JP2008031371A - Ink composition for writing utensil and writing utensil using this - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a writing utensil which can make full use of an ink composition filled in an ink cartridge with an ink composition not adhering to the ink cartridge. <P>SOLUTION: This ink composition for a writing utensil comprises a colorant, a liquid medium, hydroquinone sulfonic acid and/or a salt thereof and triethanolamine. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ink composition that does not adhere to an ink storage tube even after being left for a long period of time, and more particularly to a writing instrument that can use up the ink composition filled in the ink storage tube.

  One of the characteristics of a writing instrument formed by directly filling an ink containing tube with an ink composition is that the ink composition in the ink containing tube decreases as the ink is consumed, and the remaining amount of ink can be clearly recognized. Conventionally, polyethylene and polypropylene have been used for ink storage tubes of ballpoint pens from the viewpoints of low evaporation property, transparency, productivity, and cost of the ink composition. These materials have low surface free energy and are difficult to adsorb and adhere to substances. However, the ink composition for writing instruments contains various components such as an activator, and the colorant in the ink composition may be adsorbed and colored on the inner surface of the ink containing tube due to the reaction over time. In particular, in the case where the colorant contains a chlorine group, the chlorine group becomes an adsorption site with the ink storage tube, and the adhesion to the inner surface of the ink storage tube occurred remarkably. When adhesion to the inner surface of the ink storage tube occurs, it may appear that the ink still remains despite the fact that the ink is not ejected, or substantially the amount of ink composition initially filled in the ink storage tube. There was a problem that the amount of ink composition that can be written is reduced and the assumed writing distance is shortened.

In order to solve these problems, silica is added to the ink to prevent the ink from adhering to the ink containing tube (see Patent Document 1), or oil that is not compatible with fatty acid amide wax is added to the ink. (See Patent Document 2), an example of preventing ink from adhering to the inner surface of the ink containing tube is known.
JP 2004-002541 (48th line from the top of the right column on page 2 to 49th line of the left column on page 3) Japanese Patent Laid-Open No. 11-310743 (from page 38, left column, 38th line to right column, 33rd line)

  In Patent Document 1, since silica agglomerates are dispersed and added, the silica collects in a part of the writing instrument depending on the direction of the pen tip when left standing for a long time, and the ink adheres to the ink containing tube. End up. As a result, the ink composition adhering to the inner surface of the ink containing tube remains, and an ink composition that does not become handwriting is produced.

  In Patent Document 2, oil that is incompatible with the fatty acid amide wax in the ink exists as a lubricant layer between the ink and the ink storage tube so that the ink does not adhere to the ink storage tube. However, since the oil used is not compatible with the ink from the beginning, the oil aggregates and does not form a uniform layer on the inner surface of the ink containing tube when left for a long period of time. The part which contacts directly is made. As a result, the ink composition adhering to the inner surface of the ink containing tube remains, and an ink composition that does not become handwriting is produced.

  That is, the gist of the present invention is a writing instrument ink composition containing at least a colorant, a liquid medium, hydroquinonesulfonic acid and / or a salt thereof, and triethanolamine.

  Hydroquinonesulfonic acid and / or a salt thereof and triethanolamine in the ink composition adhere to the inner surface of the ink containing tube when the ink composition is filled in the ink containing tube. Therefore, it can suppress that the coloring agent in an ink composition adheres to an ink storage pipe inner surface, and can use up the ink composition accommodated in the ink storage pipe as much as possible handwriting. This effect is presumed as follows. Polyolefin resins and the like used for ink containing tubes are easily negatively charged. On the other hand, hydroquinonesulfonic acid and / or a salt thereof contains a sulfone group that is negatively charged in an aqueous solution, and therefore, a portion having no substituent and an ink containing tube are likely to adhere. On the other hand, triethanolamine is always positively charged and easily attached to the ink containing tube because the proton in the ink composition is always coordinated to the nitrogen atom having an unshared electron pair. Furthermore, when hydroquinonesulfonic acid and / or a salt thereof and triethanolamine coexist, a neutralization reaction occurs, and this reaction product easily adheres, and the steric hindrance of triethanolamine causes a colorant or an activator in the ink composition. Since it cannot adhere to the ink containing tube, the effect continues over time. Therefore, the ink composition cannot be attached to the ink storage tube over a long period of time, and the ink composition existing in the ink storage tube can be used up.

