 2 and the ball house 9. FIG. 8 also shows the portion of the first ballpoint pen tip that is in contact with the ball seat 15 as shown in FIG. 5 by dotted lines, as in FIG. 9 shows the projected area of the ink passage to be supplied into the interior 9. Note that the value of T2 is the total value of the lattice-like ranges of the four radial grooves 14 at four locations.
The dimension values and area values of the second ballpoint pen tip are shown below.
(Second ballpoint pen tip)
Ball diameter A2: 1.0 mm
Tip opening diameter B2: 0.970 mm
Tip opening gap width C2: 0.041 mm
Ball protrusion length D2: 0.260 mm
Ball back-and-forth movement amount E2: 0.140 mm
Ball house diameter F2: 1.085mm
Ball receiving seat and ball contact diameter G2: 0.643 mm
Medium hole diameter H2: 0.560mm
Rear hole diameter J2: 1.10mm
Radial groove width K2: 0.17 mm
Radial groove radial direction depth L2: 0.224 mm
Tip opening area S2: 0.121 mm ²
Radial groove total opening area T2: 0.136 mm ²
Caulking angle α2: 90 degrees Ball seat opening angle β2: 100 degrees

The third ballpoint pen tip is shown in FIG. 9 and FIG. 10 which is a sectional view taken along the line II-II ′ of FIG. 9 and FIG. 11 which is a sectional view taken along the line III-III ′ of FIG. The third ballpoint pen tip is a ball having substantially the same curvature as the ball 2 by pressing the ball 2 against the inward projecting portion 12 for the purpose of stabilizing the position of the ball 2 during writing and causing smooth rotation with little unnecessary vibration. A receiving seat 16 is formed. FIG. 9 shows the ball 2 in a state in which the ball 2 is in contact with the tip opening 13 as shown in FIG. 3 of the first ball-point pen tip with a dotted line. The movement amount E3 is shown. FIG. 10 shows the size of the tip opening 13 through which ink is ejected from the ball-point pen tip 1 when the ball 2 is seated on the ball receiving seat 16 as in FIG. 4 of the first ball-point pen tip. S <b> 3 indicates the projected area of the tip opening 13 formed between the ball 2 and the ball house portion 9. Although the ball 2 is not shown in FIG. 11 for convenience of explanation, the ball 2 is in contact with the ball receiving seat 16 at the time of writing, and the ink passage for supplying ink into the ball house portion 9 is substantially the ball receiving seat 16. The radial grooves 14 are opened to the outside of the maximum outer peripheral diameter, and the projected area of the ink passage is indicated by a lattice-shaped range T3. Note that the value of T3 is the total value of the lattice-like ranges of the three radial grooves 14 at three locations.
The dimension values and area values of the third ballpoint pen tip are shown below.
(Third ballpoint pen tip)
Ball diameter A3: 1.0 mm
Tip opening diameter B3: 0.980 mm
Tip opening gap width C3: 0.046 mm
Ball protrusion length D3: 0.260 mm
Ball back-and-forth movement amount E3: 0.130 mm
Ball house diameter F3: 1.085mm
Medium hole diameter H3: 0.56mm
Rear hole diameter J3: 1.10mm
Radial groove width K3: 0.30 mm
Radial groove radial direction depth L3: 0.262 mm
Ball seat outer diameter M3: 0.720 mm
Tip opening area S3: 0.134 mm ²
Radial groove total opening area T3: 0.147 mm ²
Caulking angle α3: 80 degrees

  The ball 2 of each of the first to third ball-point pen tips is made of a ceramic sintered body mainly composed of silicon carbide (trade name: Black Safari, manufactured by Tsubaki Nakashima Co., Ltd.). The thickness Ra (JIS B 0601) was 3.0 nm. The ball holder was made of stainless steel (trade name: SF20T, manufactured by Shimomura Special Seiko Co., Ltd.) and had a Vickers hardness (HV) of 240.

  The tip holder 4 is formed of polybutylene terephthalate resin, and the minimum inner diameter of the through hole 4 from the back of the ballpoint pen tip 1 to the ink containing tube is 1.31 mm.

