JP2013014647A - Water-based ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based ink composition which exhibits antifungal effect and is stable even when stored for a long period of time.SOLUTION: The water-based ink composition includes: water; a colorant; and as antiseptic agent and antifungal agent, 400 to 800 ppm of 2-benzisothiazolin-3-one and 600 to 1,300 ppm of 2-pyridinethiol-1-oxide sodium salt.

Description

  The present invention relates to a water-based ink composition. More specifically, the water-based ink composition has an antifungal effect and excellent storage stability.

Conventionally, it is known that water-based ink compositions are prepared by dissolving water-soluble direct dyes, acid dyes and basic dyes in an aqueous medium and adding additives such as wetting agents, pH adjusting agents, and antifungal agents. (See Non-Patent Document 1).
In Example 4 of the water-based ink of Patent Document 1, a black direct dye, C.I. I. A water-based ink using 8% by weight of direct black 19 and 10,000 ppm of 2-pyridinethiol-1-oxide sodium salt as an antifungal agent is disclosed.
In Example 4 of the water-based ink composition for a writing instrument of Patent Document 2, C.I. I. By using 0.8% of Proxel XL-2 containing 8% by weight of direct black 19 and 10% of 1,2-benzisothiazolin-3-one as an antifungal agent, 1,2-benzisothiazoline-3 An ink using 800 ppm of ON is disclosed.
Furthermore, the water-based ink composition for a writing instrument of Patent Document 3 contains 1,2-benzisothiazolin-3-one and 2-pyridinethiol-1-oxide sodium salt as antibacterial substances in a ratio of 1: 0.3 to 1. : 3 in combination, 200 ppm to 900 ppm added, Pesilomyces sp. It is disclosed to obtain antibacterial properties.

"Synthesis of Organic Chemistry" edited by "Dye Handbook" Maruzen Co., Ltd., July 20, 1957 (pages 237 to 239)

Japanese Patent No. 2769838 JP 2007-217592 A JP 2011-046893 A

However, the aqueous dye ink composition using a black direct dye as a colorant has a problem that it causes a writing defect such as blurring in a writing instrument using a batting which is an ink occlusion material. However, if the amount used is reduced, the amount of the orthophenyldiamine group in the dye having an antifungal effect is reduced, so that the antifungal effect cannot be obtained.
Thus, as disclosed in Patent Document 1, when a large amount of 2-pyridinethiol-1-oxide sodium salt is used, an antifungal effect can be obtained, but the color will change over time. Has a point.
Further, as disclosed in Patent Document 2, even if a large amount of 1,2-benzisothiazolin-3-one is used, it will be directly adsorbed to the dye over time, resulting in a weak antifungal effect.
Furthermore, as disclosed in Patent Document 3, the blending ratio and blending amount of 1,2-benzisothiazolin-3-one and 2-pyridinethiol-1-oxide sodium salt are, for example, JIS designated Aspergillus. niger FERM S-1, Aspergillus niger FERM S-2, Aspergillus niger FERM S-3, Eurotium tonophilum FERM S-4, Penicillium citrinum FERM S-5, Penicillium funiculosum FERM S-6, Cladosporium Cladosporioides FERM S-8, Aureobasidium pullulans FERM S-9, Gliocladium virens It is not possible to obtain a sufficient protective effect against FERM S-10, Chaetomium globosum FERM S-11, Fusarium proliferate FERM S-12, Mirothelium verrucaria FERM S-13, and the like.
An object of the present invention is to provide a water-based ink composition having an antifungal effect and excellent in storage stability.

  The present invention provides a water-based ink composition in which water, a colorant, 1,2-benzisothiazolin-3-one is 400 ppm to 800 ppm, and 2-pyridinethiol-1-oxide sodium salt is 600 ppm to 13000 ppm. And

  The water-based ink composition of the present invention can obtain an initial antifungal effect by using 1,2-benzisothiazolin-3-one at 400 ppm to 800 ppm, but it is adsorbed by the black direct dye over time. The defense effect will be weakened. Therefore, by further adding 2-pyridinethiol-1-oxide sodium salt in an amount of 600 ppm to 13000 ppm, it is possible to compensate for the deterioration of the antifungal property due to the passage of time.