  Hydroquinone sulfonic acid and / or its salt is a polyphenol type reducing agent, but unlike other polyphenol type reducing agents, dissolved oxygen present in the ink composition and oxygen entering through the ink containing tube. Even when oxidized to form a quinone structure, the solubility in the liquid medium constituting the ink composition in which the sulfonic acid group is present remains good. Therefore, the effect is not lost even after being left for a long time.

  The hydroquinone sulfonic acid and / or salt thereof used in the present invention adheres to the ink containing tube and prevents substances such as colorants in the ink composition from adhering to the inner surface of the ink containing tube. The ink composition filled in the container can be used up. Specific examples thereof include potassium hydroquinone sulfonate (manufactured by Samsung Chemical Industry Co., Ltd.). And as the usage-amount, 0.05 to 5.0 weight% is preferable. If the amount used is less than 0.05% by weight, the amount of hydroquinonesulfonic acid and / or its salt present is too small with respect to the surface area of the inner surface of the ink containing tube, so that there is no sufficient adhesion preventing effect. Even if the amount used is more than 5.0% by weight, other substances in the ink composition react with hydroquinonesulfonic acid and / or its salt, causing aggregation, precipitation, etc. in the ink composition. I can't write.

  The triethanolamine used in the present invention adheres to the ink containing tube together with the hydroquinonesulfonic acid and / or salt thereof, and prevents substances such as colorants in the ink composition from adhering to the inner surface of the ink containing tube. The ink composition filled in the ink storage tube can be used up. And as the usage-amount, 0.05 to 5.0 weight% is preferable. If the amount used is less than 0.05% by weight, the amount of triethanolamine used is too small relative to the amount of hydroquinonesulfonic acid and / or its salt used, and therefore there is no sufficient anti-adhesion effect. Further, even if the amount used is more than 5.0% by weight, the pH of the ink composition becomes too high, and the components of the ink composition are aggregated and precipitated, faint or cannot be written.

  A transparent or translucent ink container that is visible from the outside directly fills the ink composition, and as the ink composition is consumed, the ink composition in the ink container decreases and the remaining amount of ink composition can be clearly seen. Used for. Therefore, the functions of the ink storage tube require visibility, strength, low evaporation property of the ink composition, and blocking of the outside air, and other costs and ease of manufacture are required. Materials for the ink storage tube include polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins, fluororesins, silicone resins, polyamide resins such as nylon, polyethylene terephthalate, polymethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly Polyester resins such as butylene naphthalate and polyethylene terephthalate polyethylene naphthalate, and acrylic resins such as polyacrylonitrile can be used.

  In the present invention, as an ink composition for forming handwriting / application marks, an ink containing a liquid medium, a colorant, a viscosity modifier, a surfactant and the like can be used.

