Water-based pigment ink composition for writing instruments

Abstract

To provide a water-based pigment ink composition for writing instruments that can form good writing marks even after let stand in a subzero temperature environment at about -5°C for 3 months or longer.SOLUTION: A water-based pigment ink composition for writing instruments has a pigment, an amino acid anionic surfactant composed of an unsaturated fatty acid, an amino acid anionic surfactant composed of a saturated fatty acid, and water.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an aqueous pigment ink composition for writing instruments, which uses a pigment as a coloring component to obtain a concealing effect for a base, a lustrous effect for applied marks, and water resistance for applied marks, as a coating liquid to be built into an applicator and used. [Background technology]

[0002] Conventionally, aqueous pigment ink compositions for writing instruments have used pigments as coloring components to provide a concealing effect for the base, a shining effect for application marks, and water resistance for application marks. However, because pigments have a higher specific gravity than dyes and are dispersed and mixed rather than dissolved, the pigments gradually aggregate and settle over time as they are left to stand, forming a so-called hard cake that separates from the liquid, making it difficult to dispense from the application point of the writing instrument. In ink compositions using such pigments, known means for delaying pigment aggregation and sedimentation include surface modification of the pigment with various surfactants and reducing the fluidity of the liquid by using thickeners or gelling agents. For example, the invention described in Patent Document 1 discloses an aqueous ink composition for writing instruments that uses water-soluble resins such as acrylic resins, vinyl resins, and various resin emulsions, water-soluble polysaccharides such as cellulose derivatives, and inorganic thickeners such as montmorillonite-based clay minerals to produce an ink with a specific viscosity for a specific shear rate, thereby achieving good redispersibility even when left to stand at 40°C for two weeks. Patent Document 2 discloses an aqueous pigment ink composition for use in ballpoint pens that uses a combination of multiple specific water-soluble polysaccharides to maintain the ink dispersion system stable and produce good handwriting even after storage for about two months at room temperature as well as at a low temperature of around 0°C or a high temperature of around 60°C. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2011-202086 A [Patent Document 2] JP 2006-45429 A Summary of the Invention [Problem to be solved by the invention]

[0004] The invention described in the above-mentioned patent document had a problem in that the pen could not be written properly when left in a negative temperature environment of less than -5°C for an extremely long period of time of more than three months.

[0005] An object of the present invention is to provide an aqueous pigment ink composition for a writing instrument which is capable of forming a good applied mark even when left to stand in a minus temperature environment of about -5°C for three months or more. [Means for solving the problem]

[0006] A first gist of the present invention is an aqueous pigment ink composition for a writing instrument, which comprises at least a pigment, an amino acid anionic surfactant composed of an unsaturated fatty acid, an amino acid anionic surfactant composed of a saturated fatty acid, and water. A second gist of the present invention is an aqueous pigment ink composition for a writing instrument, which further comprises a resin emulsion and a plate-like inorganic compound. Effect of the Invention

[0007] According to an embodiment of the present invention, it is possible to provide an aqueous pigment ink composition for writing instruments that can be filled into writing instruments such as marking pens, brush pens, ballpoint pens, and correction fluid applicators, and that can be used for writing with the composition even when stored for a long period of time in a negative environment and then used in a similar low-temperature environment.

[0008] That is, it is presumed that the aqueous pigment ink composition for writing implements of the present invention is such that the amino acid anionic surfactant made of unsaturated fatty acid and the amino acid anionic surfactant made of saturated fatty acid are bonded to the surface of the pigment, and the pigment surface is covered with the amino acid anionic surfactant made of unsaturated fatty acid and the amino acid anionic surfactant made of saturated fatty acid to form a composite, and the interaction between the pigments is three-dimensionally gentle, so that the fluidity of the entire composition is not impaired even in a low-temperature environment. Also, when a resin emulsion or plate-like inorganic particles is added to this, a gentle gel structure that envelops the pigment is formed by the gelling action of the plate-like inorganic particles such as bentonite, in addition to the thickening effect of the solid matter blended, and in particular, a large gel structure composite is formed by the interaction between the amino acid anionic surfactant made of unsaturated fatty acid and the amino acid anionic surfactant made of saturated fatty acid and the gel structure formed by the plate-like inorganic particles, and it is presumed that this also suppresses the situation in which large plate-like pigments such as glittering plate-like aluminum or aluminum flakes are aligned and aggregated as pigment particles. [Brief description of the drawings]

[0009] [Figure 1] FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The pigment used in the aqueous pigment ink composition for writing implements of the present invention is used as a coloring component to obtain the concealing effect of the base, the brilliance effect of the coating mark, the water resistance of the coating mark, etc. Pigments that can be used are not particularly limited, and include organic pigments such as azo pigments, nitroso pigments, nitro pigments, basic dye pigments, acid dye pigments, vat dye pigments, mordant dye pigments, and natural dye pigments used in conventional aqueous inks and oil-based inks, inorganic pigments such as yellow ocher, barium yellow, Prussian blue, cadmium red, barium sulfate, titanium oxide, red iron oxide, iron black, and carbon black, and glitter pigments such as metal powders such as aluminum powder and bronze powder, metal-coated glass flakes, and metal-deposited films, and aqueous pigment bases in which pigments are dispersed in aqueous media. In particular, glitter pigments are used to form beautiful handwriting with a glittering feel.

[0011] Luminous pigments include 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, LG neo RED #100, LG neo BLUE #100, LG neo GREEN #100, LG neo VIOLET #100, LG neo BLACK #100, LG neo COPPER #100, LG neo PINK #100, LG neo YELLOW #100, LG neo R-GOLD #150, LG neo B-GOLD #150, LG neo S-GOLD #150, LG neo RED #150, LG neo BLUE #150, LG neo GREEN #150, LZ neo VIOLET #150, LZ neo BLACK #150, LZ neo COPPER #150, LZ neo PINK #150, LZ neo YELLOW #150, LZ neo R-GOLD #200, LZ neo B-GOLD #200, LZ neo S-GOLD #200, LZ neo RED #200, LZ neo BLUE #200, LZ neo GREEN #200, LZ neo VIOLET #200, LZ neo BLACK #200, LZ neo COPPER #200, LZ neo PINK #200, LZ neo YELLOW #200, LZ neo R-GOLD #325, LZ neo B-GOLD #325, LZ neo S-GOLD #325, LZ neo RED #325, LZ neo BLUE #325, LZ neo GREEN #325, LZ neo VIOLET #325, LZ neo BLACK #325, LZ neo COPPER #325, LZ neo PINK #325, LZ neo YELLOW #325, LZ neo SILVER #325, LZ neo R-GOLD #500, LZ neo B-GOLD #500, LZ neo S-GOLD#500 (all 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 Piece Blue 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 PiecePink CO-40UC, Diamond Peace Lavender CO-40UC (all manufactured by Diamond Industries Co., Ltd.), Super Fine No. 22000, No. 22000WN, No. 1800WN, No. 18000, Fine No. 900, No. 800 (all manufactured by Yamato Metal Powder Co., Ltd.), AA12, AA8, No. 900, No. 1800, PaleGold E5, 2L5, RichGold L7, 3L7, ECopper (all manufactured by Fukuda Metal Foil & Powder Co., Ltd.), Aluminum Powder 1000, 2700 (all manufactured by Nakatsuka Metal Foil & Powder Co., Ltd.), WB0230, WXM0630, Friend Color D452BL, Friend Color D462BL, Friend Color D851BL, Friend Color D451RE, Friend Color D462RE, Friend Color D111RE, Friend Color D452YE, Friend Color D462YE, Friend Color D85 1YE (all manufactured by Toyo Aluminium K.K.), stainless steel powder pigment, tin powder pigment, zinc powder pigment, nickel powder pigment, gold powder pigment, silver powder pigment, Metashine MT1030GP, Metashine MT2080GP, Metashine 2025PS, Metashine 1030PS, Metashine 2080PS, Metashine 5090PS, Metashine 5150PS, Metashine 5230PS, Metashine 5480PS (all manufactured by Nippon Sheet Glass Co., Ltd.). When using a glittering pigment, the average particle size is preferably 10 μm or more in order to form beautiful handwriting with a glittering feel, and an average particle size of 30 μm or more is particularly preferable because it provides an even stronger glittering feel.

[0012] Inorganic pigments include aniline black (CI50440), cyanine black, naphthol yellow S (CI10316), Hansa Yellow 10G (CI11710), Hansa Yellow 5G (CI11660), Hansa Yellow 3G (CI11670), Hansa Yellow G (CI11680), Hansa Yellow GR (CI11730), Hansa Yellow A (CI11735), Hansa Yellow RN (CI1740), Hansa Yellow R (CI12710), Pigment Yellow L (C. I.12720), Benzidine Yellow (CI21090), Benzidine Yellow G (CI21095), Benzidine Yellow GR (CI21100), Permanent Yellow NCG (CI20040), Balkan Fast Yellow 5G (CI21220), Balkan Fast Yellow R (CI21135), Tartrazine Lake (CI19140), Quinoline Yellow Lake (CI47005), Anthragen Yellow 6GL (CI60520), Permanent Yellow FGL, Permanent Yellow H10G , Permanent Yellow HR, Anthrapyrimidine Yellow (CI 68420), Sudan I (CI 12055), Permanent Orange (CI 12075), Lithol Fast Orange (CI 12125), Permanent Orange GTR (CI 12305), Hansa Yellow 3R (CI 11725), Balkan Fast Orange GG (CI 21165), Benzidine Orange G (CI 21110), Persian Orange (CI 15510), Indanthrene Brilliant Orange GK (CI 59305), In Danthren Brilliant Orange RK (CI59105), Indanthren Brilliant Orange GR (CI71105), Permanent Brown FG (CI12480), Para Brown (CI12071), Permanent Red 4R (CI12120), Para Red (CI12070), Fire Red (CI12085), Parachlor Orthoaniline Red (CI12090), Lithol Fast Scarlet, Brilliant Fast Scarlet (CI12315), Brilliant Carmine BS, Permanent Permanent Red F2R (CI12310), Permanent Red F4R (CI12335), Permanent Red FRL (CI12440), Permanent Red FRLL (CI12460), Permanent Red F4RH (CI12420), Fast Scarlet VD, Balkan Fast Rubin B (CI12320), Balkan Fast Pink G (CI12330), Light Fast Red Toner B (CI12450), Light Fast Red Toner R (CI12455), Permanent Carmine FB (CI12490), Pyrazolone Red (CI12120), Lysol Red (CI15630), Lake Red C (CI15585), Lake Red D (CI15500), Anthocine B (CI18030), Brilliant Scarlet G (CI15800), Lysol Rubin GK (CI15825), Permanent Red F5R (CI15865), Brilliant Carmine 6B (CI15850), Pigment Scarlet 3B (CI16105), Bordeaux 5B (CI12170), Luigi Maroon (CI12350), Permanent Bordeaux F2R (CI12385), Helio Bordeaux BL (CI14830), Bordeaux 10B (CI15880), Bon Maroon Light (CI15825), Bon Maroon Medium (CI15880), Eosin Lake (CI45380), Rhodamine Lake B (CI45170), Rhodamine Lake Y (CI45160), Alizarin Lake (CI58000), Thioindigo Red B (CI73300), Thioindigo Maroo (CI 73385), Permanent Red FGR (CI 12370), PV Carmine HR, Watching Red, Monolight Fast Red YS (CI 59300), Permanent Red BL, Fast Violet B, Methyl Violet Lake (CI 42535), Dioxazine Violet, Alkaline Blue Lake (CI 42750A, CI 42770A), Peacock Blue Lake (CI 42090), Peacock Blue Lake (CI 42025), Victoria Blue Lake ( CI44045), Phthalocyanine Blue (CI74160), Fast Sky Blue (CI74180), Indanthrene Blue RS (CI69800), Indanthrene Blue BC (CI69825), Indigo (CI73000), Pigment Green B (CI10006), Naphthol Green B (CI10020), Green Gold (CI12775), Acid Green Lake, Malachite Green Lake (CI42000), Phthalocyanine Green, etc.