  The ink containing tube 6 is a pipe formed by extrusion molding of polypropylene resin, and the inner diameter is a pipe having a diameter of 2.6 mm and a thickness of 0.7 mm. The ink amount was 0.6 g and the ink backflow prevention composition 0.1 g was filled.

  A test ballpoint pen in which the first to third ballpoint pen tips are respectively mounted on the above-described ballpoint pens, and directly filled with ink composition examples 1 to 18, comparative examples 1 to 3, and ink backflow prevention composition 1 or 2. The handwriting and writing performance were evaluated. Table 1 shows the combinations and evaluation results of the mounted ballpoint pen tip, the filled ink composition, and the ink backflow prevention composition.

Handwriting dryness test Under the environment of room temperature 20 ° C and humidity 65%, write 2 x 2 characters "Ei" on the test paper shown in JIS S 6061 7.3, eraser (high polymer) , Manufactured by Pentel Co., Ltd.), the time until the paper surface was not soiled was determined.

Write-through test of handwritten paper on paper Under the environment of room temperature 20 ° C and humidity 65%, write the letter "Yong" of 2x2 size on the test paper shown in 7.3 of JIS S6061 A cross section of the handwriting part was created with a cutter, and the ink penetration depth was measured.

Preparation of hand grease paper A solution (hereinafter referred to as a 30% hand fat diluted solution) prepared by diluting the hand fat prepared with the artificial oil preparation 1 prepared with the following composition to 30% with acetone is prepared. The diluted solution for hand grease was sprayed uniformly on a test paper shown in 7.3 of JIS S6061, and then dried at room temperature for 2 hours to remove acetone and contaminated with hand grease. A hand grease paper was prepared. Similarly, a 60% hand grease diluted solution was prepared to prepare hand grease paper 2 that was significantly contaminated with hand grease.
(Contains artificial hand fat)
Squalane 10.0% by weight
Isopropyl myristate 20.0% by weight
Olive oil 40.0% by weight
Cholesterol 2.0% by weight
Palmitic acid 2.0% by weight
Oleic acid 13.0% by weight
Isostearic acid 13.0% by weight
The above ingredients were mixed with stirring to obtain hand fat.

(Hand grease testability test using hand grease paper 1)
Using a test ballpoint pen, Tribity Lab Co., Ltd.'s Tribo-master (Type: TL201Sa) is used for the grease paper 1 under a writing condition of a writing speed of 7 cm / sec, a writing angle of 70 °, and a writing load of 100 gf. I wrote a straight line. After the writing, the distance of jumping in the straight line was measured.
(Brightness confirmation test using hand grease paper 1)
The writing lines obtained in the hand grease writing test using the hand grease paper 1 were visually confirmed and evaluated according to the following criteria.
◯: A glittering pigment containing metal uniformly in the handwriting exists and has a glitter feeling.
X: It is divided into a portion having no glitter and a portion having a glitter, and there is unevenness.
(Hand grease testability test using hand grease paper 2)
Using a test ballpoint pen, Tribity Lab Co., Ltd.'s Tribo-master (Type: TL201Sa) is used on a hand-grown paper 2 with a writing speed of 7 cm / sec, a writing angle of 70 °, and a writing load of 100 gf. I wrote a straight line. After the writing, the distance of jumping in the straight line was measured.
(Brightness confirmation test using hand grease paper 2)
The writing lines obtained in the hand grease writing test using the hand grease paper 2 were visually confirmed and evaluated according to the following criteria.
◯: A glittering pigment containing metal uniformly in the handwriting exists and has a glitter feeling.
X: It is divided into a portion having no glitter and a portion having a glitter, and there is unevenness.

Sounding test Under the environment of room temperature 20 ° C and humidity 65%, write the letter of “Yong” of 2 × 2 size on the test paper shown in 7.3 of JIS S6061, and sound at that time The state of was evaluated according to the following criteria.
○: Sound can be heard.
×: No sound can be heard.