  As the colorant used in the ink, both dyes and pigments conventionally used in ink compositions can be used without limitation. Specific examples include dyes such as Japan Fast Black D Conch (CI Direct Black 17), Water Black 100L (19), Water Black 108L (19), Water Black 191L (same as above). 19), Water Black L-200 (19), Water Black # 7 (19), Kaya Set Black W9 (19), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black EX (same 38), Direct Deep Black (similar 38), Direct Fast Black Conk (same 51), Kayara Spragley VGN (71), Kayak Direct Brilliant Yellow G (CI Direct Yellow 4) ) Direct fast erotic 5GL (same as 26), Eisenburra Yellow GCLH (same as 44), Direct Fast Yellow R (same as 50), Daiwa Ij Yellow 306H (same as 132), Eisen Direct Fast Red FH (C.I. Direct Red 1), Nippon Fast Scarlet GSX (same 4), Direct Fast Scarlet 4BS (same 23), Eisen Direct Durin BH (same 31), Direct Scarlet B (same 37), Kayak Direct Scarlet 3B (same 39), Eisen Buri Murabin Conk 2BLH ( 75), Sumilite Red F3B (80), Eisen Burimura Red 4BH (81) Kayaras Spral Bin BL (83), Kayaras Light Red F5G (225), Kayaras Light Red F5B (226) ), Kayarasla Trose FR (227) Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (15), Benzo Brilliant Sky Blue 8GS (41), Sumilite Spula Blue BRR Conch (71), Daibogen Turquoise Blue S (86), Water Blue # 3 (86), Kayara Star Coyze Blue GL (86), Daiwa Blue 215H (87), Kayala Supra Blue FF2GL (106), Kayara Supra Direct dyes such as Blue FFRL (108) Calas Splatter Turquoise Blue FBL (199), Acid Blue Black 10B (CI Acid Black 1), Nigrosine (2), Water Black R455 (2), Water Black R510 (2), Sumi Nord Milling Black 8BX (same as 24), Kayanol Milling Black VLG (same as 26), Kayanol Milling Black BR Conk (same as 31), Mitsui Nylon Black GL (same as 52), Eisen Opal Black WH Extra Conk (same as 52), Sumilan Black WA (52), Ranil Black BG Extra Conk (107), Kayanol Milling Black TLB (109), Suminol Milling Black B (109), Kayanol Milling Black TLR (110), Eisen Opal Black New Conque (119), Water Black 187-L (154) Acid Yellow # 10 (C.I. I. Acid Yellow 1), Kayak Acid Brilliant Flavin FF (7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Water Yellow # 1 (same as above) 23), Daiwa Torazine (same 25), Kyakuto Tolazine (same 23), Suminol Fast Yellow R (same 25) Diacid Light Yellow 2GP (same 29), Suminol Milling Yellow O (same 38), Sumi Knoll Milling Yellow MR (42), Water Yellow # 6 (42), Kayanol Yellow NFG (49), Suminol Milling Yellow 3G (72), Suminol Fast Yellow G (61), Suminol Milling Yellow G (78), Cayanole Yellow N5G (110), Sumino Milling Yellow 4G 200% (same as 141), Kayanol Yellow NG (same 135), Kayanol Milling Yellow 5GW (same as 127), Kayanol Milling Yellow 6GW (same 142), Sumitomo Fast Scarlet A (CI Acid Red 8) ), Kayak Silk Scarlet (same 9), Solar Rubin Extra (same 14), Daiwa New Coxin (18), Water Scarlet (18), Daiwa Red 102 (18), Eisenbonso RH (same 26) ), Daiwa Red 2 (same as 27), Suminol Leveling Brilliant Red S3B (same as 35), Kayasil Rubinol 3GS (same as 37), Eisen Erythrosine (same as 51), Kayaqua acid Rhodamine FB (same as 52), Daiwa red 106 (52), Suminol Leveling Ruby 3GP (57), diacy alizarin rubinol F3G 200% (82), alizarin rubinol 5G (83), Eiseneosin GH (87), Water Red # 2 (87), Daiwa Red 103WB ( 87), Water Pink # 2 (92), Eisen Acid Phloxin PB (92), Daiwa Red No. 104 (92), Rose Bengal (94), Kayanol Milling Scarlet FGW (111), Kayanol Milling Lubin 3BW (129), Suminol Milling Brilliant Red 3BN Conch (131), Suminol Milling Brilliant Red BS (138), Eisen Opal Pink BH (186), Suminol Brilliant Red B Conch (249) , Kayak acid brilian Tread 3BL (same as 254), kayak acid brilliant red BL (same as 265), Kayanor Milling Red GW (same as 276), Mitsui Acid Violet 6BN (C.I. I. Acid Violet 15), Mitsui Acid Violet BN (17), Water Violet # 1 (49), Water Violet # 5 (49), Daiwa Purple 1 (49), Violet L10 (49), Sumitomo Patent Pure Blue VX (CI Acid Blue 1), Water Blue # 106 (1), Patent Blue AF (7), Water Blue # 9 (9), Daiwa Blue No. 1 (9), Blue L20 (same 9), Supranol Blue B (same 15), Water Blue # 116 (same 15), Orient Soluble Blue OBC (same 22), Orient Soluble Blue OBX (same 22), Suminol Leveling Blue 4GL ( 23), Mitsui Nylon Fast Blue G (25), Kayasil Blue AGG (40) Kayasil Blue BR (41), Mitsui Alizarin Saphirol SE (43), Suminol Leveling Sky Blue R Extraconk (62), Mitsui Nylon Fast Sky Blue R (78), Sumitomo Brilliant Indocyanine 6Bh / e ( 83), Sandlancyanine N-6B 350% (90), Water Blue # 115 (90), Water Blue # 105 (90), Orient Soluble Blue OBB (93), Spranol Cyanine 7BF (same as above) 100), Sumitomo Brilliant Blue 5G (103), Acid Blue (103), Asilane Brilliant Blue FFR (104), Cyanol Milling Ultra Sky SE (112), Cyanol Milling Cyanine 5R (113), Aizeno Rucyanin 2GLH (158), Daiwa Guinea Green B (CI Acid Green 3) Acid Brilliant Milling Green (9), Daiwa Green # 70 (16), Cyanol Cyanine Green G (25), Suminol Acid dyes such as Milling Green G (27), Water Orange # 17 (CI Acid Orange 56), Food Dyes such as Water Yellow # 2 (CI Food Yellow 3), Malachite Green (CI) 42000), Victoria Blue FB (C.I. 44045), Methyl Violet FN (C.I. 42535), Rhodamine F4G (C.I. 45160), Rhodamine 6GCP (C.I. 45160), SPILON BLACK GMH SPECIAL , SPILON RED C GH, SPILON RED C-BH, SPILON BLUE C-RH, SPILON BLUE BPNH, SPILON YELLOW C-2GH, SPILON VIOLET C-RH, S. P. T.A. ORANGE6, S. P. T.A. Eisenspiron color such as BLUE111 (manufactured by Hodogaya Chemical Co., Ltd.), Eisen SOT dye, ORIENT SPRIT BLACK AB, VALIFAST BLACK 3804, VALIFAST RED 1320, VALIFAST RED 1360, VALIFAST ORANGE ST VALIFAST BLUE 1601, VALIFAST BLUE 1603, VALIFAST BLUE 1621, VALIFAST BLUE 2601, VALIFAST YELLOW 1110, VALIFAST YELLOW 3104, VALIFAST YELLOW 3105, VALIFAST 1105 (Orient Chemical Co., Ltd.) etc. Varifast Color, Orient Oil Color, Rhodamine B Base, Soldan Red 3R, Methyl Violet 2B Base, Victoria Blue F4R, Nigrosine Base LK, Neo Super Blue C-555 (Central Synthesis) (Chemical Co., Ltd.).