[0013] As water-based pigments, there are Fuji SP Black 8031, Fuji SP Black 8119, Fuji SP Black 8167, Fuji SP Black 8276, Fuji SP Black 8381, Fuji SP Black 8406, Fuji SP Red 5096, Fuji SP Red 5111, Fuji SP Red 5193, Fuji SP Red 5220, Fuji SP Bordeaux 5500, 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 Yellow 4178, Fuji SP Violet 9011, Fuji SP Pink 9524, Fuji SP Pink 9527, Fuji SP Orange 534, Fuji SP Brown 3074, Fuji SP RED 5543, FUJI SP RED 5544 (all of the above are manufactured by Fuji Pigment Co., Ltd.), Emacol Black CN, Emacol Blue FBB, Emacol Blue FB, Emacol Blue KR, Emacol Green LXB, Emacol Violet BL, Emacol Brown 3101, Emacol Carmine FB, Emacol Red BS, Emacol Orange R, Emacol Yellow FD, Emacol Yellow IRN, Emacol Yellow 3601, Emacol Yellow FGN, Emacol Yellow GN, Emacol Yellow GG, Emacol 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, Sandye Super Green L5G, Sandye Super GreenGXB, Sandye Super Navy Blue HRL, Sandye Super Navy Blue GLL, Sandye Super Navy Blue HB, Sandye Super Navy Blue FBLH, Sandye Super Navy Blue FBL-160, Sandye Super Navy Blue FBB, Sandye Super Violet BL H / C, Sandye Super Violet BL, Sandye Super Bordeaux FR, Sandye Super Pink FBL, Sandye Super Pink F5B, Sandye Super Rubine FR, Sandye super Carmine FB, Sandye Super Red FFG, Sandye Super Red RR, Sandye Super Red BS, Sandye Super Orange FL, Sandye Super Orange R, Sandye Super Orange BO, Sandye Gold Yellow 5GR, Sandye Gold Yellow R, Sandye Gold Yellow 3R, Sandye Yellow GG, Sandye Yellow F3R, Sandye Yellow IRC, Sandye Yellow FGN, Sandye Yellow GN, Sandye Yellow GRS, Sandye Yellow GSR-130, Sandye Yellow GSN-130, Sandye Yellow GSN, Sandye Yellow 10GN (all of the above are manufactured by Sanyo Shikiso Co., Ltd.), Rio Fast Black Fx 8012, Rio Fast Black Fx 8313, Rio Fast Black Fx 8169, Rio Fast Red Fx 8209, Rio Fast Red Fx 8172, Rio Fast Red S Fx 8315, 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 Fx8314 (all manufactured by Toyo Ink Co., Ltd.), NKW-2101, NKW-2102, NKW-2103, NKW-2104, NKW-2105, NKW-2106, NKW-2107, NKW-2108, NKW-2117, NKW-2127, NKW-2137, NKW-2167, NKW-2101P, NK W-2102P, NKW-2103P, NKW-2104P, NKW-2105P, NKW-2106P, NKW-2107P, NKW-2108P, NK W-2117P, NKW-2127P, NKW-2137P, NKW-2167P, NKW-3002, NKW-3003, NKW-3004, NKW-3 005, 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-3677, NKW-3608, NKW-3702, NKW-3703, NKW-3704, NKW-3705, NKW-3777, NKW-3708, NKW-6013, NKW-6038, NKW-6559 (all manufactured by Nippon Fluorescent), Cosmo Color S1000F Series (manufactured by Toyo Soda), Victoria Yellow Examples include 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, and G-25 (all manufactured by Mikuni Color Co., Ltd.), as well as the Pollux series such as Pollux PC5T1020, Pollux Black PC8T135, and Pollux Red IT1030 (all manufactured by Sumika Color Co., Ltd.).

[0014] These pigments may be used alone or in combination of two or more kinds. The pigment content is preferably 0.5% by weight or more and 20.0% by weight or less based on the total weight of the aqueous pigment ink composition, and more preferably 1.0% by weight or more and 10.0% by weight or less. Within the above numerical range, the ink can be discharged stably without clogging the pen tip or brush tip with the pigment while maintaining the fluidity at low temperatures.