Hereinafter, the present invention will be described in detail.
As the colorant used in the present invention, dyes and pigments used in conventional water-based inks can be used. As the dye, any of acid dyes, direct dyes, basic dyes and the like can be used. For example, Japanol Fast Black D Conch (CI Direct Black 17), Water Black 100L (19), Water Black L-200 (19), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black EX (38), Direct Fast Black Conk (51), Kayala Spragley VGN (71), Kayalas Direct Brilliant Yellow G (CI Direct Yellow 4) ), Direct Fast Yellow 5GL (26), Eisen Primula Yellow GCLH (44), Direct Fast Yellow R (50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet G X (4), Direct Fast Scarlet 4BS (23), Eisen Direct Rhodulin BH (31), Direct Scarlet B (37), Kayak Direct Scarlet 3B (39), Eisen Primula Pink 2BLH (75) ), Sumilite Red F3B (80), Eisen Primula Red 4BH (81), Kayara Spral Bin BL (83), Kayara Light Red F5G (225), Kayara Light Red F5B (226), Caillas Light Rose FR (same as 227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (same as 15), Sumilite Splash Blue BRR Conch (same as 71), Dibogen Turquoise Blue S 86), Water Blue # 3 (same as above) 6), direct dyes such as Kayala Star Coyze Blue GL (86), Kayala Supra Blue FF2GL (106), Kayara Supra Turquoise Blue FBL (199), Acid Blue Black 10B (CI Acid Black) 1), Nigrosine (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (26), Suminol Fast Black BR Conk (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conk (52), Sumilan Black WA (52), Ranil Black BG Extra Conk (107), Kyanol Milling Black TLB (109), Suminol Milling Black B (109), Kaya NORMILLING BLACK TLR ( 110), Eisen Opal Black New Conque (119), Water Black 187-L (154), Kayaku Acid Brilliant Flavin FF (C.I. I. Acid Yellow 7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Daiwa Tarrazine (23), Kayaktor Torazin (23) , Suminol Fast Yellow R (25), Diacid Light Yellow 2GP (29), Suminoll Milling O O (38), Suminol Milling MR MR (42), Water Yellow # 6 (42), Kayanol Yellow NFG (49), Suminol Milling Yellow 3G (72), Suminol Fast Yellow G (61), Suminol Milling Yellow G (78), Kayanol Yellow N5G (110), Suminol Milling Yellow 4G 200% (same 141), Kayanor Yellow NG (same 135), Kayano Lumiling Yellow 5 GW (127), Kayanol Milling 6 GW (142), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (9), Solar Rubin Extra (14), Daiwa New Coxin (18), Eisenbonso RH (26), Daiwa Red No. 2 (27), Suminol Leveling Brilliant Red S3B (35), Kayasil Rubinol 3GS (37), Eisen Erythrosin ( 51), kayak acid rhodamine FB (52), Suminol leveling rubinol 3GP (57), diacid alizarin rubinol F3G 200% (82), Eiseneosin GH (87), water pink # 2 (same) 92), Eisen Acid Phloxin PB 92), Rose Bengal (94), Cyanol Milling Scarlet FGW (111), Cyanol Milling Lubin 3BW (129), Sinoall Milling Brilliant Red 3BN Conch (131), Suminol Milling Brilliant Red BS ( 138), Eisen Opal Pink BH (186), Suminoll Milling Brilliant Red B Conch (249), Kayaku Acid Brilliant Red 3BL (254), Kayaku Acid Brilliant Red Brilliant Red BL (265), Kayanol Milling Red GW (276), Mitsui Acid Violet 6BN (CI Acid Violet 15), Mitsui Acid Violet BN (17), Sumitomo Patent Pure Blue VX (CI Acid Blue) 1), Water Blue # 106 (same 1), Patent Blue AF (same 7), Water Blue # 9 (same 9), Daiwa Blue 1 (same 9), Spranol Blue B (same 15), Orient Solve Blue OBC (22), Suminol Leveling Blue 4GL (23), Mitsui Nylon Fast Blue G (25), Kayasil Blue AGG (40), Kayasil Blue BR (41), Mitsui Alizarin Saphirol SE (43) , Suminol Leveling Sky Blue R Extra Conk (62), Mitsui Nylon Fast Sky Blue B (78), Sumitomo Brilliant Indocyanine 6Bh / c (83), Sandlancyanine N-6B 350% (90), Water Blue # 115 (90), Orient Soluble Blue OBB The same 93), Sumitomo brilliant blue 5G (the 103), Kaya Nord milling Ultra Sky SE (the 112), Kaya Nord milling cyanine 5R (the 113), Aizen Opal Blue 2GLH (the 158), Daiwa Guinea green B (C. I. Acid Green 3), Acid Brilliant Milling Green B (same 9), Daiwa Green # 70 (same 16), Cyanol Cyanine Green G (same 25), Suminol Milling Green G (same 27), etc. Ron Yellow 3GLH (CI Basic Yellow 11), Eisen Cachiron Brilliant Yellow 5GLH (13), Sumiacryl Yellow E-3RD (15), Maxilon Yellow 2RL (19), Astrazone Yellow 7GLL (same) 21), Kayacrill Golden Yellow GL-ED (same 28), Astrazone Yellow 5GL (same 51), Eisen Cachiron Orange GLH (CI Basic Orange 21), Eisen Katyron Brown 3GLH (same 30), Rhodamine 6 GCP (C.I. Cred 1), Eisen Astrafloxin (12), Sumiacryl Brilliant Red E-2B (15), Astrazone Red GTL (18), Eisen Cathlon Brilliant Pink BGH (27), Maxilon Red GRL (same) 46), Eisenmethyl Violet (CI Basic Violet 1), Eisen Crystal Violet (Same 3), Eisen Rhodamine B (Same 10), Astrazone Blue G (CI Basic Blue 1), Astrazone Blue BG (Same 3), methylene blue (same 9), maxilon blue GRL (same 41), Eisen Cachiron blue BRLH (same 54), Eisen Diamond Green GH (CI Basic Green 1), Eisen Malachite Green (same 4) ), Bismarck Blau G include basic dye (C.I. Basic Brown 1) and the like.