  As the pigment, Special Black 6, S170, S610, 5, 4, 4A, 550, 35, 250, 100, Printex 150T, U, V, 140U, 140V, 95 90, 85, 80, 75, 55, 45, P, XE2, L6, L, 300, 30, 30, 35, 25, 200, A, G (above, Degussa Japan Co., Ltd.), # 2400B, # 2350, # 2300, # 2200B, # 1000, # 950, # 900, # 850, # MCF88, MA600, MA100, MA7, MA11 , # 50, # 52, # 45, # 44, # 40, # 33, # 32, # 30, CF9, # 20B, # 4000B (Mitsubishi Chemical Industry Co., Ltd.), MONARCH1300, 1100, 1000, 900, 880, 800, 700, MOGUL L, REGAL 400R, 660R, 500R, 330R, 300R, 99R, ELFTEX8, 12, BLACK PEARLS 2000 (or more, USA, Cabot Co. LTD), Raven7000, 5750, 5250, 5000, 3500, 2000, 1500, 1255, 1250, 1200, 1170, 1060, 1040, 1035, 1020, 1000, 890H, 890, 850, 790, 780, 780, 780, 500, 450, 430, 420, 410, 22, 22, 16, 825 OilBeads H20, C, Conductex 975, 90 SC (above, Colombian Carbon Japan Co., Ltd.), Printex 3, 25, 30, 35, 40, 45, 55, 60, 75, 80, 85, 90, 95, 300, Special Black 4, 5, 100, 250, 550 (Degussa Huls Japan Co., Ltd.). Mitsubishi Carbon Black # 2700, # 2650, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, Same # 950, Same # 900, Same # 850, Same # 750, Same # 650, Same # 52, Same # 52, Same # 50, Same # 47, Same # 45, Same # 45L, Same # 44, Same # 40, Same # # 33, # 32, # 30, # 25, # 20, # 10, # 5, # 95, # 260, CF9, MCF88, MA600, MA77, MA7, MA11, MA100, MA100R, MA100S, MA100S, MA220, MA230 (manufactured by Mitsubishi Chemical Corporation), Talker Black # 8500 / F, # 8300 / F, # 7550SB / F, # 7400, # 7360 B / F, # 7350 / F, # 7270SB, # 7100 / F, # 7050 (above Tokai Carbon Co., Ltd.) and other carbon black, KA-10, 10P, 15, 20 30, 35, 60, 80, 90, KR-310, 380, 460, 480 (above, manufactured by Titanium Industry Co., Ltd.), P25 (produced by Nippon Aerosil Co., Ltd.), etc. Inorganic pigments such as titanium, black iron oxide, yellow iron oxide, red iron oxide, ultramarine, cobalt blue, chrome green, chromium oxide, Hansa Yellow 10G, 5G, 3G, 4, GR, AG, Benzidine Yellow, Permanent Yellow NCG, Tartarine Lake, Quinoline Yellow, Sudan 1, Permanent Orange, Indanthren Brilliant Orange GN, Permanent Brown FG, Parabrow Permanent Red 4R, Fire Red, Brilliant Carmine BS, Pyrazolone Red, Lake Red C, Quinacridone Red, Brilliant Carmine 6B, Bordeaux 5B, Thioindigo Red, Fast Violet B, Dioxane Violet, Alkaline Blue Lake, Phthalocyanine Blue, Indigo, Acid Green lake, phthalocyanine green, C.I. I. Pigment Blue 2, 9, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 16, 17, 28, 29, 36, 60, 68, 76, 80, C.I. I. PigmentRed 2, 3, 5, 8, 14, 17, 22, 22, 31, 31, 48: 1, 48: 2, 48: 3, 48: 4, 53: 1, 53: 2, 57: 1, 112, 122, 144, 146, 149, 166, 170, 175, 176, 177, 179, 184, 185 187, 188, 202, 207, 208, 209, 210, 211, 211, 213, 214, 242, 253, 254, 255, 256, 256, 257, H.264, 266, 268, 270, 272, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 79, 81, 83, 93, 94, 95, 97 109, 110, 111, 120, 128, 133, 136, 138, 139, 147, 151, 154, 155, 167, 173, 174, 175, 176, 180, 185, 191, 194, 213, C.I. I. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 62, 68, 72, 74, C.I. I. PigmentGreen 7, 36 and 37 are C.I. I. Pigment Violet 19, 23, etc. Organic pigments, BS-605, 607 (above, manufactured by Toyo Aluminum Co., Ltd.), Bronze Powder P-555, P-777 (above, manufactured by Nakajima Metal Foil Industry Co., Ltd.), Examples thereof include metal powder pigments such as bronze powder 3L5 and 3L7 (above, manufactured by Fukuda Metal Foil Industry Co., Ltd.). In addition, inorganic fluorescent pigments such as zinc sulfide, zinc silicate, cadmium zinc sulfate, calcium sulfide, strontium sulfide, and calcium tungstate, and other known organic fluorescent pigments can be used. The above-described colorants can be used alone or in combination with others, and the amount used varies depending on the color tone and the like, but is preferably 0.5 to 20% by weight based on the total amount of the ink composition.