[0015] As the colorant, a dye can be used in combination with the above pigments. As the dye, direct dyes, acid dyes, basic dyes, etc., which are used in conventional water-based inks and oil-based inks, can be used. Specifically, Japanol Fast Black D Concentrate (CI Direct Black 17), Water Black 100L (CI Direct Black 19), Water Black L-200 (CI Direct Black 19), Water Black 256L, 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 Concentrate (CI Direct Black 51), Kayalas Spragray VGN (CI Direct Black 71), Kayalas Direct Brilliant Yellow G (CI Direct Yellow 4), Direct Fast Yellow 5GL (CI Direct Yellow 26), Aizen Primula Yellow GCLH (CI Direct Yellow 44), Direct Fast Yellow R (CI Direct Yellow 50), Aizen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX (CI Direct Red 4), Direct Fast S Carlet 4BS (CI Direct Red 23), Aizen Direct Rhoduline BH (CI Direct Red 31), Direct Scarlet B (CI Direct Red 37), Kayak Direct Scarlet 3B (CI Direct Red 39), Aizen Primula Pink 2 BLH (CI Direct Red 75), Sumi Light Red F3B (CI Direct Red 80), Aizen Primula Red 4BH (CI Direct Red 81), Kayalas Spralubin BL (CI Direct Red 83), Kayalas Light Red Do F5G (CI Direct Red 225), Kayalas Light Red F5B (CI Direct Red 226), Kayalas Light Rose FR (CI Direct Red 227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (CI Direct Blue 15), Sumilight Sprat Blue BRR Conc (CI Direct Blue 71), Daibogen Turquoise Blue S (CI Direct Blue 86), Water Blue 3 (CI Direct Blue 86), Kayalas Turquoise Blue GL (CIDirect Blue 86), Kayalas Splat Blue FF2GL (CI Direct Blue 106), Kayalas Splat 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 ​​Conc (CI Acid Black 31), Mitsuina Ilon Black GL (CI Acid Black 52), Aizen Opal Black WH Extra Conc (CI Acid Black 52), Sumilan Black WA (CI Acid Black 52), Ranil Black BG Extra Conc (CI Acid Black 107), Kayanol Milling Black TLB (CI Acid Black 109), Sumilan Milling Black B (CI Acid Black 109), Kayanol Milling Black TLR (CI Acid Black 110), Aizen Opal Black New Conc (CI Acid Black 119), Water Black 187-L (CI Acid Black 154), Kayaku Acid Brilliant Flavin FF (CI Acid Yellow 7:1), Kayasil Yellow GG (CI Acid Yellow 17), Xylene Light Yellow 2G 140% (CI Acid Yellow 17), Suminol Leveling Yellow NR (CI Acid Yellow 19), Daiwa Tatrazine (CI Acid Yellow 23), Kayaku Tatrazine (CI Acid Yellow 23), Suminol Fast Yellow -R (CI Acid Yellow 25), Diacid Light Yellow 2GP (CI Acid Yellow 29), Suminol Milling Yellow (CI Acid Yellow 38), Water Yellow 6 (CI Acid Yellow 42), Water Yellow 6C (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 (CIAcid Yellow 78), Kayanol Yellow N5G (CI Acid Yellow 110), Suminol Milling Yellow 4G 200% (CI Acid Yellow 141), Kayanol Yellow NG (CI Acid Yellow 135), Kayanol Milling Yellow 5GW (CI Acid Yellow 127), Kayanol Milling Yellow 6GW (CI Acid Yellow 142), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayaku Silk Scarlet (CI Acid Red 9), Solar Rubin Ex Stra (CI Acid Red 14), Daiwa New Kokushin (CI Acid Red 18), Water Red 1 (CI Acid Red 18), Aizen Bonso 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), Aizen Erythrosine (CI Acid Red 51), Daiwa Red No. 106WB (CI Acid Red 52), Suminol Leveling Rubinol 3GP (CI Acid Red 57), Diacid Alizarin Rubinol F3G 200% (CI Acid Red 82), Aizen Eosin GH (CI Acid Red 87), Daiwa Red No. 104WB (CI Acid Red 92), Aizen Acid Phloxine PB (CI Acid Red 92), Rose Bengal (CI Acid Red 94), Kayanol Milling Scarlet FGW (CI Acid Red 111), Kayanol Milling Rubin 3BW (CI Acid Red 129) , Suminol Milling Brilliant Red 3BN Concentrate (CI Acid Red 131), Suminol Milling Brilliant Red BS (CI Acid Red 138), Aizen Opal Pink BH (CI Acid Red 186), Suminol Milling Brilliant Red B Concentrate (CI Acid Red 249), Kayaku Acid Brilliant Red 3BL (CI Acid Red 254), Kayaku Acid Brilliant Red BL (CI Acid Red 265), Kayanol Milling Red GW (CIAcid Red 276), Mitsui Acid Violet 6BN (CI Acid Violet 15), Mitsui Acid Violet BN (CI Acid Violet 17), Sumitomo Patent Pure Blue VX (CI Acid Blue 1), Water Blue 106 (CI Acid Blue 1), Water Blue 119, Patent Blue AF (CI Acid Blue 7), Water Blue 9 (CI 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 (CI Acid Blue 23), Mitsui Nylon Fast Blue G (CI Acid Blue 25), Kayasil Blue AGG (CI Acid Blue 40), Kayasil Blue BR (CI Acid Blue 41), Mitsui Alizarin Sapphirol SE (CI Acid Blue 43), Suminol Leveling Sky Blue R Extra Conc (CI Acid Blue 62), Mitsui Nylon Fast Sky Blue B (CI Acid Blue 78), Sumitomo Brilliant Indocyanine 6Bh / c (CI Acid Blue 83), Sandran Cyanine 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 (CI Acid Blue 103), Kayanol Milling Ultra Sky SE (CI Acid Blue 112), Kayanol Milling Cyanine 5R (CI Acid Blue 113), Aizen Acid dyes such as Opal Blue 2GLH (CI Acid Blue 158), Daiwa Guinea Green B (CI Acid Green 3), Acid Brilliant Milling Green B (CI Acid Green 9), Daiwa Green 70 (CI Acid Green 16), Kayanol Cyanine Green G (CI Acid Green 25), Suminol Milling Green G (CI Acid Green 27), Eisen Katilon Yellow 3GLH (CI Basic Yellow 11), Eisen Katilon Brilliant Yellow 5GLH (CIBasic Yellow 13), Sumiacrylic Yellow E-3RD (CI Basic Yellow 15), Maxillon Yellow 2RL (CI Basic Yellow 19), Astrazon Yellow 7GLL (CI Basic Yellow 21), Kayakryl Golden Yellow GL-ED (CI Basic Yellow 28), Astrazon Yellow 5GL (CI Basic Yellow 51), Eisen Katiron Orange GLH (CI Basic Orange 21), Eisen Katiron Brown 3GLH (CI Basic Orange 30), Rhodamine 6GCP (CI Basic Red 1), Eisen Astraphloxine (CI Basic Orange 12), Sumiacrylic Brilliant Red E-2B (CI Basic Orange 15), Astrazon Red GTL (CI Basic Orange 18), Eisen Katiron Brilliant Pin Basic dyes include CI Basic Orange 27, CI Basic Orange 27, CI Basic Orange 46, CI Basic Violet 1, CI Basic Violet 3, CI Basic Violet 4, CI Basic Violet 5, CI Basic Violet 6, CI Basic Violet 7, CI Basic Violet 8, CI Basic Violet 9, CI Basic Violet 10, CI Basic Violet 11, CI Basic Violet 12, CI Basic Violet 13, CI Basic Violet 14, CI Basic Violet 15, CI Basic Violet 16, CI Basic Violet 17, CI Basic Violet 18, CI Basic Violet 19, CI Basic Violet 20, CI Basic Violet 21, CI Basic Violet 22, CI Basic Violet 23, CI Basic Violet 24, CI Basic Violet 25, CI Basic Violet 26, CI Basic Violet 27, CI Basic Violet 28, CI Basic Violet 29, CI Basic Violet 30, CI Basic Violet 31, CI Basic Violet 32, CI Basic Violet 33, CI Basic Violet 34, CI Basic Violet 35, CI Basic Violet 36, CI Basic Violet 37, CI Basic Violet 38, CI Basic Violet 39 ... These dyes may be used alone or in combination of two or more. The dye content is preferably 0.001% by weight or more and 30.0% by weight or less based on the total amount. If it is less than 0.001% by weight, the color tone cannot be adjusted sufficiently, and if it is more than 30.0% by weight, the viscosity of the ink increases excessively, and the writing feel tends to deteriorate.

[0016] The amino acid anionic surfactant comprising an unsaturated fatty acid and the amino acid anionic surfactant comprising a saturated fatty acid used in the present invention are used in combination. The amino acid anionic surfactant is preferably used in an amount of 0.1% by weight to 5.0% by weight based on the total amount of the aqueous pigment ink composition. Within this range, stable ink ejection properties can be obtained while maintaining dispersion stability at low temperatures.

[0017] Examples of amino acid anionic surfactants made of unsaturated fatty acids include NIKKOL Sarcosinate OH (oleoyl sarcosine (condensation product of oleic acid and methylglycine)) and NIKKOL Sarcosinate OHV (oleoyl sarcosine (condensation product of oleic acid and methylglycine)) (both manufactured by Nikko Chemicals Co., Ltd.). Note that the unsaturated fatty acid is a fatty acid having a carbon-carbon double bond, and it is preferable for the carbon-carbon double bonds to have more cis-type carbon-carbon double bonds than trans-type carbon-carbon double bonds, as this will provide better fluidity.

[0018] Amino acid anionic surfactants consisting of saturated fatty acids include Amisoft CS-11 (N-coconut oil fatty acid acyl-L-glutamic acid sodium), Amisoft CA (N-coconut oil fatty acid acyl-L-glutamic acid), Amisoft LA-D (N-lauroyl-L-glutamic acid), Amisoft HA-P (N-stearoyl-L-glutamic acid), Amisoft LS-11 (N-lauroyl-L-glutamic acid sodium), Amisoft MK-11 (N-myristoyl-L-glutamic acid potassium), Amisoft MS-11 (N-myristoyl-L-glutamic acid sodium), Amisoft GS-11P (N-acyl-L-glutamic acid sodium), Amisoft HS-11P (N-stearoyl-L-glutamic acid sodium), Amisoft CT-12 (N-coconut oil fatty acid acyl-L-glutamic acid) triethanolamine salt), Amisoft LT-12 (aqueous solution of lauroyl-L-glutamic acid triethanolamine salt), Amisoft CK-22 (aqueous solution of N-coconut fatty acid acyl-L-glutamic acid potassium salt), Amisoft CS-22 (aqueous solution of N-coconut fatty acid acyl-L-glutamic acid sodium salt) (all manufactured by Ajinomoto Healthy Supply Co., Ltd.), NIKKOL Alaninate LN-30 (30% aqueous solution of sodium lauroyl methylalanine), NIKKOL Sarcosinate CN-30 (30% aqueous solution of sodium cocoyl sarcosine (sodium salt of condensation product of coconut oil fatty acid and methylglycine)), NIKKOL Sarcosinate CT-30 (30% aqueous solution of cocoyl sarcosine (condensation product of coconut oil fatty acid and methylglycine) triethanolamine salt), NIKKOL Sarcosinate LH (lauroyl sarcosine), NIKKOL Sarcosinate LN (sodium lauroyl sarcosine), NIKKOL Sarcosinate LN-30 (sodium lauroyl sarcosine, 30% aqueous solution), NIKKOL Sarcosinate LK-30 (potassium lauroyl sarcosine, 30% aqueous solution), NIKKOL Sarcosinate MN (sodium myristoyl sarcosine), NIKKOL Sarcosinate PN (sodium palmitoyl sarcosine) (all manufactured by Nikko Chemicals Co., Ltd.), and the like.The amino acid anionic surfactant whose amino acid portion is glutamic acid is preferred because it has two carboxylic acids and therefore has a stable bond with the pigment. The amino acid anionic surfactant made of coconut oil fatty acid contains not only the amino acid anionic surfactant made of saturated fatty acid but also the amino acid anionic surfactant made of unsaturated fatty acid in an amount of several weight percent as an impurity, but the amino acid anionic surfactant made of unsaturated fatty acid is less than 10 weight percent when used alone, and the substantial effect of the combined use is not exhibited. It is substantially necessary that the content of each of the amino acid anionic surfactant made of unsaturated fatty acid and the amino acid anionic surfactant made of saturated fatty acid is 10 weight percent or more relative to the total amino acid anionic surfactant content of the ink composition. If the content of the amino acid anionic surfactant made of unsaturated fatty acid is 20 weight percent or more relative to the total amino acid anionic surfactant content of the ink composition, and the content of the amino acid anionic surfactant made of saturated fatty acid is 20 weight percent or more relative to the total amino acid anionic surfactant content of the ink composition, the interaction between the pigments is three-dimensionally gentle, so that the fluidity of the entire composition is not impaired even in a low-temperature environment, and the effect of good writing is enhanced, which is preferred. Furthermore, when the content of the amino acid anionic surfactant consisting of an unsaturated fatty acid is 30% by weight or more relative to the total content of amino acid anionic surfactants in the ink composition, and the content of the amino acid anionic surfactant consisting of a saturated fatty acid is 30% by weight or more relative to the total content of amino acid anionic surfactants in the ink composition, this is particularly preferred because it makes the interactions between the pigments three-dimensionally gentle, does not impair the fluidity of the entire composition even in low-temperature environments, and provides a greater effect of enabling smooth writing.