  As pigments, organic pigments such as azo pigments, nitroso pigments, nitro pigments, basic dye pigments, acidic dye pigments, building dye pigments, mordant dye pigments, and natural dye pigments, ocher, barium Examples thereof include inorganic pigments such as yellow, bitumen, cadmium red, barium sulfate, titanium oxide, petiole, iron black, and carbon black, and these can be used alone or in combination. Specific examples include aniline black (CI 50440), cyanine black, naphthol yellow S (CI 10316), Hansa Yellow 10G (CI 11710), Hansa Yellow 5G (CI 11660), Hansa Yellow. 3G (C.I. 11670), Hansa Yellow G (C.I. 11680), Hansa Yellow GR (C.I. 11730), Hansa Yellow A (C.I. 11735), Hansa Yellow RN (C.I. 11740), Hansa Yellow R (C.I. 12710), Pigment Yellow L (C.I. 12720), Benzidine Yellow (C.I. 21090), Benzidine Yellow G (C.I. 21095), Benzidine Yellow GR (C.I. 21100) ), Permanent Aero NCG (C.I. 20040), Balkan Fastoe -5G (C.I. 21220), Vulcan Fast Yellow R (C.I. 21135), Tartrazine Lake (C.I. 19140), Quinoline Yellow Lake (C.I. 47005), Anslagen Yellow 6GL (C I.60520), permanent yellow FGL, permanent yellow H10G, permanent yellow HR, anthrapyrimidine yellow (CI 68420), Sudan I (CI 12055), permanent orange (CI 12075), resole Fast Orange (C.I. 12125), Permanent Orange GTR (C.I. 12305), Hansa Yellow 3R (C.I. 11725), Vulcan Fast Orange GG (C.I. 21165), Benzidine Orange G (C.I 21110), Persian ole Di (C.I.15510), Indanthrene brilliant orange GK (C.I.59305), Indanthrene brilliant orange RK (C.I.59105), Indanthrene brilliant orange GR (C.I.71105) Permanent Brown FG (C.I. 12480), Para Brown (C.I. 12071), Permanent Red 4R (C.I. 12120), Para Red (C.I. 12070), Fire Red (C.I. 12085) ), Parachlor ortho aniline red (C.I. 12090), resol fast scarlet, brilliant fast scarlet (C.I. 12315), brilliant carmine BS, permanent red F2R (C.I. 12310), permanent red F4R (C I.1 2335), permanent red FRL (C.I. I. 12440), Permanent Red FRLL (C.I. 12460), Permanent Red F4RH (C.I. 12420), Fast Scarlet VD, Vulcan Fast Rubin B (C.I. 12320), Vulcan Fast Pink G (C.I. 12330), Light Fast Red Toner B (C.I. 12450), Light Fast Red Toner R (C.I. 12455), Permanent Carmine FB (C.I. 12490), Pyrazolone Red (C.I. 12120), Resol Red (C.I. 15630), Lake Red C (C.I. 15585), Lake Red D (C.I. 15500), Anthosine B (C.I. 18030), Brilliant Scarlet G (C.I. 15800), Risol rubin GK (C.I.158) 5), Permanent Red F5R (C.I. 15865), Brilliant Carmine 6B (C.I. 15850), Pigment Scarlet 3B (C.I. 16105), Bordeaux 5B (C.I. 12170), Toluidine Maroon (C Perm. Bordeaux F2R (C.I. 12385), Helio Bordeaux BL (C.I. 14830), Bordeaux 10B (C.I. 15880), Bon Maroon Light (C.I. 15825), Bonn Maroon Medium (C.I. 15880), Eosin Lake (C.I. 45380), Rhodamine Lake B (C.I. 45170), Rhodamine Lake Y (C.I. 45160), Alizarin Lake (C.I. 58000) ), Thioindigo red B (C.I. 73300), thioindigo Rune (C.I. 73385), Permanent Red FGR (C.I. 12370), PV Carmine HR, Watching Red, Monolite Fast Red YS (C.I. 59300), Permanent Red BL, Fast Violet B, Methyl Violet Lake (C.I. 42535), Dioxazine Violet, Alkaline Blue Lake (C.I. 42750A, C.I. 42770A), Peacock Blue Lake (C.I. 42090), Peacock Blue Lake (C.I. 42025), Victoria Blue Lake (C.I. 44045), Phthalocyanine Blue (C.I. 74160), Fast Sky Blue (C.I. 74180), Indanthrene Blue RS (C.I. 69800), Indance Ren Blue BC (C.I.6 9825), Indigo (C.I. I. 73000), Pigment Green B (C.I. 10006), Naphthol Green B (C.I. 10020), Green Gold (C.I. 12775), Acid Green Lake, Malachite Green Lake (C.I. 42000), Examples include phthalocyanine green. The amount of these colorants used is preferably 0.5 to 30% by weight based on the total amount of ink.