  Further, in the case of a pigment ink composition, it is advantageous in producing a pigment ink composition to use an ink composition base in which a pigment is dispersed in a liquid medium. Specifically, uniperse series manufactured by Ciba Specialty Chemicals Co., Ltd., Hostfine series manufactured by Clariant Japan Co., Ltd., Disperse series manufactured by Dainippon Ink & Chemicals, Inc., Ryudye series, manufactured by Fuji Dye Co., Ltd. Fuji. SP series, Sanyo Dye Co., Ltd. Emacol series, Sandye series, Orient Chemical Industry Co., Ltd. MicroPigmo series, MicroJet series, Toyo Ink Co., Ltd. Rio Fast series, EM Color series, Sumika Color Co., Ltd. ) Polux series, (Dispersion of inorganic and organic pigments), NKW series manufactured by Nippon Fluorochemicals, Cosmo Color series manufactured by Toyo Soda Co., Ltd., Sinloi Color Base Series manufactured by Sinloi Co., Ltd. (Dispersion of fluorescent pigment), Renol Yellow GG-HW30, HR-HW30, Orange RL-HW30, Red HF2B-HW30, FGR-HW30, F5RK-HW30, Carmine FBB-HW30, V olet RL-HW30, Blue B2G-HW30, CF-HW30, Green GG-HW30, Brown HFR-HW30, Black R-HW30 (manufactured by Clariant Japan Co., Ltd.), UTCO-001 Yellow, 012 Yellow 021 Orange, 031 Red, 032 Red, 042 Violet, 052 Violet, 051 Blue, 052 Blue, 061 Green, 591 Black, 592 Black (manufactured by Daiichi Seika Kogyo Co., Ltd.), MICROLIT Yellow 4G-A, MX-A, 2R-A, Brown 5R-A, Scarlet RA, Red 2C-A, 3R-A, Magenta 2B-A, Violet B-A, Blue 4G-A, Green G-A (above Ciba Special Is those-party Chemicals Corp.) and the like, it may be used by mixing one kind or two or more kinds. In addition, dyes, pigments, and dispersed pigments can be used in combination.