[0019] As the plate-like inorganic compound of the present invention, smectites and bentonites that can be dispersed in water to form a gel structure can be used. Bentonite is an inorganic mineral that is composed mainly of montmorillonite and is accompanied by secondary components such as quartz, cristobalite, feldspars, and carbonate minerals. A gentle gel structure that envelops the pigment is formed by the gelling action of plate-like inorganic particles such as bentonite, and in particular, a large gel structure complex is formed by the interaction between the amino acid activator made of unsaturated fatty acid and the amino acid activator made of saturated fatty acid and the gel structure formed by the plate-like inorganic particles, and this is used to suppress the situation in which large plate-like pigments such as glittering plate-like aluminum or aluminum flakes as pigment particles are aligned and aggregated, and to enable the pigment to be stably discharged onto the writing surface. Specific examples of the plate-like inorganic compound include OPTIGEL-WX, OPTIGEL-CG, OPTIGEL-CK, OPTIGEL-CK XR, OPTIGEL-CL, OPTIGEL-CMO, OPTIGEL-LX, OPTIGEL-W 724, OPTIGEL-WA, OPTIGEL-WH, OPTIGEL-WM, OPTIGEL-WX XR, LAPONITE-RD, LAPONITE-EP, LAPONITE-RDS, LAPONITE-JS, and LAPONITE-S482 (all manufactured by BYK Japan Co., Ltd.), Wenger, Wenger HV, Wenger FW, Wenger 15, Wenger 23, Wenger SH, Wenger A, Wenger W-100, Wenger W-100U, Wenger W-200U, Wenger W-300U, and Wenger W-300H. Examples of suitable antibacterial agents include P, Esben NX, Esben NX80, Esben NZ, Esben NZ, 70 Esben NEZ, Esben NO12S, Esben NO12 (all manufactured by Hojun Co., Ltd.), Kunipia-F, Kunipia-G, Kunipia-G4, Moistnight-U, Moistnight-S, Sumecton-SA, Sumecton-ST, Sumecton-SWN, Sumecton-SWF, Sumecton-SEN (all manufactured by Kunimine Co., Ltd.). These plate-like inorganic compounds may be used alone or in combination of two or more. The plate-like inorganic compound is preferably 0.05% by weight or more and 3.0% by weight or less based on the total amount of the aqueous pigment ink composition. More preferably, it is 0.1% by weight or more and 2.0% by weight or less. Within the above numerical range, the pigment does not clog the pen tip or tip while maintaining dispersion stability at low temperatures, and stable ink discharge is obtained. If it is more than 3.0% by weight, the viscosity of the ink increases extremely and the writing feel is likely to deteriorate.

[0020] In the resin emulsion of the present invention, the hydrophobic portion binds to the amino acid anionic surfactant, imparting flexibility to the composite of amino acid surfactants consisting of unsaturated fatty acids and saturated fatty acids that covers the pigment surface, thereby imparting fluidity even at ultra-low temperature conditions where diffusion phenomena are minimal. Examples of resin emulsions include urethane resin emulsions, acrylic resin emulsions, acrylic-urethane resin emulsions, and vinyl acetate resin emulsions. Specifically, the polyurethane resin emulsions include U-coat UWS-145 (solid content 35%), U-coat UX-300 (solid content 38%), U-coat UX-310 (solid content 40%), Permarin UA-150 (solid content 30%), Permarin UA-200 (solid content 30%), Permarin UA-368 (solid content 50%), Permarin UA-4000 (solid content 38%) (all manufactured by Sanyo Chemical Industries, Ltd.), Acrito WBR-016U (solid content 30%) (manufactured by Taisei Fine Chemical Co., Ltd.), Neo Sticker 200 (solid content 35%), Neo Sticker 400 (solid content 37%), Neo Sticker 700 (solid content 37%), Neo Sticker 1200 (solid content 37%), Evafanol HA-15 (solid content 30%), Evafanol HA-107C (40% solids), Evafanol HA-50C (35% solids), Evafanol HA-170 (37% solids), Evafanol HA-560 (35% solids) (all manufactured by Nicca Chemical Co., Ltd.), acrylic resin emulsions, Bonron XGS-001 (45% solids), Bonron XPL-100 (30% solids), Bonron XPL-200 (44% solids), Bonron PS-001 (50% solids), Bonron PS-002 (45% solids), Bonron XPS-004 (45% solids), Bonron XHS-20 (40% solids), Bonron XHS-21S (45% solids), Bonron XHS-50 (20% solids), Bonron S-119H (50% solids), Bonron S-416BF (44.5% solids), Bonron S-415 (44% solids), Bonron S-403 (25% solids), Bonron S-476 (45% solids), Bonron S-1120 (45% solids), Bonron S-483TBF (45% solids), Bonron S-434 (45% solids), Bonron S-1360 (44.5% solids) (all manufactured by Mitsui Chemicals, Inc.), DM772 (46% solids), DM774 (46% solids) (all manufactured by Japan Coating Resins, Inc.), Acrylic AKW-107 (30% solids), Acrylic ATW-008S (29.5% solids) (all manufactured by Taisei Fine Chemicals, Inc.), Joncryl 7100 (48.0% solids), Joncryl 711 (solids 42.0%), Joncryl PDX-7370 (solid content 42.0%), Joncryl PDX-7323 (solid content 42.0%), Joncryl PDX-7611 (solid content 36.5%), Joncryl 352D (solid content 45.0%), Joncryl 538J (solid content 45.0%), Joncryl PDX-7700 (solid content 48.0%), Joncryl PDX-7177 (solid content 36.0%), Joncryl 7001 (solid content 87.0%) (all manufactured by BASF (Germany)), Aquabrid 46777 (solid content 30%), Aquabrid UX-100 (solid content 48%), Aquabrid UX-110 (solid content 48%), Aquabrid AST531 (solid content 56%), Aquabrid AST499 (40% solids), Cevian-A886 (42% solids) (all manufactured by Daicel FineChem Co., Ltd.), BONCOAT 40-418EF (55% solids), BONCOAT 5400EF (55% solids), BONCOAT 5495EF (55% solids), BONCOAT CG-8400 (50% solids), BONCOAT CG-8490 (50% solids), BONCOAT CG-8520 (49% solids), BONCOAT CG-8680 (50% solids), BONCOAT CM-8430 (40% solids), BONCOAT CP-6450 (40% solids), BONCOAT DV-961 (40% solids), BONCOAT EC-740EF (40% solids), BONCOAT EC-905EF (50% solids), BONCOAT SFC-55 (solid content 40%) (all manufactured by DIC Corporation), Acrylic-urethane resin emulsions ACRYL T WEM-202U (solid content 40%), ACRYL T WEM-321U (solid content 38%), ACRYL T WEM-3008 (solid content 32.5%) (all manufactured by Taisei Fine Chemical Co., Ltd.), polysol S-5J (solid content 52%), polysol AX-590 (solid content 49%), polysol AX-751 (solid content 46%), polysol AX-428J (solid content 46%), polysol AX-510ZL (solid content 43%), polysol AX-951 (solid content 41%), polysol AX-1000 (solid content 39%), polysol BX-8004 (solid content 48%), polysol AX-747L (solid content 50%), polysol P-503 (solid content 40%), polysol PS-120 (solid content 50%), polysol Examples of suitable copolymers include S-65 (solid content 50%) (all manufactured by Showa Denko K.K.), Cevian-A210 (solid content 52%), Cevian-A215 (solid content 52.5%), Cevian-A217 (solid content 52.5%), Cevian-A218 (solid content 59%), Cevian-A220 (solid content 48%), Cevian-A240 (solid content 53.5%), Cevian-A415 (solid content 55%), and Cevian-A435 (solid content 57%) (all manufactured by Daicel FineChem Co., Ltd.). These resin emulsions may be used alone or in combination of two or more. The resin emulsion preferably has a solid content of 1.0% by weight to 10.0% by weight based on the total amount of the aqueous pigment ink composition. Within this range, stable ink dischargeability can be obtained while maintaining fluidity at low temperatures.

[0021] Water is used as the main solvent of the ink. In the present invention, the main solvent means a solvent that accounts for 50% by weight or more of the total amount of solvents in the total amount of the ink composition. It is preferable to use ion-exchanged water or purified water. Furthermore, the organic solvent is not particularly limited and may be used in combination as long as it is an organic solvent that has been conventionally known for the purpose of achieving various qualities as an ink, such as preventing the ink from freezing at low temperatures and preventing the ink from drying at the pen tip. Specific examples of organic solvents include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, thiodiethylene glycol, glycerin, benzyl glycol, and benzyl diglycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, sulfolane, dipropylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monohexyl ether. Examples of the organic solvent include 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, and tripropylene glycol monophenyl ether, alcohol solvents such as isopropyl alcohol, 3-methyl-3-methoxy-1-butanol, benzyl alcohol, α-methylbenzyl alcohol, lauryl alcohol, tridecyl alcohol, isododecyl alcohol, and isotridecyl alcohol, as well as propylene glycol methyl ether acetate, propylene glycol diacetate, 2-pyrrolidone, N-methyl-2-pyrrolidone, sulfolane, and γ-butyrolactone. These organic solvents may be used alone or in combination of two or more.

[0022] The pH of the ink composition can be adjusted by using a pH adjuster such as a basic substance such as sodium hydroxide, lithium hydroxide, triethanolamine, diethanolamine, monoethanolamine, aminomethylpropanediol, or a conventionally known acidic substance, and by adjusting the pH to 6.0 or more and 10.0 or less using these pH adjusters, the fluidity maintaining effect of the ink composition is further improved. Furthermore, by adjusting the pH to 7.0 or more and 9.0 or less, it becomes easier to form bonds between the amino acid anionic surfactant made of unsaturated fatty acid and the amino acid anionic surfactant made of saturated fatty acid and the pigment surface, and it is expected that the fluidity of the aqueous pigment ink composition for writing instruments will be maintained for a long time. These pH adjusters may be used alone or in combination of two or more types.