  When a pigment is used as the colorant, a dispersant may be used to stably disperse the pigment. As the dispersant, those used as pigment dispersants such as water-soluble resins or water-soluble resins or anionic or nonionic surfactants generally used can be used. Examples of the polymer dispersant include natural polymers such as lignin sulfonate and shellac, polyacrylate, salt of styrene-acrylic acid copolymer, salt of vinylnaphthalene-maleic acid copolymer, β-naphthalene Examples thereof include anionic polymers such as sodium salt and phosphate of sulfonic acid formalin condensate, and nonionic polymers such as polyvinyl alcohol and polyethylene glycol. In addition, as surfactants, alkyl sulfates, polyoxyethylene alkyl ether sulfates, N-acyl amino acids and salts thereof, N-acyl methyl taurine salts, polyoxyethylene alkyl ether acetates, alkyl sulfocarboxylates, α- Nonionic surfactants such as olefin sulfonates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl ethers, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters Surfactant is mentioned. These water-soluble resins and surfactants may be used alone or in combination of two or more. The amount used is preferably 0.05 to 20 parts by weight with respect to 10 parts by weight of the pigment.

  In the case of pigments, it is further advantageous in producing pigment inks to use an aqueous ink base dispersed in an aqueous medium. Specifically, FujiSP Black 8031, 8119, 8167, 8276, 8276, 8381, 8406, Fuji SP Red 5096, 5111, 5193, 5220, FujiSP Bordeaux 5500, Fuji SP Blue 6062, 6133, 6134, 6401, Fuji SP Green 7051, Fuji SPYellow 4060, 4178, Fuji SP Violet 9011, Fuji SP Pink 9524, 9527, Fuji SP Orange 534, FUJi SP Brown 35, FUJi SP Brown 35 Dye Co., Ltd.), Emacol Black CN, Emacol Blue FBB, FB, K R, EmacolGreen LXB, Emacol Violet BL, Emacol Brown 3101, Emacol Carmine FB, Emacol Red BS, Emacol Orange R, Ecolol Yellow FD, GN7 GFN, GGN , 10G, Sandy SuperBlack K, C, Sandy Super Gray B, Sandy Super Brown SB, FRL, RR, Sandy Super Green L5G, GXB, Sandy Super G FBL-160, FBB, Sandye Super Violet BL H C, Same BL, Sandy Super Bordeaux FR, Sandy Super Pink FBL, F5B, Sandy Super Rubine FR, Sandy Super Carmine FB, Sandy Super Red FFG, Sandy Super Carbine FB, Sandy Super Red FFF R, 3R, Sandye Ywlow GG, F3R, IRC, FGN, GN, GRS, GSR-130, GSN-130, GSN, 10GN (above, manufactured by Sanyo Dye Co., Ltd.), RioFast BlackFx 8012, 8313, 8169, Rio Fast Red Fx8209, 8172, Rio Fast ed S Fx 8315, 8316, RioFast Blue Fx 8170, Rio Fast Blue FX 8170, Rio Fast Blue SFx 8312, Rio Fast Green SFx 8314, 102, Toyo Ink Co., Ltd. 2104, 2105, 2106, 2107, 2108, 2117, 2127, 2137, 2167, 2101P, 2102P, 2103P, 2104P, 2105P, 2106P, 2106P, 2107P 2108P, 2117P, 2127P, 2127P, 2137P, 2167P, NKW-3002, 3003, 3004, 3005, 3007, 3077, 3008, 3402, 3404, 3405, 3407, 3408, 3477, 3602, 3603, 3604, 3605, 3607, 3777, 3608, 3702, 3703, 3704, 3705, 3777, 3708 6013, 6038, 6559 (manufactured by Nippon Fluorescence Co., Ltd.), Cosmo Color S1000F Series (manufactured by Toyo Soda Co., Ltd.), Victoria Yellow G-11, G-20, Victoria Orange G-16, G-21, Victoria Red G-19, G-22, Victoria Pink G-17, G-23, Victoria Green G-18, G-24, Victoria Blue G-15, G-25 (and above) , Gokoku Dye Co., Ltd.), Pollux PC5T1020, Pollux Black PC8T135, Pollux Red I 1030, etc. Pollux series (or, by Sumika Color Co., Ltd.) in are those like, these are what can be used in combination to select one or more.

  1. Cell wall synthesis function for synthesizing 1,2-benzisothiazolin-3-one that inhibits the respiratory function to acquire energy for growing the cocoon that is the essence of the present invention and peptide glucan constituting the cell wall of cocoon from glucoseamine and the like 2-pyridinethiol 1-oxide sodium salt, which is regularly adsorbed to black direct dyes and inhibits synthetic functions such as protein synthesis function to synthesize enzyme proteins, cell constituent proteins and peptides, is an antifungal agent It is what is used. These substances can exhibit sufficient antifungal properties when used in combination with a black aqueous dye ink composition. Specific examples of 1,2-benzoisothiazolin-3-one include Proxel GXL (S) (manufactured by Arch Chemicals Japan), Suneye Back FX (manufactured by Sanai Oil Co., Ltd.), Topside 600 (( Permachem Asia Co., Ltd.). As a specific example of 2-pyridinethiol-1-oxide / sodium salt, sun eyebac sodium omazine (manufactured by Sanai Oil Co., Ltd.) and the like can be mentioned. Alternatively, Sun Eyebac P-100 (manufactured by Sanai Petroleum Co., Ltd.) using 1.2-benzoisothiazolin-3-one and 2-pyridinethiol 1-oxide sodium salt together can be used. The amount used is 1,2-benzisothiazolin-3-one from 350 ppm to 850 ppm based on the total amount of the black aqueous dye ink composition, considering the antifungal effect and the viscosity increase of the black dye ink composition due to the amount used. Preferably, it is 400 ppm to 800 ppm. Furthermore, since 2-pyridinethiol 1-oxide sodium salt will discolor a black direct dye with progress of time if it adds much, it is 560 ppm-1310 ppm, More preferably, it is 600 ppm-1300 ppm.