  Moreover, you may add a thickener as needed in order to obtain the appropriate viscosity physical property as an ink composition for writing instruments. Specific examples thereof include natural gum arabic, tragacanth gum, guar gum, locust bean gum, alginic acid, carrageenan, gelatin, casein, welan gum, rumzan gum, xanthan gum, dextran, leozan gum, alkasy gum, semi-synthetic methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxy Methyl cellulose, sodium starch glycolate, sodium alginate, propylene glycol alginate, synthetic polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, sodium polyacrylate, carboxyvinyl polymer, polyethylene oxide, copolymer of vinyl acetate and polyvinyl pyrrolidone, Acrylic acid and alkyl methacrylate copolymer, acrylic Alkali metal salts of resins, condensation resins of ketones and formaldehyde such as cyclohexanone, acetophenone and urea, condensation resins of cyclohexanone and resins hydrogenated thereof, maleic acid resins, copolymers of styrene and maleic esters, styrene and Copolymers with acrylic acid or its esters, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetal, polyamides that are condensates of polymerized fatty acids and polyamines, epoxy resins, polyvinyl alkyl ethers, coumarone-indene resins, polyterpenes, xylene resins, Rosin resin and its hydrogenated product, rosin modified maleic acid resin, vinylpyrrolidone-vinyl acetate copolymer, polymethacrylic acid ester, polyacrylic acid polymethacrylic acid copolymer, polyoxyethylene A phenol resin, a polymer of a hydrophilic monomer having a carboxylic acid group in its molecule or a copolymer with a lipophilic monomer, or a rosin-modified resin, tall oil-modified resin, fatty acid amide, long-chain fatty acid ester polymer, polyethylene oxide, Organic bentonite type, silica type, cellulose derivatives and the like can be mentioned.

  Water can be used as the main solvent of the liquid medium for preparing the ink composition. Furthermore, conventionally known organic solvents can be used for the purpose of various qualities as the ink composition, for example, prevention of ink freezing at low temperatures and prevention of ink drying at the nib. Specific examples of the organic solvent include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, hexylene glycol, 1,3-butylene glycol, thiodiethylene glycol, glycerin, benzyl glycol, and benzyl diglycol, Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene Glycol monohe Glycol ethers such as sil ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether Alcohol solvents such as benzyl alcohol, α-methylbenzyl alcohol, lauryl alcohol, tridecyl alcohol, isododecyl alcohol, isotridecyl alcohol, propylene glycol methyl ether acetate, propylene glycol diacetate, 2-pyrrolidone, N-methyl -2-pyrrolidone It is done. These water-soluble organic solvents can be used alone or in combination. The amount used is preferably 10.0% by weight or more and 60.0% by weight or less based on the total amount of the ink composition.

  In addition to the above, various polymer dispersants and surfactants can be used. For example, as a polymer dispersant, natural rubbers such as gum arabic and tragacanth, glucosides such as saponin, cellulose derivatives such as methylcellulose, carboxycellulose and hydroxymethylcellulose, natural polymers such as lignin sulfonate and shellac, Anionic polymers such as polyacrylate, salt of styrene-acrylic acid copolymer, salt of vinylnaphthalene-maleic acid copolymer, salt of β-naphthalenesulfonic acid formalin condensate, phosphate, and polyvinyl Nonionic polymers such as alcohol, polyvinyl pyrrolidone, and polyethylene glycol are listed. In addition, surfactants include anionic surfactants such as fatty acid salts, higher alcohol sulfates, liquid fatty acid sulfates, alkylallyl sulfonates, polyoxyethylene alkyl ethers, sorbitan alkyl esters, polyoxyethylene Nonionic surfactants such as sorbitan alkyl esters are listed.

  In addition, styrene-acrylic copolymer alkali metal salts, amine salts, ammonium salts, α to fix benzothiazoline-based and omadin-based antiseptics, benzotriazole-based rust-preventing agents, pigments, etc. to the writing surface. -Water-soluble resins such as alkali metal salts, amine salts and ammonium salts of methylstyrene-acrylic acid copolymers, water-insoluble resins such as vinyl acetate resins and styrene-butadiene copolymers, carbonates such as sodium tripolyphosphate and sodium carbonate PH adjusters such as alkali metal hydroxides such as sodium hydroxide, phosphoric acid, alkali metal hydroxides such as sodium hydroxide, ammonia, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1,3-propanediol, Antifoaming agents such as silicone emulsion, ascorbic acid, etc. It may be used as necessary s additive.

  In the production of the writing instrument of the present invention, the ink composition is filled with a method generally used conventionally without any problem. For example, when filling the ink composition directly into the ink containing tube, the ink composition is allowed to stand under reduced pressure to fill the ink composition in which the dissolved gas in the ink composition is unsaturated, or to fill the ink composition. The written writing instrument is centrifuged under normal pressure or reduced pressure to remove bubbles present in the ink composition or the backflow preventer. Here, in order to centrifuge under reduced pressure, the method of reducing the pressure gradually or all at once while centrifuging, the method of centrifuging after first reducing the pressure, the pressure reducing while centrifuging and then releasing the reduced pressure and then reducing the pressure again And a method of repeatedly performing this decompression and the relaxation of the decompression, etc.