Written test under low temperature environment Tribo-master (Type: TL201Sa manufactured by Trinity Lab Co., Ltd.) is used on a test paper shown in 7.3 of JIS S6061, using a test ballpoint pen in an environment of room temperature 5 ° C. and humidity 20%. ), A 15 cm straight line was written under the writing conditions of a writing speed of 7 cm / sec, a writing angle of 70 °, and a writing load of 100 gf. After the writing, the faint distance in the straight line was measured.

As shown in Table 1, Examples 1 to 18 have bright pigments containing metal in the ink and xanthan gum and welan gum as polysaccharides, so that the handwriting has good drying properties and can prevent the penetrating of the handwriting to paper. There was no squeaking when writing, handwriting with a glittering feel was obtained even on hand-grown paper, and there was no problem of blurring even at low temperatures.
In particular, Examples 1 to 7 contain polyglycerin fatty acid ester having an HLB value of 8 or more and 18 or less and 3-methyl-3-methoxy-1-butanol. A handwriting with a feeling was obtained, and no blurring occurred even at low temperatures.
On the other hand, in Comparative Example 1, the ink contains a glittering pigment containing metal and welan gum, but since it does not contain xanthan gum, writing dryness is poor, and there is a lot of penetrating paper on the handwriting. It was impossible to write even on paper with hand grease attached with a glittering handwriting, and it squeaked at the time of writing and faded over time at low temperatures.
In Comparative Example 2, the ink contains a glitter pigment containing metal and xanthan gum, but because it does not contain welan gum, writing dryness is poor, and there is a lot of penetrating paper on the handwriting, and a sufficient glitter feeling. In other words, it was impossible to write on paper with hand grease on it, and it would sound when writing and faded over time at low temperatures.
In Comparative Example 3, the ink contains a glittering pigment containing metal, xanthan gum, and a water-soluble soy polysaccharide, but because it does not contain welan gum, improvement in handwriting dryness such as a combination with welan gum is It is not seen, writing dryness is poor, there is a lot of penetrating through the paper of the handwriting, it is not possible to write on paper with hand grease with sufficient radiance, sounds at the time of writing, at low temperatures, over time It was faint.

  As described above, the ink of the present invention is capable of forming handwriting with a glitter feeling, has good handwriting dryness, does not show through to the paper, and can be written on paper with hand-grease with sufficient glitter feeling. It is a water-based glittering ink composition for ballpoint pens that does not squeal during writing and does not fade over time at low temperatures.

DESCRIPTION OF SYMBOLS 1 Ball-point pen tip 2 Ball 3 Ball holder 4 Tip holder through-hole 5 Tip holder 6 Ink storage tube 7 Ink 8 Ink backflow prevention composition 9 Ball house part 10 Medium hole 11 Rear hole 12 Inward protrusion part 13 Tip opening part 14 Radial groove 15, 16 Ball seat A1, A2, A3 Ball diameter B1, B2, B3 Tip opening diameter C1, C2, C3 Tip opening gap width D1, D2, D3 Ball protrusion length E1, E2, E3 Ball longitudinal movement Amount F1, F2, F3 Ball house part diameter G1, G2 Contact part diameter of ball receiving seat and ball H1, H2, H3 Medium hole diameter J1, J2, J3 Rear hole diameter K1, K2, K3 Radial groove width L1, L2, L3 Radial groove radial depth M3 Ball seat outer circumference S1, S2, S3 Tip opening area T1, T2, T3 Radial groove total opening area α1, α2, α3 Caulking angle β1, β2 Ball seat opening angle

Claims (4)

  A water-based glittering ink composition for ballpoint pens comprising at least a glittering pigment containing a metal, water, xanthan gum, and welan gum.   a / b = 0.35 or more and 4.0 or less when a: content of xanthan gum in ink [wt%], b: content of welan gum in ink [wt%], and xanthan gum 2. The water-based glittering ink composition for ballpoint pens according to claim 1, wherein a + b, which is the content of the welan gum in the ink, is 0.3 wt% or more and 0.7 wt% or less.   Furthermore, the water-based glittering ink composition for ball-point pens of Claim 1 or Claim 2 containing the polyglyceryl fatty acid ester whose HLB value is 8-18.   The aqueous glittering ink composition for ballpoint pens according to claim 1 or 2, further comprising 3-methyl-3-methoxy-1-butanol.

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