[0023] In addition, various additives can be used as necessary. For example, wax emulsions can be used to improve pigment adhesion. Specifically, RK-185 (solid content 45%) (manufactured by GOO Chemical Industry Co., Ltd.) and WE-65 (solid content 35%) (manufactured by Konishi Co., Ltd.) made of paraffin wax, and Chemipearl W100 (solid content 40%), Chemipearl W200 (solid content 40%), Chemipearl W300 (solid content 40%), Chemipearl W310 (solid content 40%), Chemipearl W400 (solid content 40%), Chemipearl W4005 (solid content 40%), Chemipearl W401 (solid content 40%), Chemipearl W410 (solid content 40%), Chemipearl W500 (solid content 40%), Chemipearl WF640 (solid content 40%), Chemipearl W700 (solid content 40%), Chemipearl W800 (solid content 40%), Chemipearl W900 (solid content 40%), ...10 W950 (solid content 40%) (all manufactured by Mitsui Chemicals, Inc.), HYTEC E-6500 (solid content 35%), HYTEC E-9015 (solid content 40%), HYTEC E-6400 (solid content 35%), HYTEC E-8237 (solid content 40%), HYTEC E-5403P (solid content 30%), HYTEC E-1000 (solid content 35%), HYTEC E-4A (solid content 35%) (all manufactured by Toho Chemical Industry Co., Ltd.), HYTEC P-9018 (solid content 35%), HYTEC P-5300 (solid content 30%), HYTEC P-5800 (solid content 30%), HYTEC P-5060P (solid content 40%) (all manufactured by Toho Chemical Industry Co., Ltd.), which are made of polypropylene wax, and Chemipearl, which is made of ethylene-alpha-olefin copolymer. A100 (solid content 40%) (manufactured by Mitsui Chemicals, Inc.), Chemipearl V100 (solid content 40%), Chemipearl V200 (solid content 40%), and Chemipearl V300 (solid content 40%) made of ethylene vinyl acetate copolymer resins (all manufactured by Mitsui Chemicals, Inc.), HYTEC S-3121 (solid content 25%), HYTEC S-3800 (solid content 25%), HYTEC S-9242 (solid content 20%), HYTEC S-9200 (solid content 20%), HYTEC S-8512 (solid content 25%), and HYTEC S-3148K (solid content 25%) made of polyethylene copolymer resins (all manufactured by Toho Chemical Industry Co., Ltd.), and the like. These wax emulsions may be used alone or in combination of two or more kinds. In addition, sodium dehydroacetate, 1,2-benzisothiazarin-3-one, 2-pyridinethiol-1-oxide sodium salt, etc. can be used as preservatives and antifungals for the aqueous pigment ink composition. These preservatives and antifungals have a synergistic effect when combined with 1,2-benzisothiazarin-3-one and 2-pyridinethiol-1-oxide sodium salt, and the preservative and antifungal effect can be obtained with a smaller content.

[0024] The viscosity of the aqueous pigment ink composition for writing instruments of the present invention is not particularly limited and is appropriately adjusted according to the embodiment of a direct-fill marker, ballpoint pen, brush, calligraphy pen, correction fluid, etc. By appropriately adjusting the viscosity according to the embodiment, writing performance and storage stability such as writing feel, uniformity of handwriting, handwriting density, suppression of bleeding, ink discharge stability, control of handwriting strike-through onto paper, suppression of handwriting smearing, suppression of drying of the pen tip and tip, writing performance when dry, and dispersion stability of the pigment are ensured, which is preferable.

[0025] In producing the aqueous pigment ink composition for writing instruments of the present invention, various conventionally known methods can be employed. For example, water and bentonite are put into a Henschel mixer, propeller agitator, homogenizer, turbo mixer, high-pressure homogenizer, fine flow mill, or other agitator having high shear force, and then the pigment dispersed by a dispersing machine such as a Henschel mixer, propeller agitator, homogenizer, turbo mixer, high-pressure homogenizer, ball mill, bead mill, roll mill, or other dispersing machine and other remaining components are put in and further mixed and stirred to easily obtain the composition. In addition, in these preparation steps, the generated dispersion heat can be used as it is for stirring, or heating can be applied, or stirring can be performed by cooling. Removal of bubbles by a defoamer or filtration of coarse particles by a filter may be performed as necessary. These various mixing steps, dispersion steps, filtration steps, heating steps, or cooling steps may each be performed alone, or two or more steps may be performed in parallel.

[0026] The aqueous pigment ink composition for writing instruments of the present invention can be suitably used by filling it into a writing instrument, but the use is not limited to writing instruments and may also be used in cosmetic applicators such as eyeliner and eyebrow applicators. In addition, a system may be used that includes a temporary ink reservoir member having a comb-like cross section that directly stores ink in the coating liquid storage chamber without using an ink absorbing body such as a fiber bundle, or a system that includes a valve mechanism that automatically opens and closes in response to operation or changes in internal pressure. When the aqueous pigment ink composition used uses titanium oxide or a large-diameter plate-shaped glittering pigment, it is preferable to directly store the ink composition in a fiber bundle called batting so that the ink stored in the coating liquid storage chamber is used up, and the ink supply mechanism to the coating destination is preferably one that uses a valve mechanism that can ensure a relatively large ink passage rather than one that passes through fine holes in a fiber bundle or a temporary ink reservoir member with a comb-like cross section, or one that is equipped with a ballpoint pen or tip valve mechanism that controls the ink discharge with a valve formed at the pen tip. Furthermore, by using a brush-type coating destination that can freely form wide coating marks as desired, wide coating marks that demonstrate the glittering properties of the ink can be formed.

[0027] FIG. 1 shows an example of the structure of a writing implement. This is a brush pen type applicator that uses a relatively soft object such as a brush tip as the application tip, has a valve mechanism located at the connection between the application tip and the application liquid storage chamber, and opens and closes the valve mechanism by knocking the rear end to control the ink supply to the application tip, a so-called rear end knock type valve mechanism. The barrel 1 is provided with an application tip 2 at its tip and a push-in type operating part 3 at its rear end, and a cap 4 that protects the application tip 2 can be fitted to the tip of the barrel 1. The cap 4 has anti-rolling ribs 4a on its side wall that prevent the applicator from rolling when attached. Barrel 1 has a front barrel 1a having an opening through which application tip 2 protrudes, and a rear barrel 1b to which operating part 3 is connected.

[0028] The front part of the front barrel 1a is small in diameter to match the diameter of the pen tip, and the rear part is large in diameter to connect with the rear barrel 1b. The inner wall of the small diameter part has vertical ribs 5 evenly arranged around the circumference to support the pen tip. The grooves 6 formed between the vertical ribs 5 also serve as air passages to take in the volume of the ink composition discharged by writing and application. The rear large diameter part of the front barrel 1a has a valve seat member 7 of a valve mechanism that controls the flow of ink. The valve seat member 7 has a central hole 7a at its center, which serves as an ink passage, and its peripheral part serves as a valve seat portion that can be in circumferential contact with a valve rod, which will be described later. The valve seat member 7 has a coil spring 9 fixed to its rear end, which urges the valve rod 8 backward to keep it in close contact with the valve seat at all times when not in operation.

[0029] The rear barrel 1b has a rear hole 10 at its rear end, in which the operating part 3 is disposed. A connecting rod 11 that transmits the pushing operation of the operating part 3 to the valve rod 8 protrudes from the rear hole 10 and is liquid-tightly sealed by a packing member 12 made of a material having rubber elasticity and having a soft hinge part 12a. When the operating part 3 is pushed toward the inside of the barrel, it comes into contact with the rear end of the packing member 12, and the packing member 12 receives a pushing force, causing the hinge part 12a to deform and transmit the pushing force to the connecting rod 11. As the connecting rod 11 advances, the valve rod 8 advances against the elastic force of the coil spring 9, releasing the valve mechanism and allowing the ink composition to flow. The coil spring 9 abuts against the tip surface of the connecting rod 11, which is the connecting step between the connecting rod 11 and the valve rod 8, and urges the connecting rod 11 and the valve rod 8 backward. When the pressing operation is released, the connecting rod 11 and the valve rod 8 move backward to close the valve mechanism.

[0030] An application target connection pipe 13 is attached to the front end of the valve rod 8, and a brush-shaped application target 2 is connected to the front end of the application target connection pipe 13. Thus, the application target 2 also moves forward in conjunction with the pushing operation of the operation part 3, and when the pushing operation is released, the application target 2 also moves backward by the elastic force of the coil spring 9. In this way, it is possible to prevent the ink composition present in the space around the application target 2 from drying and solidifying due to the application of an external force every time an operation is performed, and it also assists in discharging the ink composition. Such a mechanism is particularly effective when using a liquid with a relatively high solid content.

[0031] The inside of the rear barrel 1b is mainly a coating liquid storage chamber, and a volume adjuster 14 made of cylindrical polypropylene for adjusting the volume of the coating liquid storage chamber is arranged to surround the connecting rod 11 as an internal member. The volume adjuster 14 may be fixed to the rear barrel 1b, but it is preferable to keep it in an unfixed state so that it can move back and forth freely in relation to the operating connecting rod 11. Reducing the volume of the coating liquid storage chamber in this way suppresses the ink composition from being blown out by the expanded gas when the valve mechanism is opened, as the gaseous matter resulting from the evaporation of the air or solvent of the ink composition contained therein expands due to changes in temperature or pressure. In addition, by using a transparent or translucent material for the rear barrel, when a glittering pigment or white titanium oxide is used as a colorant, it is possible to narrow at least a portion of the gap to make it easier to visually check the color of the ink composition contained therein and the remaining amount of the ink composition. In addition, the color of the volume adjuster 14 can be made black, white, milky white, or the like to make the color of the ink composition even easier to visually check.

[0032] When the ink composition is to be ejected by pressing the rear shaft 1b, the rear shaft 1b can be made of a flexible material such as a polyolefin resin such as low-density polyethylene, high-density polyethylene, or polypropylene, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate, polyamide, polyacrylonitrile, polycarbonate, polyvinyl chloride, polystyrene, polyoxymethylene, or various elastomers. EXAMPLES

[0033] The present invention will now be described in detail with reference to examples.

[0034] (Preparation of Ink Composition) See table 1 below. 35 The blending composition shown in Examples 1 to 281 and Comparative Examples 1 to 54 , Reference examples 1~5 The ink composition was prepared as follows.