  A conventionally known water-soluble organic solvent can be used as an ink solvent responsible for various qualities of the ink, such as anti-freezing of the ink at low temperatures, a dye solubilizer, and a pigment dispersion medium. Specific examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, hexylene glycol, 1,3-butylene glycol, thiodiethylene glycol, glycerin, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, Glycol ethers such as diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone Etc. These water-soluble organic solvents can be used alone or in combination.

  Various resins can be used in combination for fixing the colorant on the paper surface. For example, shellac, styrene-maleic acid copolymer and salt thereof, styrene-acrylic acid copolymer and salt thereof, Α-methylstyrene-acrylic acid copolymer and salt thereof, acrylic resin, maleic acid resin, urea resin, Polyvinyl butyral, polyvinyl alcohol, polyethylene oxide, polyvinyl acetal, polyamide resin, epoxy resin, polyvinyl alkyl ether, coumarone-indene resin, rosin resin and its hydrogenated product, ketone resin, polyacrylic acid polymethacrylic acid copolymer, etc. Can be mentioned.

  In order to adjust the pH of the ink, a basic substance such as sodium hydroxide, lithium hydroxide, triethanolamine, monoethanolamine or aminomethylpropanediol, or an acidic substance such as sulfuric acid may be added.

  In addition to the components listed above, various additives such as pen tip drying inhibitors, antifoaming agents, plasticizers, various activators, and organic solvents that do not interfere with the solubility of the resin are selected appropriately. Can be used.

  The production method of the black aqueous dye ink composition of the present invention comprises mixing the necessary amounts of the above components and mixing and dispersing them with a stirrer such as a high speed stirrer such as a propeller stirrer, homomixer, or lab mixer. Can be easily obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited only to an Example.

Example 1
WATER BLACK L-200 (Aqueous solution containing 20% purified CI Direct Black 19 manufactured by Orient Chemical Co., Ltd.) 40.0 parts Daiwa Red No. 103 WB (CI Acid Red 87, manufactured by Daiwa Kasei Co., Ltd.) 0.1 part Suneye Back P-100 (1.2-benzoisothiazolin-3-one and 2-pyridinethiol 1-oxide sodium salt Antifungal agent contained at a ratio of 1: 1.7, active ingredient 19%, manufactured by Sanai Oil Co., Ltd.) 1.05 parts ethylene glycol 5.0 parts thiodiglycol 8.0 parts ethylene urea 10.0 parts Neugen P (Polyoxyethylene alkyl ether aqueous solution, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 0.2 part water 35.65 parts The above components were stirred with a homomixer for 1 hour to obtain a black aqueous dye ink composition.

(Example 2)
Daiwa Blue No. 1WB (CI Acid Blue 9, manufactured by Daiwa Kasei Co., Ltd.) 3.5 parts Daiwa Red No. 106WB (CI Acid Red 52, manufactured by Daiwa Kasei Co., Ltd.) 0.8 parts Proxel GXL (S) (1.2-benzoisothiazolin-3-one-containing antiseptic agent, active ingredient 20%, Arch・ Chemical Japan Co., Ltd.) 0.2 part sun eye buck sodium omadin (an antifungal agent containing 2-pyridinethiol 1-oxide sodium salt, active ingredient 40%, manufactured by Sanai Oil Co., Ltd.) 0 .2 parts ethylene glycol 9.0 parts diethylene glycol 8.0 parts propylene glycol 10.0 parts Neugen P (previously described) 0.2 parts water 68.1 parts The above ingredients are stirred in a homomixer for 1 hour to give a blue aqueous dye. An ink composition was obtained.

(Example 3)
Daiwa Red No. 103WB (CI Acid Red 87, manufactured by Daiwa Kasei Co., Ltd.)
3.5 parts WATER YELLOW # 6 (CI Acid Yellow 42, manufactured by Orient Chemical Co., Ltd. 3.5 parts Proxel GXL (S) (previously described) 0.4 part Sun Iback sodium omadin (previously described) 0 .15 parts ethylene glycol 10.0 parts glycerin 10.0 parts Neugen P (previously described) 0.2 parts water 72.25 parts The above ingredients were stirred with a homomixer for 1 hour to obtain a red aqueous dye ink composition. .

Example 4
FUJI SP BLACK 8922 (Aqueous pigment dispersion in which carbon black is dispersed, manufactured by Fuji Dye Co., Ltd.) 20.0 parts Proxel GXL (S) (described above) 0.4 parts Sun Iback Sodium Omagine (described above) 0.325 Parts ethylene glycol 15.0 parts glycerin 15.0 parts Jonkrill 734 (styrene acrylic copolymer, manufactured by BASF Japan Ltd. 1.0 parts water 48.275 parts The above ingredients were stirred in a homomixer for 1 hour, A black aqueous pigment ink composition was obtained.

(Example 5)
WATER BLACK 187-LM (an aqueous solution containing 15% purified CI Direct Black 154, manufactured by Orient Chemical Co., Ltd.) 60.0 parts Proxel GXL (S) (previously described) 0.2 parts Sun Iback Sodium Oma Gin (previously described) 0.325 parts ethylene glycol 7.0 parts diethylene glycol 7.0 parts propylene glycol 10.0 parts Neugen P (previously described) 0.2 parts water 15.275 parts The above ingredients are stirred in a homomixer for 1 hour. Thus, a black aqueous dye ink composition was obtained.

(Example 6)
FUJI SP BLUE 6401 (aqueous pigment dispersion in which phthalocyanine blue is dispersed, manufactured by Fuji Dye Co., Ltd.) 26.0 parts Jonkrill 734 (previously described) 1.0 part Suneye Back P-100 (previously described) 0.5 part Proxel GXL (S) (described above) 0.2 parts ethylene glycol 10.0 parts glycerin 10.0 parts water 52.3 parts The above components were stirred for 1 hour with a homomixer to obtain a blue aqueous pigment ink composition.

(Example 7)
WATER BLACK 191-L (Aqueous solution containing 15% purified CI Direct Black 19 manufactured by Orient Chemical Co., Ltd.) 50.0 parts Edible Yellow 4 (CI Food Yellow 4, Daiwa Kasei) 0.2 parts Proxel GXL (S) (previously described) 0.25 parts sun eye buck sodium azine (previously described) 0.25 parts ethylene glycol 8.0 parts diethylene glycol 8.0 parts propylene glycol 8. 0 parts Neugen P (described above) 0.2 parts water 25.1 parts The above components were stirred for 1 hour with a homomixer to obtain a black aqueous dye ink composition.

(Example 8)
Lumicol NKW-3902E (Aqueous fluorescent pigment dispersion obtained by mixing and dispersing CI Basic Yellow 40, CI Basic Blue 3 and styrene / acrylonitrile copolymer,
40.0 parts Suneye Back P-100 (previously described) 0.6 parts propylene glycol 5.0 parts glycerin 20.0 parts Neugen P (previously described) 0.2 parts water 34.2 parts above The components were stirred with a homomixer for 1 hour to obtain a green aqueous pigment ink composition.

Example 9
FUJI SP RED 5657 (Aqueous pigment dispersion in which CI Pigment Red 170 is dispersed, manufactured by Fuji Dye Co., Ltd.) 25.0 parts Proxel GXL (S) (described above) 0.4 parts Sun Iback Sodium Omagine ( 0.15 parts Jonkrill 734 (previously described) 1.0 part ethylene glycol 12.0 parts glycerin 13.0 parts water 48.45 parts The above ingredients are stirred in a homomixer for 1 hour to obtain a red aqueous pigment ink composition. I got a thing.

(Comparative Example 1)
Black aqueous dye as in Example 1, except that 1.05 part of sun eye bag P-100 (described above) of Example 1 was changed to 0.3 part and 35.65 parts of water was changed to 36.4 parts. An ink composition was obtained.

(Comparative Example 2)
Example 2 Blue Aqueous Dye Ink in the same manner as in Example 2 except that 0.2 part of Suneye Back P-100 (described above) was changed to 0.35 part and 59.1 parts of water was changed to 58.9 parts. A composition was obtained.

(Comparative Example 3)
Black aqueous dye as in Example 3, except that 0.55 part of sun eye bag P-100 (described above) of Example 3 was changed to 1.1 part and 66.55 parts of water was changed to 66.0 parts. An ink composition was obtained.

  A fungus resistance test and a color tone change test were performed using the inks prepared in Examples 1 to 9 and Comparative Examples 1 to 3. The results are shown in Table 1.

Mold resistance test 1 (initial)
The black aqueous dye ink compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 6 were subjected to mold resistance according to the method described in Japanese Industrial Standard (JIS Z 2911 Mold Resistance Test Method). A test was conducted and a product with an evaluation of “good” was regarded as a good product.
Evaluation criteria ○: With a blocking circle Δ: With a slight blocking circle ×: Without a blocking circle Wrinkles occur in the black aqueous dye ink composition.

Mold resistance test 2 (Aged)
The black aqueous dye ink compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 6 were put in a glass bottle with a capacity of 50 ml, covered, and left in a thermostatic bath at 50 ° C. and 30% for 3 months. In accordance with the method described in Japanese Industrial Standards (JIS Z 2911 Mold Resistance Test Method), a mold resistance test was conducted, and a product with an evaluation of “good” was regarded as a good product. In addition, 12 types of JIS-designated spider spores described below were collected and used as a suspension aqueous solution mixed and dispersed in a 1% octylphenol poly (ethylene glycol ether) aqueous solution.
JIS-designated ｅｒ Aspergillus niger FERM S-1, Aspergillus niger FERM S-2, Aspergillus niger FERM S-4, Eurotomium citrum FERM S-4, Penicillium cigar FERM S-4 FERM S-8, Aureobasidium pullulans FERM S-9, Gliocladium virens FERM S-10, Chaetomium globosum FERM S-11, Fusarium proliferate FERMroS-12, FERMro S-12 m verrucaria FERM S-13
Evaluation criteria ○: There is a prevention circle,
Δ: There is a slight inhibition circle ×: There is no inhibition circle. Wrinkles occur in the black aqueous dye ink composition.

Tonal change (ΔE)
The black aqueous dye ink compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 6 were initially placed in a glass bottle with a capacity of 50 ml, covered, and placed in a thermostatic bath at 50 ° C. and 30% for 3 months. After leaving, ink is uniformly applied to writing paper (basis weight 50-100g / _m ² , whiteness 75% or more) once in the vertical and horizontal directions with an acrylic ink absorber, dried, and then the spectrophotometer NF777 (Nippon Denki) Color difference (ΔE) at the initial stage and after being left standing was measured by Color Kogyo Co., Ltd. When the value of ΔE is 1.5 or less, no color difference is visually recognized. However, when the value is more than that, a color difference is visually recognized.

  Filling the writing instruments (SF-15, manufactured by Pentel Co., Ltd.) using the polyurethane nib and acrylic fiber ink absorber with the inks prepared in Examples 1 to 9 and Comparative Examples 1 to 6. A written test was conducted.

In Examples 1 to 9, in a black aqueous dye ink composition comprising water, a black direct dye, and an antifungal agent, 1,2-benzoisothiazolin-3-one as an antifungal agent is 400 ppm to 800 ppm, and 2 -By making pyridinethiol-1-oxide sodium salt into 600 ppm to 1,300 ppm, an antifungal effect can be obtained, and color change with time is also eliminated.
In Comparative Example 1, the effect of the antifungal agent cannot be obtained because the amount of the antifungal agent is small.
In Comparative Example 2, although the antifungal effect is obtained, since the amount of 2-pyridinethiol-1-oxide sodium salt used is large, the color tends to change over time.
Comparative Example 3
Even if the amount of 1,2-benzisothiazolin-3-one is increased, the amount of 2-pyridinethiol-1-oxide sodium salt is small, so that the antifungal effect over time cannot be obtained.

Claims (1)

A water-based ink composition comprising 400 ppm to 800 ppm of water, a colorant, 1,2-benzisothiazolin-3-one, and 600 ppm to 13000 ppm of 2-pyridinethiol-1-oxide sodium salt.