The composition of the ink used is as follows. The part in an example shows a weight part.
(Example 1)
Daiwa Red 104WB (CI Acid Red 92, manufactured by Daiwa Kasei Co., Ltd.)
2.2 parts BASONYL RED 540 (CI Basic Violet 10, manufactured by BASF Japan Ltd.) 0.6 parts ethylene glycol 10.0 parts diethylene glycol 8.0 parts proxel GXL (1,2-benzoisothiazoline-3- ON, antiseptic, manufactured by Avicia Co., Ltd.) 0.2 parts sarcosinate OH (oleoyl sarcosine, manufactured by Nikko Chemicals Co., Ltd.) 3.0 parts potassium hydroquinone sulfonate (manufactured by Samsung Chemical Co., Ltd.) 0.3 parts Kelzan AR (Xanthan Gum, manufactured by Sanki Co., Ltd.) 0.75 parts Triethanolamine 2.0 parts Water 72.95 parts Among the above components, the whole amount of Kelzan AR and the whole amount of water are added with stirring, and the mixture is stirred with a propeller stirrer for 1 hour. A solution of Kelzan AR was obtained by stirring. This liquid and the remaining components were mixed and stirred for another 5 hours until uniform, and then filtered through a 1 micron spool filter to obtain a pink ink having a viscosity of 1950 mPa · s.

(Example 2)
Daiwa Red 106WB (CI Acid Red 52, manufactured by Daiwa Kasei Co., Ltd.)
1.0 parts Daiwa Blue 1WB (CI Acid Blue 9, manufactured by Daiwa Kasei Co., Ltd.) 0.6 parts glycerin 10.0 parts diethylene glycol 8.0 parts Proxel GXL (1,2-benzoisothiazoline-3-one , Antiseptic, manufactured by Avicia Co., Ltd.) 0.2 parts sarcosinate OH (oleoyl sarcosine, manufactured by Nikko Chemicals Co., Ltd.) 3.0 parts potassium hydroquinone sulfonate (manufactured by Samsung Chemical Industry Co., Ltd.) 0.1 part Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.45 parts Triethanolamine 0.5 part Water 76.15 parts Among the above components, the whole amount of Kelzan AR and the whole amount of water are added with stirring, and stirred with a propeller stirrer for 1 hour. Thus, a solution of Kelzan AR was obtained. This liquid and the remaining components were mixed and stirred for another 5 hours until uniform, and then filtered through a 1 micron spool filter to obtain a purple ink having a viscosity of 1050 mPa · s.

(Example 3)
Water Yellow 6C (CI Acid Yellow 42, manufactured by Orient Chemical Co., Ltd.) 1.8 parts Daiwa Blue 1WB (CI Acid Blue 9, manufactured by Daiwa Kasei Co., Ltd.) 1.8 parts glycerin 15. 0 parts ethylene glycol 5.0 parts Proxel GXL (1,2-benzisothiazolin-3-one, preservative, manufactured by Avicia Co., Ltd.) 0.2 parts GF-185 (alkyl phosphoric acid, manufactured by Toho Chemical Industry Co., Ltd.) ) 0.3 part potassium hydroquinone sulfonate (manufactured by Samsung Chemical Industry Co., Ltd.) 1.0 part Kelzan AR (xanthan gum, manufactured by Sanki Co., Ltd.) 0.90 part triethanolamine 3.0 parts water 71.0 parts Among the above components, the whole amount of Kelzan AR and the whole amount of water were added with stirring, and stirred for 1 hour with a propeller stirrer to obtain a solution of Kelzan AR. This liquid and the remaining components were mixed and stirred for another 5 hours until uniform, and then filtered through a 1 micron spool filter to obtain a green ink having a viscosity of 2580 mPa · s.

Example 4
Daiwa Blue 1WB (CI Acid Blue 9, manufactured by Daiwa Kasei Co., Ltd.) 1.0 part Water Blue 117-L (20% liquid product of CI Direct Blue 87, manufactured by Orient Chemical Industry Co., Ltd.) 2.0 parts Edible Yellow No. 4 (CI Acid Yellow 23, manufactured by Daiwa Kasei Co., Ltd.) 0.1 parts Ethylene glycol 10.0 parts Glycerin 8.0 parts Proxel GXL (previously described) 0.2 part Hydroquinonesulfone Potassium acid 1.0 parts Triethanolamine 3.5 parts Water 74.2 parts The above ingredients were stirred with a magnetic stirrer for 5 hours and then filtered with a 1 micron spool filter to obtain a light blue ink having a viscosity of 50 mPa · s.