[0035] Table 1~ 35 Specifically, the following materials were used for each composition shown in . <Pigments> GP-1: LG neo RED #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-2: LG neo GREEN #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-3: LG neo BLUE #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-4: LG neo YELLOW #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-5: LG neo PINK #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-6: LG neo B-GOLD #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-7: LG neo SILVER #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-8: LG neo VIOLET #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-9: LG neo R-GOLD #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-10: LG neo S-GOLD #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-11: LG neo BLACK #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-12: LG neo COPPER #325 (metal-coated film powder glitter pigment, average particle size 35 μm, manufactured by Oike Imaging Co., Ltd.) GP-13: LG neo B-GOLD #35 (metal-coated film powder glitter pigment, manufactured by Oike Imaging Co., Ltd.) GP-14: LG neo GREEN #100 (metal-coated film powder glitter pigment, average particle size 115 μm, manufactured by Oike Imaging Co., Ltd.) GP-15: LG neo GREEN #150 (metal-coated film powder glitter pigment, average particle size 95 μm, manufactured by Oike Imaging Co., Ltd.) GP-16: LG neo YELLOW #150 (metal-coated film powder glitter pigment, average particle size 95 μm, manufactured by Oike Imaging Co., Ltd.) GP-17: LG neo GREEN #200 (metal-coated film powder glitter pigment, average particle size 60 μm, manufactured by Oike Imaging Co., Ltd.) GP-18: LG neo BLUE #200 (metal-coated film powder glitter pigment, average particle size 60 μm, manufactured by Oike Imaging Co., Ltd.) GP-19: LG neo B-GOLD #500 (metal-coated film powder glitter pigment, average particle size 15 μm, manufactured by Oike Imaging Co., Ltd.) CB-1: FUJI SP BLACK 8041 (black pigment dispersion, carbon black, Fuji Pigment Co., Ltd.) CB-2: Carbon black MA-100 (Carbon black, manufactured by Mitsubishi Chemical Corporation) CB-3: Lovecolor 220 (MD) Black (acrylic copolymer fine particles, manufactured by Dainichiseika Color & Chemicals Co., Ltd.) OP-1: FUJI SP BLUE 6555 (blue pigment dispersion, organic pigment, Fuji Pigment Co., Ltd.) OP-2: FUJI SP BLUE 6401 (blue pigment dispersion, organic pigment, Fuji Pigment Co., Ltd.) TO-1: CR-50 (titanium oxide, manufactured by Ishihara Sangyo Kaisha, Ltd.) JR-1: Ropeake OP-84J (hollow resin particles, manufactured by Rohm and Haas Japan) JR-2: Eposter S6 (melamine, benzoguanamine-based fine particles, Nippon Shokubai Co., Ltd.)

[0036] <Anionic surfactants made from unsaturated fatty acids> UFAA-1: NIKKOL Sarcosinate OH (Oleoyl Sarcosine (condensation product of oleic acid and methylglycine), manufactured by Nikko Chemicals Co., Ltd.) UFAA-2: NIKKOL Sarcosinate OHV (Oleoyl Sarcosine (condensation product of oleic acid and methylglycine), manufactured by Nikko Chemicals Co., Ltd.)

[0037] <Amino acid anionic surfactants made from saturated fatty acids> SFAA-1: Amisoft CS-11 (N-coconut oil fatty acid acyl-L-sodium glutamate, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-2: Amisoft CA (N-coconut oil fatty acid acyl-L-glutamic acid, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-3: Amisoft LA-D (N-lauroyl-L-glutamic acid, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-4: Amisoft HA-P (N-stearoyl-L-glutamic acid, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-5: Amisoft LS-11 (Sodium N-lauroyl-L-glutamate, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-6: Amisoft MK-11 (potassium N-myristoyl-L-glutamate, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-7: Amisoft MS-11 (N-myristoyl-L-glutamic acid monosodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-8: Amisoft GS-11P (N-acyl-L-sodium glutamate, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-9: Amisoft HS-11P (N-stearoyl-L-glutamic acid sodium, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-10: Amisoft CT-12 (aqueous solution of N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine salt, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-11: Amisoft LT-12 (aqueous solution of lauroyl-L-glutamic acid triethanolamine salt, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-12: Amisoft CK-22 (aqueous solution of N-coconut oil fatty acid acyl-L-glutamic acid potassium salt, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-13: Amisoft CS-22 (aqueous solution of N-coconut oil fatty acid acyl-L-glutamic acid sodium salt, manufactured by Ajinomoto Healthy Supply Co., Ltd.) SFAA-14: NIKKOL Alaninate LN-30 (a 30% aqueous solution of sodium lauroylmethylalanine, manufactured by Nikko Chemicals Co., Ltd.) SFAA-15: NIKKOL Sarcosinate CN-30 (30% aqueous solution of sodium cocoyl sarcosine, manufactured by Nikko Chemicals Co., Ltd.) SFAA-16: NIKKOL Sarcosinate CT-30 (30% aqueous solution of cocoyl sarcosine triethanolamine salt, manufactured by Nikko Chemicals Co., Ltd.) SFAA-17: NIKKOL Sarcosinate LH (Lauroyl Sarcosine, manufactured by Nikko Chemicals Co., Ltd.) SFAA-18: NIKKOL Sarcosinate LN (sodium lauroyl sarcosine, manufactured by Nikko Chemicals Co., Ltd.) SFAA-19: NIKKOL Sarcosinate LN-30 (sodium lauroyl sarcosine, 30% aqueous solution, manufactured by Nikko Chemicals Co., Ltd.) SFAA-20: NIKKOL Sarcosinate LK-30 (Potassium Lauroyl Sarcosine, 30% aqueous solution, manufactured by Nikko Chemicals Co., Ltd.) SFAA-21: NIKKOL Sarcosinate MN (sodium myristoyl sarcosine, manufactured by Nikko Chemicals Co., Ltd.) SFAA-22: NIKKOL Sarcosinate PN (Sodium Palmitoyl Sarcosine, manufactured by Nikko Chemicals Co., Ltd.)

[0038] <Phosphate ester type anionic surfactant> REA-1: Phosphanol RB-410 (polyoxyethylene lauryl ether phosphate, manufactured by Toho Chemical Industry Co., Ltd.)

[0039] <Resin emulsion> EM-1: U-coat UWS-145 (urethane resin emulsion, solid content 35%, Sanyo Chemical Industries, Ltd.) EM-2: U-coat UX-300 (urethane resin emulsion, solid content 38%, Sanyo Chemical Industries, Ltd.) EM-3: U-coat UX-310 (urethane resin emulsion, solid content 40%, Sanyo Chemical Industries, Ltd.) EM-4: Permarin UA-150 (urethane resin emulsion, solid content 30%, Sanyo Chemical Industries, Ltd.) EM-5: Permarin UA-200 (urethane resin emulsion, solid content 30%, Sanyo Chemical Industries, Ltd.) EM-6: Permarin UA-368 (urethane resin emulsion, solid content 50%, Sanyo Chemical Industries, Ltd.) EM-7: Permarin UA-4000 (urethane resin emulsion, solid content 38%, Sanyo Chemical Industries, Ltd.) EM-8: Acrit WBR-016U (urethane resin emulsion, solid content 30%, manufactured by Taisei Fine Chemical Co., Ltd.) EM-9: Bonlon XGS-001 (acrylic resin emulsion, solid content 45%, manufactured by Mitsui Chemicals, Inc.) EM-10: Bonlon XPL-100 (acrylic resin emulsion, solid content 30%, manufactured by Mitsui Chemicals, Inc.) EM-11: Bonlon XPL-200 (acrylic resin emulsion, solid content 44%, manufactured by Mitsui Chemicals, Inc.) EM-12: Bonlon PS-001 (acrylic resin emulsion, solid content 50%, manufactured by Mitsui Chemicals, Inc.) EM-13: Bonlon PS-002 (acrylic resin emulsion, solid content 45%, manufactured by Mitsui Chemicals, Inc.) EM-14: Bonlon XPS-004 (acrylic resin emulsion, solid content 45%, manufactured by Mitsui Chemicals, Inc.) EM-15: Bonlon XHS-20 (acrylic resin emulsion, solid content 40%, manufactured by Mitsui Chemicals, Inc.) EM-16: Bonlon XHS-21S (acrylic resin emulsion, solid content 45%, manufactured by Mitsui Chemicals, Inc.) EM-17: Bonlon XHS-50 (acrylic resin emulsion, solid content 20%, manufactured by Mitsui Chemicals, Inc.) EM-18: Bonlon S-119H (acrylic resin emulsion, solid content 50%, manufactured by Mitsui Chemicals, Inc.) EM-19: Bonlon S-416BF (acrylic resin emulsion, solid content 44.5%, manufactured by Mitsui Chemicals, Inc.) EM-20: Bonlon S-415 (acrylic resin emulsion, solid content 44%, manufactured by Mitsui Chemicals, Inc.) EM-21: Bonlon S-403 (acrylic resin emulsion, solid content 25%, manufactured by Mitsui Chemicals, Inc.) EM-22: Bonlon S-476 (acrylic resin emulsion, solid content 45%, manufactured by Mitsui Chemicals, Inc.) EM-23: Bonlon S-1120 (acrylic resin emulsion, solid content 45%, manufactured by Mitsui Chemicals, Inc.) EM-24: Bonlon S-483TBF (acrylic resin emulsion, solid content 45%, manufactured by Mitsui Chemicals, Inc.) EM-25: Bonlon S-434 (acrylic resin emulsion, solid content 45%, manufactured by Mitsui Chemicals, Inc.) EM-26: Bonlon S-1360 (acrylic resin emulsion, solid content 44.5%, manufactured by Mitsui Chemicals, Inc.) EM-27: DM772 (acrylic resin emulsion, solid content 46%, manufactured by Japan Coating Resin Co., Ltd.) EM-28: DM774 (acrylic resin emulsion, solid content 46%, manufactured by Japan Coating Resin Co., Ltd.) EM-29: Acrylit ATW-008S (acrylic resin emulsion, solid content 29.5%, manufactured by Taisei Fine Chemical Co., Ltd.) EM-30: Joncryl 7100 (acrylic resin emulsion, solid content 48%, manufactured by BASF (Germany)) EM-31: Joncryl 711 (acrylic resin emulsion, solid content 42%, manufactured by BASF (Germany)) EM-32: Joncryl PDX-7370 (acrylic resin emulsion, solid content 42%, manufactured by BASF (Germany)) EM-33: Joncryl PDX-7323 (acrylic resin emulsion, solid content 42%, manufactured by BASF (Germany)) EM-34: Joncryl PDX-7611 (acrylic resin emulsion, solid content 36.5%, manufactured by BASF (Germany)) EM-35: Joncryl352D (acrylic resin emulsion, solid content 45%, manufactured by BASF (Germany)) EM-36: Joncryl 538J (acrylic resin emulsion, solid content 45%, manufactured by BASF (Germany)) EM-37: Joncryl PDX-7700 (acrylic resin emulsion, solid content 48%, manufactured by BASF (Germany)) EM-38: Joncryl PDX-7177 (acrylic resin emulsion, solids content 36%, manufactured by BASF (Germany)) EM-39: Joncryl 7001 (acrylic resin emulsion, solid content 87%, manufactured by BASF (Germany)) EM-40: Acrit WEM-321U (acrylic urethane resin emulsion, solids content 38%, manufactured by Taisei Fine Chemical Co., Ltd.) EM-41: Polysol S-5J (vinyl acetate resin emulsion, solid content 52%, manufactured by Showa Denko K.K.) EM-42: Polysol AX-590 (vinyl acetate resin emulsion, solids content 49%, Showa Denko Co., Ltd.) EM-43: Polysol AX-751 (vinyl acetate resin emulsion, solids content 46%, Showa Denko Co., Ltd.) EM-44: Polysol AX-428J (vinyl acetate resin emulsion, solid content 46%, Showa Denko Co., Ltd.) EM-45: Polysol AX-510ZL (vinyl acetate resin emulsion, solid content 43%, Showa Denko Co., Ltd.) EM-46: Polysol AX-951 (vinyl acetate resin emulsion, solid content 41%, Showa Denko Co., Ltd.) EM-47: Polysol AX-1000 (vinyl acetate resin emulsion, solids content 39%, Showa Denko Co., Ltd.) EM-48: Polysol BX-8004 (vinyl acetate resin emulsion, solids content 48%, Showa Denko Co., Ltd.) EM-49: Polysol AX-747L (vinyl acetate resin emulsion, solids content 50%, Showa Denko Co., Ltd.) EM-50: Polysol P-503 (vinyl acetate resin emulsion, solid content 40%, Showa Denko Co., Ltd.) EM-51: Polysol PS-120 (vinyl acetate resin emulsion, solids content 50%, Showa Denko Co., Ltd.) EM-52: Polysol S-65 (vinyl acetate resin emulsion, solids content 50%, manufactured by Showa Denko K.K.)

[0040] <Water-soluble resin> WS-1: SMA1440 (water-soluble resin, styrene-maleic acid resin, manufactured by Arco Chemical Co., Ltd.) WS-2: Joncryl52J (styrene acrylic resin aqueous solution, solid content: 60%, manufactured by BASF (Germany)) WS-3: Joncryl62J (water-soluble resin, manufactured by BASF (Germany))

[0041] <dye> D-1: Water Black 256L (a 14% aqueous solution of black dye, manufactured by Orient Chemical Industries Co., Ltd.) D-2: Water Red 1 (CI Acid Red 18, Orient Chemical Industry Co., Ltd.) D-3: Daiwa Red No. 104WB (CI Acid Red 92, manufactured by Daiwa Chemical Industries, Ltd.) D-4: Daiwa Red No. 106WB (CI Acid Red 52, manufactured by Daiwa Chemical Industries, Ltd.) D-5: Water Yellow 6C (CI Acid Yellow 42, Orient Chemical Industry Co., Ltd. D-6: Water Blue 119 (Orient Chemical Industry Co., Ltd.) D-7: Daiwa Blue No. 1 (CI Acid Blue 9, Daiwa Chemical Co., Ltd.)

[0042] <Plate-shaped inorganic compound> BT-1: OPTIGEL-WX (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-2: OPTIGEL-CG (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-3: OPTIGEL-CK (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-4: OPTIGEL-CK XR (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-5: OPTIGEL-CL (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-6: OPTIGEL-CMO (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-7: OPTIGEL-LX (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-8: OPTIGEL-W 724 (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-9: OPTIGEL-WA (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-10: OPTIGEL-WH (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-11: OPTIGEL-WM (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-12: OPTIGEL-WX XR (modified bentonite, manufactured by BYK Japan Co., Ltd.) BT-13: Bengel (refined bentonite, manufactured by Hojun Co., Ltd.) BT-14: Bengel HV (refined bentonite, manufactured by Hojun Co., Ltd.) BT-15: Bengel FA (refined bentonite, manufactured by Hojun Co., Ltd.) BT-16: Bengel W-100 (modified bentonite, manufactured by Hojun Co., Ltd.) BT-17: Bengel W-100U (modified bentonite, manufactured by Hojun Co., Ltd.) BT-18: Esben NX (refined bentonite, manufactured by Hojun Co., Ltd.) BT-19: Kunipia-F (refined bentonite, manufactured by Kunimine Co., Ltd.) BT-20: Kunipia-G (refined bentonite, manufactured by Kunimine Co., Ltd.) BT-21: Moistnite-U (bentonite, manufactured by Kunipia Co., Ltd.) ST-1: LAPONITE-RD (synthetic hectorite, manufactured by BYK Japan Co., Ltd.) ST-2: LAPONITE-EP (synthetic hectorite, manufactured by BYK Japan Co., Ltd.) ST-3: LAPONITE-RDS (synthetic hectorite, manufactured by BYK Japan Co., Ltd.) ST-4: LAPONITE-JS (synthetic hectorite, manufactured by BYK Japan Co., Ltd.) ST-5: LAPONITE-S482 (synthetic hectorite, manufactured by BYK Japan Co., Ltd.) ST-6: Sumecton-SA (synthetic saponite, manufactured by Kunimine Co., Ltd.) ST-7: Sumecton-ST (synthetic stevensite, manufactured by Kunimine Co., Ltd.) ST-8: Sumecton-SWN (synthetic hectorite, manufactured by Kunimine Co., Ltd.) ST-9: Sumecton-SWF (synthetic hectorite, manufactured by Kunimine Co., Ltd.)

[0043] <Polysaccharide> GM-1: Kelcocrete 200 (Diutan gum, manufactured by Sansho Co., Ltd.) GM-2: Kelzan (xanthan gum, manufactured by Sansho Co., Ltd.) GM-3: MEYPRO-GAT (Guar gum, manufactured by Sansho Co., Ltd.) GM-4: K1A96 (Welan gum, Sansho Co., Ltd.) GM-5: Maprodin 200 (locust bean gum, manufactured by Sansho Co., Ltd.) GM-6: GENU pectin type BETA (pectin, manufactured by Sansho Co., Ltd.) GM-7: Leozan (succinoglycan, manufactured by Sansho Co., Ltd.)

[0044] <Main solvent> W-1: Ion-exchanged water

[0045] <Organic solvent> SOL-1: Diethylene glycol SOL-2: Ethylene glycol SOL-3: Glycerin SOL-4: 3-methyl-3-methoxy-1-butanol SOL-5: Diethylene glycol monomethyl ether SOL-6: Propylene glycol

[0046] <Wax emulsion> WEM-1: RK-185 (paraffin wax, manufactured by GOO Chemical Industry Co., Ltd.) WEM-2: WE-65 (Paraffin wax, manufactured by Konishi Co., Ltd.) WEM-3: Chemipearl W900 (polyethylene wax, manufactured by Mitsui Chemicals, Inc.) WEM-4: Chemipearl A100 (ethylene-alpha-olefin copolymer, manufactured by Mitsui Chemicals, Inc.) WEM-5: Chemipearl V100 (ethylene vinyl acetate copolymer resin, manufactured by Mitsui Chemicals, Inc.)

[0047] <Anti-mold agent> AM-1: Proxel GXL(S) (mold inhibitor, manufactured by Lonza Japan Co., Ltd.) AM-2: Proxel GXL (mildew preventive, manufactured by Lonza Japan Co., Ltd.) AM-3: Sun Eye Back Sodium Omadine (mildew preventive, manufactured by San-Ai Sekiyu Co., Ltd.)

[0048] <Rust preventive agent> RI-1: Benzotriazole (rust preventive agent, manufactured by E-CHEM ENTERPRISE CORPORATION)

[0049] <pH adjuster> PC-1: NaOH PC-2: Triethanolamine PC-3: Diethanolamine PC-4: Aminomethylpropanol

[0050] Each example and comparative example , reference example The ink compositions were prepared as follows. <Examples 1 to 281, Reference examples 1-5 > The total amount of the amino acid anionic surfactant composed of unsaturated fatty acids, the total amount of the amino acid anionic surfactant composed of saturated fatty acids, the total amount of ion-exchanged water as the main solvent, and the total amount of the organic solvent were stirred with a homomixer for 1 hour to prepare an aqueous solution of the amino acid anionic surfactant. Then, the total amount of the pigment was added and stirred with a homomixer for 1 hour. Thereafter, the total amount of the remaining formulations was added and stirred with a homomixer for 1 hour to obtain an ink composition.

[0051] <Comparative Examples 1 to 4, 51> The total amount of ion-exchanged water as the main solvent, the total amount of the organic solvent, and the total amount of the pigment were added and stirred with a homomixer for 1 hour. Then, the total amount of the remaining formulations was added and stirred with a homomixer for 1 hour to obtain an ink composition.

[0052] <Comparative Examples 5 to 14> The entire amount of the phosphate ester-based anionic surfactant, the entire amount of ion-exchanged water as the main solvent, and the entire amount of the organic solvent were stirred in a homomixer for 1 hour to prepare an aqueous solution of the phosphate ester-based anionic surfactant, and then the entire amount of the pigment was added and stirred in a homomixer for 1 hour. Thereafter, the entire amount of the remaining ingredients was added and stirred in a homomixer for 1 hour to obtain an ink composition.

[0053] <Comparative Examples 15 to 38> The entire amount of the amino acid anionic surfactant consisting of saturated fatty acid, the entire amount of ion-exchanged water as the main solvent, and the entire amount of the organic solvent were stirred in a homomixer for 1 hour to prepare an aqueous solution of the amino acid anionic surfactant, and then the entire amount of the pigment was added and stirred in a homomixer for 1 hour. Thereafter, the entire amount of the remaining ingredients was added and stirred in a homomixer for 1 hour to obtain an ink composition.

[0054] <Comparative Examples 39 to 50, 52 to 54> The entire amount of the amino acid anionic surfactant consisting of unsaturated fatty acid, the entire amount of ion-exchanged water as the main solvent, and the entire amount of the organic solvent were stirred in a homomixer for 1 hour to prepare an aqueous solution of the amino acid anionic surfactant, and then the entire amount of the pigment was added and stirred in a homomixer for 1 hour. Thereafter, the entire amount of the remaining ingredients was added and stirred in a homomixer for 1 hour to obtain an ink composition.

[0055] (Content of each amino acid anionic surfactant) The table of examples shows the content of amino acid anionic surfactants consisting of unsaturated fatty acids relative to the total content of amino acid anionic surfactants in the ink composition (represented as "UFAA (%)" in the table of examples, in units of "weight %"), and the content of amino acid anionic surfactants consisting of saturated fatty acids relative to the total content of amino acid anionic surfactants in the ink composition (represented as "SFAA (%)" in the table of examples, in units of "weight %").

[0056] Ink backflow prevention composition 1 Lucant HC100 (ethylene alpha olefin, base material, manufactured by Mitsui Petrochemical Industries, Ltd.) 94.5% by weight Aerosil R974 (fine silica particles, gelling agent, manufactured by Nippon Aerosil Co., Ltd.) 4.0% by weight Leopearl KL (dextrin fatty acid ester, manufactured by Chiba Flour Mills 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 ink backflow prevention composition 1. This ink backflow prevention composition 1 had a viscosity of 40,000 mPa·S at 25°C.

[0057] (Creation of exam writing implement 1) In order to evaluate the ink compositions according to the Examples and Comparative Examples, a brush pen-type applicator with a rear-end knock type valve mechanism for testing, as shown in FIG. 1, was created. , Reference examples 1~5 The test writing instrument 1 was filled with 2.0 g of the aqueous pigment ink composition for writing instruments. (In the table, this is indicated as "writing instrument 1" and the corresponding combination is indicated with "〇".)

[0058] (Creation of Exam Writing Instrument 2) In order to evaluate the ink compositions according to the Examples and Comparative Examples, a commercially available paint marker (MMP20-A (manufactured by Pentel Co., Ltd.) was used without the ink, and the ink compositions according to the Examples and Comparative Examples were used. 279 and Comparative Example 52 were filled with 2.0 g of the aqueous pigment ink composition for a writing instrument, and this was used as test writing instrument 2. (In the table, this is indicated as "writing instrument 2" and the corresponding combination is indicated with "◯" in the column.)

[0059] (Creation of exam writing implement 3) In order to evaluate the ink compositions according to the examples and comparative examples, a commercially available correction fluid applicator (XEZL61-W, manufactured by Pentel Co., Ltd.) was used without the correction fluid. 280 and the test writing instrument 3 was prepared by directly filling the test writing instrument with 2.0 g of the aqueous pigment ink composition for writing instruments prepared in Comparative Example 53. (In the table, this is indicated as "writing instrument 3" and the corresponding combination is indicated with "◯" in the column.)

[0060] (Creation of Exam Writing Instrument 4) To evaluate the ink compositions according to the examples and comparative examples, the inks and the ink backflow prevention composition were removed from a commercially available aqueous ballpoint pen (K110-DX, manufactured by Pentel Co., Ltd.), and the aqueous pigment ink composition for writing instruments of Example 281 and Comparative Example 54, 0.8 g, and 0.1 g of the ink backflow prevention composition 1 were directly filled therein to obtain a test writing instrument 4. (In the table, it is denoted as "Writing instrument 4", and "〇" is denoted in the column of the corresponding combination)

[0061] (Low-temperature storage and then low-temperature writing test 1) The capped test samples were placed horizontally in an environmental test chamber at room temperature - 5°C and left standing for 3 months. With the samples still in the environment of room temperature - 5°C, the caps of the test samples were removed, and the character "永" with a size of 2 cm × 2 cm was written on the test paper shown in 7.3 of JIS S 6061. It was confirmed that the ink was ejected and a good handwriting could be formed. 〇: Can write well. ×: Cannot write.

[0062] (Low-temperature storage and then low-temperature writing test 2) The capped test samples were placed horizontally in an environmental test chamber at room temperature - 5°C and left standing for 4 months. With the samples still in the environment of room temperature - 5°C, the caps of the test samples were removed, and the character "永" with a size of 2 cm × 2 cm was written on the test paper shown in 7.3 of JIS S 6061. It was confirmed that the ink was ejected and a good handwriting could be formed. 〇: Can write well. ×: Cannot write.

[0063] (Low-temperature storage and then low-temperature writing test 3) The capped test samples were placed horizontally in an environmental test chamber at room temperature - 5°C and left standing for 5 months. With the samples still in the environment of room temperature - 5°C, the caps of the test samples were removed, and the character "永" with a size of 2 cm × 2 cm was written on the test paper shown in 7.3 of JIS S 6061. It was confirmed that the ink was ejected and a good handwriting could be formed. 〇: Can write well. ×: Cannot write.

[0064] (Low-temperature storage followed by low-temperature writing test 4) Place the capped test samples horizontally in an environmental test chamber at room temperature - 5°C and let them stand for 6 months. While keeping them in the environment of room temperature - 5°C, remove the caps of the test samples and write the character "永" with a size of 2 cm × 2 cm on the test paper shown in 7.3 of JIS S 6061. It was confirmed that the ink was ejected and good handwriting could be formed. 〇: Can write well. ×: Cannot write.

[0065] (Measurement of physical property values) For Examples 1 obtained as described above ~ 281 and Comparative Examples 1 - 54 , Reference examples 1~5 the following physical property values were measured. The measured physical property values and measurement methods are as follows. Also, the measurement results of each physical property value are shown in Tables 1 - 35 shown below.

[0066] <ph> The pH (indicated as pH in the table) of the ink composition of each of the Examples and Comparative Examples was measured. The pH was measured at a temperature of 25° C. using a HORIBA pH METER D-52. The pH of the ink composition is preferably 6.0 to 10.0, and more preferably 7.0 to 9.0. If the pH of the aqueous pigment ink composition for writing instruments is within the above numerical range, it becomes easy to form a bond between the amino acid anionic surfactant consisting of an unsaturated fatty acid and the pigment surface of the amino acid anionic surfactant consisting of a saturated fatty acid, and it is expected that the fluidity of the aqueous pigment ink composition for writing instruments will be maintained for a long time. <Viscosity> The viscosity of each of the Examples and Comparative Examples was measured at a temperature of 25°C and a shear rate of 16.0 / s (indicated as viscosity @16.0 in the table). The unit of the measurement results shown in the table is [mPa·s]. The viscosity was measured using Anton Paar's "MCR-302", and the measurement conditions were a temperature of 25°C and a 50 mm cone plate (1°).

[0067] [Table 1]

[0068] [Table 2]

[0069] [Table 3]

[0070] [Table 4]

[0071] [Table 5]

[0072] [Table 6]

[0073]

Table 7

[0074]

Table 8

[0075]

Table 9

[0076]

Table 10

[0077]

Table 11

[0078]

Table 12

[0079]

Table 13

[0080]

Table 14

[0081]

Table 15

[0082]

Table 16

[0083]

Table 17

[0084]

Table 18

[0085]

Table 19

[0086]

Table 20

[0087]

Table 21

[0088]

Table 22

[0089]

Table 23

[0090]

Table 24

[0091]

Table 25

[0092]

Table 26

[0093]

Table 27

[0094]

Table 28

[0095]

Table 29

[0096]

Table 30

[0097]

Table 31

[0098]

Table 32

[0099]

Table 33

[0100]

Table 34

[0101]

Table 35

[0102] The aqueous pigment ink compositions for writing instruments of Examples 1 to 281 flowed, the ink was discharged sufficiently, and the writing marks were well formed even when left to stand for 3 months or more in an environmental testing room at room temperature of -5°C.

[0103] In contrast, in Comparative Examples 1 to 54, since an amino acid anionic surfactant made of unsaturated fatty acid and an amino acid anionic surfactant made of saturated fatty acid were not used in combination, the ink composition did not flow and writing was impossible when left for 3 months or more in an environmental test room at room temperature of -5°C. In addition, even when only an amino acid anionic surfactant made of saturated fatty acid was added as in Comparative Examples 15 to 38, the ink composition did not flow and writing was impossible when left for 3 months or more in an environmental test room at room temperature of -5°C. In addition, even when multiple kinds of amino acid anionic surfactants made of saturated fatty acid were used in combination as in Comparative Examples 37 to 38, the ink composition did not flow and writing was impossible when left for 3 months or more in an environmental test room at room temperature of -5°C. In addition, even when only an amino acid anionic surfactant made of unsaturated fatty acid was added as in Comparative Examples 39 to 50 and 52 to 54, the ink composition did not flow and writing was impossible when left for 3 months or more in an environmental test room at room temperature of -5°C.

[0104] Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and also includes modifications to the above-described embodiments and appropriate combinations of these modifications.

[0105] In this specification, expressions such as "identical," "equal," and "homogeneous" that indicate that things are in an equal state not only indicate a state of strict equality, but also indicate a state in which there is a tolerance or a difference to the extent that the same function is obtained. In addition, in this specification, the expressions "comprise," "include," or "have" a certain element are not exclusive expressions that exclude the presence of other elements. [Explanation of symbols]

[0106] 1 shaft cylinder 1a front axle 1b rear axle 2. Coating destination 3 Control section 4 Cap 4a Anti-roll ribs 5 Vertical ribs 6 grooves 7 Valve seat material 7a Center hole 8 Bento 9 Coil spring 10 Posterior foramen 11 Connecting rod 12 Packing material 12a Hinge part 13 Application destination connection pipe 14 Volume adjuster< / ph>

Claims

[Claim 1] The aqueous pigment ink composition for a writing instrument comprises at least a pigment, an amino acid anionic surfactant composed of an unsaturated fatty acid, an amino acid anionic surfactant composed of a saturated fatty acid, a resin emulsion, a plate-like inorganic compound, and water, and the content of each of the amino acid anionic surfactant composed of an unsaturated fatty acid and the amino acid anionic surfactant composed of a saturated fatty acid is 10% by weight or more relative to the total amino acid anionic surfactant content of the ink composition.

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