(Comparative Example 1)
In Example 1, a pink ink having a viscosity of 1950 mPa · s was prepared in the same manner as the ink composition 1 except that 1.0 part of sodium hydroxide was used instead of 2.0 parts of triethanolamine and the amount of water was increased accordingly. Got.

(Comparative Example 2)
In Example 1, a pink color having a viscosity of 1950 mPa · s was obtained in the same manner as in the ink composition 1 except that 0.01 part of potassium hydroquinonesulfonate and 0.03 part of triethanolamine were added, and the amount of water was increased accordingly. An ink was obtained.

(Comparative Example 3)
In Example 4, a light blue ink having a viscosity of 50 mPa · s was obtained in the same manner as the ink composition 4 except that 3.5 parts of triethanolamine was removed and the amount of water was increased accordingly.

The ink compositions of Examples 1 to 3 and Comparative Examples 5 and 6 were combined with parts of a hybrid (KN103, water-based ink ballpoint pen with a ball diameter of 0.3 mm, manufactured by Pentel Co., Ltd.). 4 and the ink composition of Comparative Example 3 were combined with cocktail line parts (CL12, pen tip is a polyester fiber line marker, manufactured by Pentel Co., Ltd.), a writing instrument for evaluation test was assembled, and the pen tip was placed on the centrifuge. The writing instrument for evaluation was obtained by centrifuging for 60 seconds with a centrifugal force of 300 G. Centrifugation with a centrifuge is an operation performed to remove air mixed in when the writing instrument is assembled, bring the pen tip into contact with ink, and allow writing without blurring from the beginning of writing.
Table 1 shows the writing instruments for evaluation tests and the evaluation results of the following tests.
In the table, “after time” indicates a writing instrument in which the above-mentioned writing instrument is left in a thermostatic bath at 25 ° C. and 30% RH for 90 days with the product placed horizontally. Moreover, the viscosity of the ink composition of an Example and a comparative example measured all using the cone rotor (1 degree 34 minutes, R24) with a TVE-20H type viscometer by Toki Sangyo Co., Ltd., and 1.0 rpm ( The shear rate was measured at 3.83 s-1). The measured temperature was 25 ° C.

(Test: Ink useability)
Each of the test ballpoint pens prepared above was subjected to a writing test until no ink was ejected, and the weight of each writing instrument before writing and after writing was measured. The difference is shown in the column of “Ink Use-up” in Table 1. It was. The closer this value is to 0, the better the ink is used up. (Ink wearability (g) = weight of writing instrument before writing−weight of writing instrument after writing) Note that the writing test of the hybrid (ball pen) is a continuous rotation spiral writing tester (MODEL TS-4C-20, Seiki Kogyo Co., Ltd.). The cocktail line (line marker) writing test was performed on a high-quality paper (JIS P3201 writing paper A) with a writing speed of 7 cm / second, a writing angle of 70 °, and a writing load of 100 g. Written continuously under conditions.

  As described above in detail, the present invention is a writing instrument that can use up the ink composition filled in the ink containing tube with the ink composition that does not adhere to the ink containing tube even after being left for a long period of time.

Claims (5)

An ink composition for a writing instrument, comprising at least a colorant, a liquid medium, hydroquinonesulfonic acid and / or a salt thereof, and triethanolamine. The blending amount of the hydroquinone sulfonic acid and / or salt thereof is 0.05% by weight or more and 5.0% by weight or less based on the total amount of the ink composition, and the blending amount of the triethanolamine is based on the total amount of the ink composition. The ink composition for a writing instrument according to claim 1, which is 0.05% by weight or more and 5.0% by weight or less. The ink composition for a writing instrument according to claim 1 or 2, wherein the colorant has a chlorine group and / or a xanthene skeleton. A writing instrument in which the ink composition for a writing instrument according to any one of claims 1 to 3 is directly filled into a transparent or translucent ink storage tube visible from the outside. The transparent or translucent ink containing tube visible from the outside is one or more selected from polyolefin resins, vinyl chloride resins, fluororesins, silicone resins, polyamide resins, polyester resins, and acrylic resins. The writing instrument according to claim 4, comprising: