JP2016124894A - Aqueous ink composition for ballpoint pen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous ink composition for ballpoint pen which prevents ink from attaching and contaminating into an inner wall of an ink housing tube and can clearly visually recognize a residual amount of the ink, even when a writing speed is high and ink is quickly consumed.SOLUTION: An aqueous ink composition for ballpoint pen contains at least a high-specific gravity pigment, resin particles, and a copolymer of at least one α-olefin selected from 1-ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene and vinylpyrrolidone.SELECTED DRAWING: None

Description

  The present invention relates to a water-based ink composition for ball-point pens, and more specifically, for ball-point pens in which the ink remaining on the inner wall of the ink containing tube is not contaminated and the remaining amount of ink is clearly visible even when the writing speed is high and the ink consumption is fast. The present invention relates to a water-based ink composition.

For water-based ballpoint pen inks, not only general colorants but also inks using metal powder pigments typified by aluminum powder and the like, glass flake pigments, pearl pigments, titanium oxide and other high specific gravity pigments are conventionally known. Inks using such special pigments are metallic luster, glittering glitter, pearl-like viewing angle dependence that changes color depending on the viewing angle, concealment to hide the background, writing that can be clearly seen even on dark paper This ink has excellent design and functionality, such as the ability to obtain lines. Such a high specific gravity pigment often has a particle size larger than that of a general writing pigment in order to have the above-mentioned design and functionality. For this reason, the pigment tends to precipitate and aggregate.
Conventionally, inks using pigments as colorants are known to use electrical repulsion or steric hindrance due to the dispersants to prevent pigment aggregation and settling and maintain dispersion stability over a long period of time. ing. However, when a pigment with a high specific gravity is used, if a large amount of dispersant is added in order to prevent agglomeration / sedimentation of the high specific gravity pigment, a large amount of the functional group of the activator is adsorbed on the inner wall of the ink containing tube. When a ball-point pen using a transparent resin ink containing tube is filled, there is a problem that the ink consumption state cannot be visually recognized due to the contamination of the ink inside the ink containing tube.
In particular, when titanium oxide was used as the high specific gravity pigment, the ink adhesion contamination on the inner wall of the ink containing tube was worse. This is because titanium oxide is surface-treated with alumina, silica, organic matter or the like to improve dispersibility, and the pigment itself is more easily adsorbed to the inner wall of the ink containing portion. In particular, titanium oxide having an oil absorption amount of 29 g / 100 g or more has extremely poor ink adhesion contamination on the inner wall of the ink containing portion because the surface treatment layer is thick.

In order to prevent ink from adhering to the inside of the ink containing tube, various methods have been conventionally proposed. For example, a method of adding various modified silicone oils to the ink (Patent Documents 1 and 2), a method of adding one kind of ether polyol obtained by addition polymerization of propylene oxide to diglycerin to the ink (Patents) Document 3), a method of adding hydroquinonesulfonic acid and / or salt and triethanolamine to ink is known (Patent Document 4).

Japanese Patent Laid-Open No. 50-152828 JP-A-53-36319 JP 2004-83881 A JP 2008-31371 A

  It is true that the contamination of ink adhering to the inner wall of the ink containing portion is reduced by the methods described in Patent Documents 1, 2, 3, and 4. However, when a high specific gravity pigment, especially titanium oxide, is used, the effect is not sufficient, and when the writing speed is fast and the ink consumption is fast, the ink adhesion to the inner wall of the ink containing tube becomes worse. The problem of ink contamination on the wall could not be completely solved.

  That is, the present invention is selected from at least a high specific gravity pigment, resin particles, 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene. The gist is a water-based ink composition for ballpoint pens containing at least one α-olefin and a copolymer of vinylpyrrolidone.

The mechanism by which the water-based ink composition for ballpoint pens of the present invention prevents ink adhesion contamination to the inner wall of the ink containing tube is not clear, but is presumed as follows.
1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and at least one α-olefin dissolved in water and vinylpyrrolidone By using a copolymer, a high specific gravity pigment, and the resin particle surface together, the entire ink becomes better, and as the ink is consumed by writing, the entire ink moves together. Will not remain. As a result, it is considered that ink adhesion to the inner wall of the ink storage tube can be prevented, and the visibility of the remaining amount of ink in the ink storage tube is improved.
A copolymer of an α-olefin having a carbon number higher than that of 1-nonene and vinylpyrrolidone is inferior in water solubility and cannot be used for water-based ink.

The invention is described in detail below.
The high specific gravity pigment used in the present invention refers to a pigment having a specific gravity of 2.5 or more. For example, titanium oxide (specific gravity 3.9 to 4.2), zinc white (specific gravity 5.5), bengara (specific gravity) 5.1-5.2), chromium oxide (specific gravity 5.2), iron black (specific gravity 5.2), zinc sulfide (specific gravity 4.0), chrome lead (specific gravity 4.0-7.0), molyb Dade orange (specific gravity 4.0 to 7.0), zinc chromate (specific gravity 3.5 to 3.8), strontium chromate (specific gravity 3.8), talc (2.8), barium sulfate (specific gravity 4.0 to 4.0) 4.5), calcium carbonate (specific gravity 2.6 to 2.7), lead white (specific gravity 6.8 to 6.9), ultramarine (specific gravity 1.8 to 2.7), aluminum powder (specific gravity 2.7) ), Metal powder pigments such as copper powder (specific gravity 8.7), zinc powder (specific gravity 7.1), brass powder (specific gravity 8.5), glass flake pigments A specific gravity of 3.0 to 3.4), pearl pigment (specific gravity 2.9 to 3.4), and the like can be used.
In particular, titanium oxide, metal powder pigments, glass flake pigments, pearl pigments and the like can be preferably used because the ink composition is rich in design and functionality.

  Various titanium oxides such as rutile type and anatase type can be used to use titanium oxide. Specific examples of titanium oxide include SR-1 (oil absorption 19 to 21 g / 100 g), R-3L (oil absorption 21 to 24 g / 100 g), R-5N (oil absorption 19 to 21 g / 100 g), R-7E. (Oil absorption 27 to 31 g / 100 g), R-24 (Oil absorption 21 to 24 g / 100 g), R-61N (Oil absorption 22 g / 100 g), R-62N (Oil absorption 19 to 21 g / 100 g), R-310 (Oil absorption 21 g / 100 g), R-650 (Oil absorption 20-22 g / 100 g), D-918 (Oil absorption 20-24 g / 100 g), FTR-700 (Oil absorption 19-23 g / 100 g), TCR-52 (Oil absorption 16 to 19 g / 100 g) (manufactured by Sakai Chemical Industry Co., Ltd.), Type R-550 (oil absorption 23 g / 100 g), R-580 (oil absorption 19 g / 100 g), R-63 (Oil absorption 19 g / 100 g), R-670 (oil absorption 22 g / 100 g), R-680 (oil absorption 19 g / 100 g), R-780 (oil absorption 33 g / 100 g), R-780-2 (Oil absorption 40 g / 100 g), R-820 (Oil absorption 24 g / 100 g), R-830 (Oil absorption 21 g / 100 g), R-930 (Oil absorption 19 g / 100 g), R-980 (Oil absorption) 19g / 100g), PR-690 (oil absorption 16g / 100g), PF-691 (oil absorption 15g / 100g), PF-711 (oil absorption 19g / 100g), PF-736 (oil absorption 15g) PF-737 (oil absorption 16 g / 100 g), PF-737 (oil absorption 21 g / 100 g), PF-739 (oil absorption 14 g / 100 g), PF-740 (absorption) 16g / 100g), PC-3 (oil absorption 16g / 100g), S-305 (oil absorption 23g / 100g), CR-50 (oil absorption 18g / 100g), CR-50-2 (oil absorption) 17 g / 100 g), CR-57 (oil absorption 17 g / 100 g), CR-58 (oil absorption 19 g / 100 g), CR-58-2 (oil absorption 18 g / 100 g), CR-Super 70 (oil absorption) 16g / 100g), CR-80 (oil absorption 20g / 100g), CR-85 (oil absorption 30g / 100g), CR-90 (oil absorption 21g / 100g), CR-90-2 (oil absorption) 20 g / 100 g), CR-93 (oil absorption 20 g / 100 g), CR-97 (oil absorption 19 g / 100 g), A-100 (oil absorption 22 g / 100 g), A-220 (oil absorption 22) g / 100g), (manufactured by Ishihara Sangyo Co., Ltd.), Kronos KR-270 (oil absorption 21 g / 100 g), KR-310 (oil absorption 17-22 g / 100 g), KR-380 (oil absorption 18- 24g / 100g), KR-380-N (oil absorption 18-24g / 100g), KR-480 (oil absorption 19-24g / 100g), KA-10 (oil absorption 18-28g / 100g), KA-15 (oil absorption 19-24 g / 100 g), KA-20 (oil absorption 18-23 g / 100 g), KA-30 (oil absorption 18-23 g / 100 g) (manufactured by Titanium Industry Co., Ltd.) , TITANIX JR-300 (oil absorption 18 g / 100 g), JR-301 (oil absorption 18 g / 100 g), JR-403 (oil absorption 19 g / 100 g), JR-405 (oil absorption 15 g) 100 g), JR-600A (oil absorption 19 g / 100 g), JR 603 (oil absorption 21 g / 100 g), JR-605 (oil absorption 19 g / 100 g), JR-600E (oil absorption 21 g / 100 g), JR-603 (oil absorption 21 g / 100 g), JR-800 (oil absorption 29 g / 100 g), JR-801 (oil absorption 40 g / 100 g), JR-805 (oil absorption 22 g / 100 g), JR- 806 (oil absorption 21 g / 100 g), JR-906 (oil absorption 22 g / 100 g), JR-701 (oil absorption 20 g / 100 g), JRNC (oil absorption 21 g / 100 g), JR (oil absorption 18 g / 100 g), JA-1 (oil absorption 23 g / 100 g), JA-C (oil absorption 23 g / 100 g), JA-3 (oil absorption 23 g / 100 g) (above TA-100 (oil absorption 22 g / 100 g), TA-200 (oil absorption 24 g / 100 g), TA-300 (oil absorption 21 g / 100 g), TA-400 (oil absorption 24 g / 100 g) ), TR-600 (oil absorption 19 g / 100 g), TR-700 (oil absorption 23 g / 100 g), TR-840 (oil absorption 24 g / 100 g), TR-900 (oil absorption 19 g / 100 g) (Fuji Made by Titanium Industry Co., Ltd., Taipure R-700 (oil absorption 13 g / 100 g), R-706 (oil absorption 13 g / 100 g), R-900, R-901 (oil absorption 14 g / 100 g), R-902 (oil absorption 16 g / 100 g), R-931 (oil absorption g / 100 g) (manufactured by DuPont Japan Limited) and the like.

Titanium oxide is surface-treated with alumina, silica, organic matter, etc. to improve dispersibility, and the pigment itself is more easily adsorbed to the inner wall of the ink containing portion. It is known that the surface treatment amount of titanium oxide greatly affects the oil absorption amount of titanium oxide, and the oil absorption amount tends to increase as the surface treatment amount increases.
In the present invention, the amount of oil absorption means that 2 g of titanium oxide is placed on a glass plate, the oil is dropped little by little on boiled sesame and mixed well with a metal spatula, and the mixture of oil and titanium oxide is putty-like in the boiled sesame. It is the amount (grams) converted to 100 g of titanium oxide as the amount of oil added to the boiled sesame until it has properties.

Specific examples of the metal powder pigment include Friend Color D45BL, Friend Color D462BL, Friend Color D851BL, Friend Color D451RE, Friend Color D462RE, Friend Color D111RE, Friend Color D45YE, Friend Color D462YE, Friend Color D851YE (above, Toyo Aluminum ( Co., Ltd.), Paliochrom Brilliant Orange L2850, Paliochrome Gold L2000, Paliochrome Gold L2020, Paliochrome Gold L2035, Palochrom Orange L2800, Palochrom Orange L2800, Palochrom Orange P2 Colored aluminum such as Copper L3011, Paliochrom Sparkling Red L3505, Paliochrome Blue Silver L6000, and Paliochrome Blue Silver L6001 (above, manufactured by BASF Corporation) can be used, and paste-like ones can be used.

  Specific examples of the glass flake pigment include Metashine MC1030RS, Metashine MC1030RY, Metashine MC1030RR, Metashine MC1030RB, Metashine MC1030RG, Metashine MC1040RS, Metashine MC1040RY, Metashine MC1040RR, Metashine MC1040RB, Metashine MC1040G, Shine MC1080RS, Metashine MC1080RY, Metashine MC1080RR, Metashine MC1080RB, Metashine MC1080RG, Metashine MC1080RS, Metashine MC1120RS, Metashine MC1120RY, Metashine MC1120RR, Metashine MC1120RB, Metashine MC1120RG, Tashine SC1018RS, Metashine SC1018RY, Metashine SC1018RR, Metashine SC1018RB, Metashine SC1018RG, Metashine MC1030TY, Metashine MC1030TZ, Metashine MC1030TP, Metashine MC1030TA, Metashine MC1080MC10TAZ80, Metashine MC1080MC10TP80 Metashine MC1080KY, Metashine MC1080KR, Metashine MT1030GP, Metashine MT2080GP (manufactured by Nippon Sheet Glass Co., Ltd.), and the like.

Specific examples of pearl pigments include Iriodin 120 Luster Satin,
123 Bright Luster Satin, 201 Rutile Fine Gold, 205 Rutile Platinum Gold, 211 Rutile Fine Red, 215 Rutile Red Pearl, 219 Ruil Pearl Pearl, 221 Ruil Pearl Pair, 221 Ruil Pearl Pair, 221 Ruil Pearl Pair 231 Rutile Fine Green, 235, 302 Gold Satin, 323 Royal Gold Satin, 520 Bronze Satin, 522 Red Brown Satin, 524 Red Satin (above, Merck Japan L) MB-100R, MG-100R, MR-1 0R, MV-100R, MRB-100R, MY-100R, MB-100RF, MB-100RF, MG-100RF, MRB-100RF, MY-100RF, ULTIMICA YB-100, YD-100, RB- 100, the same RD-100, the same VB-100, the same VD-100, the same GB-100, the same GD-100 (above, manufactured by Nippon Koken Kogyo Co., Ltd.) and the like.
These high specific gravity pigments can be used alone or in combination of two or more, and the amount used is preferably 0.5% by weight or more and 30% by weight or less based on the ink composition.

  Pigments other than the above high specific gravity pigments can also be used in combination with high specific gravity pigments for the purpose of providing color effects such as vividness, pastel tone, and handwriting fastness, azo pigments, nitroso pigments, nitro pigments, basic Organic pigments (specific gravity 1.2 to 1.9) such as dye pigments, acid dye pigments, building dye pigments, mordant dye pigments, and natural dye pigments, furnace black, channel black, thermal black Inorganic pigments such as carbon black (specific gravity 1.8 to 2.1), bitumen (specific gravity 1.7 to 1.9), white carbon (specific gravity 1.9 to 2.2) such as acetylene black, metal vapor deposition pigments (Specific gravity 1.2-1.4) etc. can be used.

  Specific examples of organic pigments include aniline black, cyanine black, naphthol yellow S, Hansa Yellow 10G, 5G, 3G, 3R, G, 4, GR, A, RN, R, and pigment yellow. L, Benzidine Yellow, Benzine Yellow G, Benzine Yellow GR, Permanent Yellow NCG, Permanent Yellow FGL, Permanent Yellow H10G, Permanent Yellow HR, Vulcan Fast Yellow 5G, Vulcan Fast Yellow R, Tartrazine Lake, Quinoline Yellow Lake, Anthracene Yellow 6GL, Anthrapyrimidine Yellow, Sudan I, Resol Fast Orange, Permanent Orange GTR, Vulcan Fast Orange GG, Benzidine Orange G, Persian Orange, Indanthrene Brilliant Orange G , Indanthrene Brilliant Orange GK, Indanthren Brilliant Orange RK, Indanthren Brilliant Orange GR, Permanent Brown FG, Para Brown, Permanent Red 4R, Fire Red, Parachlor Orthoaniline Red, Resol Fast Scarlet, Brilliant Fast Scarlet, Permanent Red F2R, Permanent Red F4R, Permanent Red FRL, Permanent Red FRLL, Permanent Red F4RH, Fast Scarlet VD, Vulcan Fast Rubin B, Vulcan Fast Pink G, Light Fast Red Toner B, Light Fast Red Toner R, Permanent Carmine FB, Brilliant Carmine BS, pyrazolone red, resol red, rake Red C, Lake Red D, Quinacridone Red, Anthosine B, Brilliant Scarlet G, Risor Rubin GK, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon (CI. 12350), Permanent Bordeaux F2R ( CI 12385), Helio Bordeaux BL (C.I. 14830), Bordeaux 10B (C.I. 15880), Bon Maroon Light (C.I. 15825), Bom 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, Thioindigo Maroon , Pa -Manten Red FGR, PV Carmine HR, Watching Red, Monolite Fast Red YS, Permanent Red BL, Methyl Violet Lake, Fast Violet B, Dioxane Violet, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue Indanthrene Blue RS, Indanthrene Blue BC, Indigo, Pigment Green B, Naphthol Green B, Green Gold Acid Green Lake, Phthalocyanine Green, Malachite Green Lake, Phthalocyanine Green, C.I. I. Pigment Blue 2, 9, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17, 17, 22, 25 28, 29, 36, 60, 66, 68, 76, 80, C.I. I. PigmentRed 2, 3, 5, 8, 14, 17, 17, 22, 31, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48 : 4, 49, 50: 1, 53: 1, 53: 2, 53: 1, 58: 2, 60, 63: 1, 63: 2, 63: 1, 64: 1, 88, 112, 122, 123, 144, 146, 149, 166, 168, 170, 175, 176, 177, 178, 179, 180, 184, 185, 187, 188, 190, 194, 202, 206, 207, 208, 209, 210, 211, 213, 214, 216, 242, 245 253, 254, 255, 256, 257, 264, 266 The 268, the 270, the 272, C. I. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 17, 24, 55, 73, 74, 79, 81, 83, 93, 94, 95 97, 99, 108, 109, 110, 111, 117, 120, 128, 133, 136, 138, 139, 147, 151, 153, 154, 155, 166, 167, 173, 174, 175, 176, 180, 185, 191, 194, 213, C.I. I. Pigment Orange 5, 10, 13, 16, 34, 36, 38, 40, 43, 61, 62, 64, 68, 71, 72, 73, 74 , C.I. I. PigmentGreen7, 10, 36, 37, C.I. I. Pigment Violet 19, 23, 31, 33, 36, 37, 38, 50, C.I. I. PIGMENT BROWN 23, 25, 26, C.I. I. PIGMENT BLACK 7 etc. are mentioned.

  Specific examples of carbon black include Mitsubishi Carbon Black # 10B, # 20B, # 14, # 25, # 30, # 33, # 40, # 44, # 45, # 45L, # 50, # 55, # 95, # 260, # 900, # 1000, # 2200B, # 2300, # 2350, # 2400B, # 2650, # 2700, ## 4000B, CF9, MA8, MA11, MA11, MA77, MA100, MA220, MA230, MA230, MA600 and MCF88 (manufactured by Mitsubishi Chemical Corporation), Monarch 120, Monarch 700, Monarch 800, Monarch 880, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Mogal L, Legal 99R, Legal 250R, Legal 300 Legal 330R, Legal 400R, Legal 500 and Legal 660R (above, manufactured by Cabot Corporation, USA), Printex A, Printex G, Printex U, Printex V, Printex 55, Printex 140U, Printex 140V , Printex 35, Printex 40, Printex 45, Printex Printex 85, Nine Pex 35, Special Black 4, Special Black 4A, Special Black 5, Special Black 6, Special Black 100, Special Black 250, Special Black 350 , Special Black 550, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color -Black FW200, Color Black S150, Color Black S160 and Color Black S170 (above, Degussa Japan Co., Ltd.), Raven 5000 Ultra II, Raven 2500 Ultra, Raven 1250, Raven 760 Ultra (above, Colombian Carbon Japan Ltd.) Manufactured) and the like.

Specific examples of the metal deposition material include: LNG neo SILVER # 35, LG neo R-GOLD # 35, LG neo B-GOLD # 35, LG neo S-GOLD # 35, LG neo SILVER # 100, LG neo R-GOLD # 100, Elgie neo B-GOLD # 100, Elgie neo S-GOLD # 100, Elgie neo RED # 100, Elgie neo BLUE # 100, Elgie neo GREEN # 100, Elgie neo VIOLET # 100, Elgie neo BLACK # 100, Elgi neo COPPER # 100, Elgie neo PINK # 100, Elgie neo YELLOW # 100, Elgie neo Silver # 150, Elgie neo R-GOLD # 50, Elgie neo B-GOLD # 150, Elgie neo S-GOLD # 150, Elgie neo RED # 150, Elgie neo BLUE # 150, Elgie neo GREEN # 150, Elgie neo VIOLET # 150, Elgie neo BLACK # 150, Elgie neo COPPER # 150, Elgie neo PINK # 150, Elgie neo YELLOW # 150, Elgie neo SILVER # 200, Elgie neo R-GOLD # 200, Elgie neo B-GOLD # 200, Elgie neo S-GOLD # 200, Elgie neo RED ## 200, Elgie neo BLUE # 200, Elgie neo GREEN # 200, Elgie neo Violet # 200, Elgie neo B ACK # 200, Elgie neo Copper # 200, Elgie neo PINK # 200, Elgie neo YELLOW # 200, Elgie neo SILVER # 325, Elgie neo R-GOLD # 325, Elgie neo B-GOLD # 325, Elgie neo S-GOLD # 200 325, Elgie neo RED # 325, Elgie neo BLUE # 325, Elgie neo GREEN # 325, Elgie neo VIOLET # 325, Elgie neo BLACK # 325, Elgie neo COPPER # 325, Elgie neo PINK # 325 EL, EL LO WY # 25 EL Elgie neo Silver # 500, Elgie neo R-GOLD # 500, Elgie neo B-Gold # 500 Eruji neo S-GOLD # 500 (manufactured by Oike Imaging Corp.), 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 Maron H55, Diamond Piece Ocean Green H55, Diamond Piece Sky Blue H55, Diamond Piece Black H55, Diamond Piece Pink H55, Diamond Piece Violet H55, Diamond Piece Emerald H55, Diamond Piece Copper H55, Diamond Piece LG Gold CO-40UC, diamond piece DG Gold CO-40UC, diamond piece Green CO-40UC, diamond piece Blue CO-40UC, diamond piece Red CO-40UC, diamond piece Pink CO-40UC, diamond piece Lavender CO- 0UC (above, Dia Kogyo Co.) and the like as a metal deposition pigment.
These pigments can be used alone or in combination of two or more, and the amount used is preferably 0.1% by weight or more and 60% by weight or less based on the total amount of the ink composition.

In order to disperse the pigment stably, a dispersant is used. As the pigment dispersant, those used as a conventionally known pigment dispersant such as a water-soluble resin or a water-soluble resin and an anionic or nonionic surfactant can be used. For example, as a polymer dispersant, natural rubbers such as gum arabic and tragacanth, glucosides such as saponin, cellulose derivatives such as methylcellulose, carboxycellulose and hydroxymethylcellulose, natural polymers such as lignin sulfonate and shellac, poly Anionic polymer such as acrylate, salt of styrene-acrylic acid copolymer, salt of vinyl naphthalene-maleic acid copolymer, sodium salt of β-naphthalene sulfonic acid formalin condensate, phosphate, etc. Nonionic polymers such as alcohol and polyethylene glycol are listed. Preferably, it is a polyacrylate or a salt of a styrene-acrylic acid copolymer. Specific examples of the polyacrylate include Aqualic L DL, YS, Aqualic HIH, FH, MH (above, Specific examples of sodium polyacrylate, manufactured by Nippon Shokubai Co., Ltd., VISCOMATE F-480SS (above, sodium polyacrylate, manufactured by Showa Denko KK), and styrene-acrylic acid copolymer salt 57J, 60J, 63J, 70J (above, aqueous solution of styrene-acrylic acid copolymer salt, manufactured by BASF Japan Ltd.).
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 dispersants can be used by selecting one or more of them in combination. The amount used is preferably 0.05% by weight or more and 20% by weight or less with respect to 10 parts by weight of the pigment.

  Furthermore, the use of a water-based ink base dispersed in an aqueous medium is advantageous for pigment ink production. Specifically, Fuji SP Black 8031, 8119, 8167, 8276, 8276, 8381, 8406, Fuji SP Red 5096, 5111, 5193, 5220, Fuji SP Bordeaux 5500, Fuji SP Blue 6062, 6133. 6134, 6401, Fuji SP Green 7051, Fuji SP Yellow 4060, 4178, Fuji SP Violet 9011, Fuji SP Pin 9524, 9527, Fuji SP Orange 534, FUji SP B 543, FUji SP Orange 534, FUji SP Orange 534, FUji SP Orange 534, FUji SP Orange 534 (Fuji Dye Co., Ltd.), Emacol Black CN, Emacol Blue FBB, FB KR, Emacol Green LXB, Emacol Violet BL, Emacol Brown 3101, Emacol Carmine FB, Emacol Red BS, Emacol Orange R, Emacol Yellow FD, Nr G601, G F7G, 10GN, 10G, Sandy Super Black K, C, Sandy Super Gray B, Sandy Super Brown SB, FRL, RR, Sandy Super Green L5G, GB , FBL-H, FBL-160, FBB, Sandye Super Viol et BL H / C, same BL, Sandy Super Bordeaux FR, Sandy Super Pink FBL, F5B, Sandy Super Rubbe FR, Sandy super Car Rine, FR Same BO, Sandy Gold Yellow 5GR, Same R, Same 3R, Sandy Ywlow GG, Same F3R, Same IRC, Same FGN, Same GN, Same GRS, Same GSR-130, Same GSN-130, Same GSN, Same 10GN (and above) Sanyo Dye Co., Ltd.), Rio Fast BlackFx 8012, 8313, 8169, Rio Fast Red Fx8209, 817 , Rio Fast Red S FX 8315, 8316, Rio Fast Blue FX 8170, Rio Fast Blue FX 8170, Rio Fast Blue S FX 8312, Rio Fast Green S Ink 83 2102, 2103, 2104, 2105, 2106, 2107, 2108, 2117, 2127, 2137, 2167, 2101P, 2102P, 2103P, 2104P, 2105P, 2105P 2106P, 2107P, 2108P, 2117P, 2117P, 2127P, 2137P, 2167P, NKW-3002, 3003, 3004, 3005, 3007, 3077, 3008 3402, 3404, 3405, 3407, 3408, 3408, 3477, 3602, 3603, 3604, 3605, 3607, 3777, 3608, 3702, 3703, 3704, 3705 3777, 3708, 6013, 6038, 6559 (above, manufactured by Nippon Fluorescence Co., Ltd.), Cosmo Color S1000F series (produced 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 (above, manufactured by Gokoku Color Co., Ltd.), Pollux PC5T1020, Pollux Black PC8 135, Po look thread IT1030 like 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.

  Also, water-based dyes that have been widely used in conventional water-based ink compositions for ballpoint pens can be used, and any of direct dyes, acid dyes, basic dyes, and the like can be used. Specific examples of water-soluble dyes include Japan 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 Conch (51), Kayara Spragley VGN (71), Kayalas Direct Brilliant Yellow G (C.I. Direct Yellow 4), Direct Fast Yellow 5GL (same 26), Eisen Primula Yellow GCLH (same 44), Direct Fast Yellow R (same 50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Ska Let GSX (same 4), Direct Fast Scarlet 4BS (same 23), Eisen Direct Rhodulin BH (same 31), Direct Scarlet B (same 37), Kayak Direct Scarlet 3B (same 39), Eisen Primula Pink 2BLH (same as above) 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) , Kayara Light Rose FR (227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (15), 41, Sumilite Spula Blue BRR Conch (71), Dibogen Turquoise Blue S (86), War -Direct dyes such as Blue # 3 (86), Kayara Star Coyze Blue GL (86), Kayala Supra Blue FF2GL (106), 108, Kayara Splatter 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 Conch (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conque (52), Sumilan Black WA (52), Ranil Black BG Extra Conk (107), Kayanol Milling Black TLB (109), Suminoll Milling Black B (109), Kayano Lumining 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), Kayakaku 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 as 141), Kayanor Yellow NG (same as 135), Kaya Lumining 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 (Same 51), kayak acid rhodamine FB (same 52), Suminol leveling rubinol 3GP (same 57), diacid alizarin rubinol F3G 200% (same 82), 83, Eiseneosin GH (same 87), water pink # 2 (92), Eisen Acid Flow Shin PB (92), Rose Bengal (94), Kayanol Milling Scarlet FGW (111), Kayanol Milling Rubin 3BW (129), Suminoall 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 BL (265), Kyanol Milling Red GW (276), Mitsui Acid Violet 6BN (CI Acid Violet 15), Mitsui Acid Violet BN (17), 49, Sumitomo Patent Pure Blue VX (C.I. I. 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 Soluble Blue OBC (same as 22), Suminol Leveling Blue 4GL (same as 23), Mitsui Nylon Fast Blue G (same as 25), Kayasil Blue AGG (same as 40), Kayasil Blue BR (same as 41), Mitsui Alizarin Saffirole SE (same as above) 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 Solve Blue OBB (93), 100, Sumitomo Brilliant Blue 5G (103), 104, Kyanol Milling Ultra Sky SE (112), Kyanol Milling Cyanine 5R (113), Eisen Opal Blue 2GLH (158) ), Daiwa Guinea Green B (CI Acid Green 3), Acid Brilliant Milling Green B (9), Daiwa Green # 70 (16), Cyanol Cyanine Green G (25), Suminol Milling Green G (Ibid. 27), acidic dyes such as acid dyes such as Acid Orange 56, C.I. I. Food dyes such as Food Yellow 3, Eisen Katylon Yellow 3GLH (CI Basic Yellow 11), Eisen Katylon Brilliant Yellow 5GLH (13), Sumiacryl Yellow E-3RD (15), Maxilon Yellow 2RL ( 19), Astrazon Yellow 7GLL (21), Kayacrill Golden Yellow GL-ED (28), Astrazon Yellow 5GL (51), Eisen Katillon Orange GLH (CI Basic Orange 21), Eisen Catillon Brown 3GLH (30), Rhodamine 6GCP (CI Basic Red 1), Eisen Astrafloxin (12), Sumiacryl Brilliant Red E-2B (15), Astrazone Red GTL (18), Aizen Cachiron Buri And Pink BGH (27), Maxilon Red GRL (46), Eisenmethyl Violet (CI Basic Violet 1), Eisen Crystal Violet (3), Eisen Rhodamine B (10), Astrazone Blue G ( CI Basic Blue 1), Astrazone Blue BG (3), Methylene Blue (9), Maxilon Blue GRL (41), Eisen Cachiron Blue BRLH (54), Eisen Diamond Green GH (C.I.) I. Basic Green 1), Eisen Malachite Green (Same 4), Bismarck Brown G (CI Basic Brown 1), Malachite Green (CI 42000), Victoria Blue FB (CI 44045), Methyl Violet FN (C.I. 4253 ), Rhodamine F4G (C.I.45160), basic dye rhodamine 6GCP (C.I.45160), etc., C. I. Solvent Black 3, 7, 20, 20, 24, C.I. I. Solvent Red 8, 49, C.I. I. Solvent Blue 2, 5, 25, 38, 44, 55, 64, 70, C.I. I. Solvent Green 3, C.I. I. Solvent Yellow 21, 34, 47, 61, 82, C.I. I. Solvent Orange 25, 37, C.I. I. Solvent Violet 8, 9 and 21, C.I. I. Basic Blue 1, 7, 7, 8, C.I. I. Basic Violet 3, C.I. I. Basic red 1 etc. are mentioned.

The resin particles used in the present invention are made of polyethylene, polypropylene, vinyl chloride, polymethacrylate, benzoguanamine, nylon, styrene-butadiene copolymer, styrene-acrylotolyl copolymer, styrene-acrylic copolymer, silicone resin, etc. Examples of the shape include a spherical shape, an irregular shape, and a hollow shape.
Specific examples of the resin particles include Eposter S, S6, S12 (above, melamine / formaldehyde condensate, manufactured by Nippon Shokubai Chemical Industry Co., Ltd.), Eposta MS, M05, L15 (above, benzoguanamine formaldehyde condensate). , Nippon Shokubai Chemical Industry Co., Ltd.), Eposter M30 (Benzoguanamine / melamine / formaldehyde condensate, Nippon Shokubai Chemical Industry Co., Ltd.), Nylon SP500 (Nylon, Toray Industries, Inc.), LX407BP (styrene-butadiene co-polymer) Polymer), LX407BP6 (styrene-butadiene copolymer) (manufactured by Nippon Zeon Co., Ltd.), Lumicol NKW2109 (styrene-acrylonitrile copolymer, manufactured by Nippon Fluorescence Co., Ltd.), and the like. Specific examples of the hollow resin particles include MH5055 (styrene-butadiene copolymer, manufactured by Nippon Zeon Co., Ltd.), SX863 (A), SX864 (B), SX865 (B) (above, styrene-acrylic copolymer). , Nippon Synthetic Rubber Co., Ltd.), Ropeke OP-62, OP-84J, HP-91 (above, acrylic-styrene copolymer, manufactured by Rohm and Haas Japan Co., Ltd.), Chemipearl W10, The same W200, the same W300, the same W400, the same W500, the same WF640, the same W308, the same W700, the same W950 (polyolefin, manufactured by Mitsui Petrochemical Co., Ltd.) and the like. Specific examples of resin particles colored with dyes include SW-11, SW-12, SW-13, SW-14, SW-15, SW-16, SW-17, SW-18, SW-27, SW -37, SW-47 (manufactured by Shinrohihi Co., Ltd.), Lumicol NKW-2101, NKW-2102, NKW-2103, NKW-2104, NKW-2108, NKW-2117, NKW-2127, NKW-2137, NKW-2167 (therefore, a styrene-acrylonitrile copolymer, manufactured by Nippon Fluorochemicals Co., Ltd.).
Specific examples of silicone resin particles include Tospearl 105, 120, 130, 145, 2000B, 1110, and 240 (manufactured by Momentive Performance Materials Japan GK).
These resin particles can be used alone or in combination of two or more, and the amount used is preferably 0.5 wt% or more and 30 wt% or less with respect to the total amount of the ink composition.

At least one α-olefin selected from 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene used in the present invention and vinylpyrrolidone; This copolymer can be prevented from adhering to the ink inner wall by being added into the ink together with the high specific gravity pigment and the resin particles. Examples of commercially available products include GANEX P-904LC, ANTARON P-904, AGRIMER AL (manufactured by ISP) and the like.
Also, a copolymer of vinyl pyrrolidone and at least one α-olefin selected from 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene. The coalescence not only prevents ink adhesion but also acts as a dispersant for the high specific gravity pigment. Therefore, it is possible to stabilize the dispersion by preventing aggregation / sedimentation of the high specific gravity pigment without using a large amount of a dispersant. Therefore, both the prevention of ink adhesion and the stabilization of dispersion of the high specific gravity pigment can be achieved. Is.
These copolymers can be used alone or in combination of two or more, and the amount used is preferably 0.1% by weight or more and 20% by weight or less based on the total amount of the ink composition.

  In addition to the above, various conventionally known resins can be added for the purpose of adjusting the viscosity and improving the fixability to the paper surface. As an example of the viscosity adjusting resin, as a binder for fixing the ink coloring material on the paper surface, specifically, shellac, styrene-maleic acid copolymer, alkali metal salt of styrene-acrylic acid copolymer Water-soluble resins such as amine salts, ammonium salts, alkali metal salts of α-methylstyrene-acrylic acid copolymers, amine salts, and ammonium salts can be used. In addition, water-insoluble resins such as acrylic resins, vinyl acetate resins, and styrene-butadiene copolymers can also be used. The water-insoluble resin is used in the form of an aqueous emulsion.

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

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

In addition to the above components, various additives conventionally used in water-based inks for writing instruments can be used as necessary. For example, sugar alcohols such as sorbit and xylit are used to prevent ink evaporation, and polyethylene glycol, polyoxyethylene glycol polyoxypropylene glycol, alkali metal salts of oleic acid and amine salts are used to improve writing feeling. A lubricant can be used. Furthermore, anionic, nonionic, cationic surfactants, silicone surfactants, fluorine surfactants and other surface tension modifiers, sodium dehydroacetate, 1,2-benzoisothiazin-3-one, etc. Antiseptic / antifungal agent, benzotriazole, rust inhibitor such as ethylenediaminetetraacetic acid,
Alkaline agents such as sodium hydroxide, alkanolamine, amine and ammonium can also be used as a pH adjuster.

  Various methods known in the art can be employed as the ink production method. A pigment dispersion is prepared by dispersing a pigment together with a solvent, a dispersion resin, and an activator, and a solvent, a resin, and an additive are added and mixed during ink adjustment. Moreover, it is possible to use the general method generally used for disperse | distributing a pigment. For example, a pigment, a solvent, and a dispersing agent are mixed and uniformly stirred with a propeller stirrer or the like, and then the pigment is dispersed with a disperser. A dispersing machine such as a roll mill, a ball mill, a sand mill, a bead mill, or a homogenizer is appropriately selected depending on the amount of the solvent of the ink and the pigment concentration.

  Filtration and centrifugation may be performed to remove coarse particles and gas. Heating, cooling, pressurization, decompression, or inert gas replacement may be performed during production. The power may be electricity or pressurized air. These may be used alone or in combination.

As the tip of the ballpoint pen, a metal tip using metal for the ball holder and a resin tip mainly using synthetic resin can be used. Commonly used materials such as white, brass, and stainless steel can be used as the material for the ball holder using metal. Further, as a main material of a ball holder mainly made of a synthetic resin, a general molding resin can be used.
% You may shape | mold with these synthetic resins. Specifically, polyacetal resin, polybutylene terephthalate resin, aromatic nylon resin, modified polyphenylene ether resin, polyacrylate resin and the like can be used. Polyacetal resins, polyethylene terephthalate resins, and polybutylene terephthalate resins are particularly preferred because of the smooth writing feel.
Various fillers can be added to these resins for the purpose of improving lubricity, improving wear resistance, improving strength, and the like. Examples of the filler include molybdenum, potassium titanate, glass fiber, calcium carbonate, mica and the like. The amount of these fillers is preferably 30% or less. If added over 40%, the filler may be unevenly formed during molding and the shape of the chip may be impaired.

As an example of the ball material to be held by the ball holder, balls such as cemented carbide whose main component is tungsten carbide, one whose main component is silicon carbide, and one whose main component is zirconia can be used.

  As the ink containing portion for containing this water-based ink composition for ballpoint pens, those made of metal or synthetic resin can be used. If it is made of transparent or translucent synthetic resin, the remaining amount of ink can be clearly indicated. In this case, as long as the resin does not dissolve or swell in the ink solvent, any resin that is used as an ink containing portion of a conventional water-based ballpoint pen can be used. For example, there are polyethylene, polypropylene, polyurethane, polyethylene terephthalate, polyamide, polyacrylonitrile resin, polyarylate, ethylene-vinyl alcohol copolymer, fluororesin, silicone resin, etc. Polypropylene can be used favorably from the viewpoint of price and visibility . Further, a backflow preventing composition may be filled at the rear end of the ink.

Hereinafter, it demonstrates still in detail based on an Example and a comparative example.
Example 1
TITANIX JR-800 (titanium oxide, oil absorption 29g / 100g, TEIKA CORPORATION
10.00 parts by weight Ropaque OP-62 (hollow resin particle acrylic-styrene copolymer,
Resin solid content: 37.5%) 38.00 parts by weight GANEX P-904LC (vinylpyrrolidone / 1-butene copolymer, manufactured by ISP)
0.35 parts by weight Kelzan AR (xanthan gum, manufactured by Sansho Co., Ltd.) 0.60 parts by weight ion-exchanged water 36.95 parts by weight ethylene glycol 5.50 parts by weight glycerin 4.50 parts by weight Proxel GXL (antifungal agent, Avicia Co., Ltd.) 0.30 parts by weight PO-20 (sugar alcohol, manufactured by Towa Kasei Kogyo Co., Ltd.) 3.00 parts by weight BYK-035 (antifoaming agent, manufactured by Big Chemie Japan Co., Ltd.) 0.30 Part by weight AKP-20 (alumina, manufactured by Sumitomo Chemical Co., Ltd.) 0.50 part by weight Of the above components, TITANIX JR-800, GANEX P-904LC, 27.55 parts by weight of ion-exchanged water, ethylene glycol, and glycerin Were mixed and stirred, and dispersed with a bead mill for 1 hour to prepare a pigment dispersion. Next, Ropaque OP-62, Proxel GXL, PO-20, BYK-035 and AKP-20 were added and mixed and stirred for 30 minutes. Further, Kelzan AR and 9.40 parts by weight of ion-exchanged water were mixed, and a Kelzan AR aqueous solution obtained by stirring for 1 hour was added, followed by stirring for 1 hour with a homogenizer to obtain a white aqueous ink composition.

(Example 2)
Taipei P-780 (titanium oxide, oil absorption 33g / 100g, manufactured by Ishihara Sangyo Co., Ltd.)
12.00 parts by weight Water Blue 119 (blue dye, manufactured by Orient Chemical Co., Ltd.) 2.00 parts by weight Eposter S (resin particles, melamine / formaldehyde condensate, manufactured by Nippon Shokubai Co., Ltd.)
18.00 parts by weight ANTARON P-904 (vinyl pyrrolidone / 1-butene copolymer, manufactured by ISP)
0.30 parts by weight Kelzan AR (described above) 0.40 parts by weight Jonkrill 60J (dispersant, aqueous solution of styrene-acrylic acid copolymer salt, manufactured by BASF) 5.00 parts by weight ion-exchanged water 48.20 parts by weight Ethylene glycol 5.50 parts by weight Glycerin 4.50 parts by weight Proxel GXL (described above) 0.30 parts by weight PO-20 (described above) 3.00 parts by weight BYK-035 (described above) 0.30 parts by weight AKP-20 (described above) ) 0.50 parts by weight Of the above components, TYPEKE R-780, ANTARON P-904, Jonkrill 60J, 41.93 parts by weight of ion-exchanged water, ethylene glycol and glycerin are mixed and stirred, and dispersed in a bead mill for 1 hour. A pigment dispersion was prepared. Next, water blue 119, Eposter S, Proxel GXL, PO-20, BYK-035 and AKP-20 were added and mixed and stirred for 30 minutes. Furthermore, Kelzan AR and 6.27 parts by weight of ion-exchanged water were mixed and a Kelzan AR aqueous solution obtained by stirring for 1 hour was added, followed by stirring for 1 hour with a homogenizer to obtain a white aqueous ink composition.

Example 3
Tycop R-780-2 (Titanium oxide, oil absorption 40g / 100g, Ishihara Sangyo Co., Ltd.)
Manufactured by) 18.00 parts by weight Lumicol NNW-2108 (colored resin particles, styrene-acrylonitrile copolymer,
Nippon Fluorescent Co., Ltd.), 28.00 parts by weight AGRIMER AL-10LC (vinyl pyrrolidone / 1-butene copolymer, manufactured by ISP) 0.60 parts by weight Alcathylan (polysaccharide, manufactured by Hakuto Co., Ltd.) 0 .45 parts by weight ion-exchanged water 38.40 parts by weight glycerin 4.50 parts by weight diethylene glycol 6.00 parts by weight Proxel GXL (described above) 0.30 parts by weight PO-20 (described above) 3.00 parts by weight BYK-035 (described above) ) 0.30 parts by weight AKP-20 (described above) 0.45 parts by weight Of the above components, TYPEKE R-780-2, AGRIMER AL-10LC, ion-exchanged water, glycerin and diethylene glycol were mixed and stirred, and 1 in a bead mill. A pigment dispersion was produced by time dispersion. Next, Lumicol NNW-2108, Proxel GXL, PO-20, BYK-035, AKP-20 and Alkathylan were added and stirred with a homogenizer for 1 hour to obtain a white aqueous ink composition.

Example 4
Taipei P-550 (titanium oxide, oil absorption 23g / 100g, manufactured by Ishihara Sangyo Co., Ltd.)
31.00 parts by weight Ropaque OP-62 (previously described) 1.25 parts by weight GANEX P-904LC (previously described) 0.40 parts by weight Kelzan AR (previously described) 0.87 parts by weight ion-exchanged water 52.88 parts by weight ethylene glycol 5 .50 parts by weight Glycerin 4.00 parts by weight Proxel GXL (previously described) 0.30 parts by weight PO-20 (previously described) 3.00 parts by weight BYK-035 (previously described) 0.30 parts by weight AKP-20 (previously described) 50 parts by weight Among the above-mentioned components, Tyco R-550, GANEX P-904LC, 39.25 parts by weight of ion-exchanged water, ethylene glycol and glycerin were mixed and stirred, and dispersed with a bead mill for 1 hour to prepare a pigment dispersion. Next, Ropaque OP-62, Proxel GXL, PO-20, BYK-035 and AKP-20 were added and mixed and stirred for 30 minutes. Furthermore, Kelzan AR and 13.63 parts by weight of ion-exchanged water were mixed, and a Kelzan AR aqueous solution obtained by stirring for 1 hour was added, followed by stirring for 1 hour with a homogenizer to obtain a white aqueous ink composition.

(Example 5)
Kronos KR-380 (titanium oxide, oil absorption 18-24 g / 100 g, manufactured by Titanium Industry Co., Ltd.) 15.00 parts by weight FUJI SP BLUE 6401 (pigment water dispersion, manufactured by Fuji Dye Co., Ltd.)
13.00 parts by weight Eposter S (described above) 2.50 parts by weight ANTARON P-904 (described above) 1.50 parts by weight Alkathylan (described above) 0.38 parts by weight ion-exchanged water 54.07 parts by weight ethylene glycol 5.50 Parts by weight glycerin 4.00 parts by weight Proxel GXL (previously described) 0.30 parts by weight PO-20 (previously described) 3.00 parts by weight BYK-035 (previously described) 0.30 parts by weight AKP-20 (previously described) 0.45 parts by weight Part Of the above components, Kronos KR-380, ANTARON P-904, ion-exchanged water, ethylene glycol, and glycerin were mixed and stirred, and dispersed for 1 hour with a bead mill to prepare a pigment dispersion. Next, FUJI SP BLUE 6401, Eposter S, Proxel GXL, PO-20, BYK-035, AKP-20, and Alkathylan were added and stirred for 1 hour with a homogenizer to obtain a pastel water-based ink composition. .

(Example 6)
Iron black 0.45 parts by weight Ropaque PO-62 (previously described) 55.00 parts by weight GANEX P-904LC (previously described) 0.80 parts by weight Kelzan AR (previously described) 0.69 parts by weight Aquaric L DL (sodium polyacrylate) Manufactured by Nippon Shokubai Co., Ltd.)
5.00 parts by weight ion-exchanged water 22.96 parts by weight glycerin 4.50 parts by weight diethylene glycol 6.50 parts by weight Proxel GXL (described above) 0.30 parts by weight PO-20 (described above) 3.00 parts by weight BYK-035 ( 0.30 parts by weight AKP-20 (described above) 0.50 parts by weight Among the above components, iron black, GANEX P-904LC, Aqualic L DL, 12.15 parts by weight of ion-exchanged water, diethylene glycol and glycerin. The mixture was stirred and dispersed with a bead mill for 1 hour to prepare a pigment dispersion. Next, Ropaque PO-62, Proxel GXL, PO-20, BYK-035 and AKP-20 were added and mixed and stirred for 30 minutes. Further, Kelzan AR and 10.81 parts by weight of ion-exchanged water were mixed, a Kelzan AR aqueous solution obtained by stirring for 1 hour was added, and the mixture was stirred for 1 hour by a homogenizer to obtain a black aqueous ink composition.

(Example 7)
Friend color D851BL (colored aluminum, manufactured by Toyo Aluminum Co., Ltd.)
12.00 parts by weight LNG neo GREEN # 150 (metal deposition pigment, manufactured by Oike Industry Co., Ltd.)
2.00 parts by weight Ropaque OP-62 (previously described) 51.00 parts by weight ANTARON P-904 (previously described) 1.20 parts by weight Kelzan AR (previously described) 0.85 parts by weight ion-exchanged water 19.35 parts by weight ethylene glycol 5 .50 parts by weight Glycerin 4.00 parts by weight Proxel GXL (previously described) 0.30 parts by weight PO-20 (previously described) 3.00 parts by weight BYK-035 (previously described) 0.30 parts by weight AKP-20 (previously described) 50 parts by weight Of the above components, Friend Color D851BL, Lg neo GREEN # 150, ANTARON P-904, 6.03 parts by weight of ion-exchanged water, ethylene glycol and glycerin are mixed and stirred, and then Ropaque PO-62 Proxel GXL, PO-20, BYK-035 and AKP-20 were added and mixed and stirred for 30 minutes. Furthermore, Kelzan AR and 13.32 parts by weight of ion-exchanged water were mixed, and a Kelzan AR aqueous solution obtained by stirring for 1 hour was added, followed by stirring for 1 hour with a homogenizer to obtain a glittering water-based ink composition.

(Example 8)
Metashine MC1030RB (Glass flakes, manufactured by Nippon Sheet Glass Co., Ltd.)
10.00 parts by weight Water Blue 119 (previously described) 5.00 parts by weight Eposter S (previously described) 20.00 parts by weight AGRIMER AL-10LC (previously described) 0.35 parts by weight Alkathylan (previously described) 0.45 parts by weight ion exchange Water 50.60 parts by weight Ethylene glycol 5.50 parts by weight Glycerin 4.00 parts by weight Proxel GXL (previously described) 0.30 parts by weight PO-20 (previously described) 3.00 parts by weight BYK-035 (previously described) 0.30 parts by weight Part AKP-20 (described above) 0.50 parts by weight Among the above components, Metashine MC1030RB, AGRIMER AL-10LC, ion-exchanged water, ethylene glycol and glycerin are mixed and stirred, and then water blue 119 and Eposter S Proxel GXL, PO-20, BYK-035, AKP-20 and Alcaceira It was added, stirred for 1 hour with a homogenizer to obtain a aqueous glittering ink composition.

Example 9
Pearl glaze MRB-100RF (Pearl pigment, manufactured by Nippon Koken Kogyo Co., Ltd.)
8.50 parts by weight Lumicol NKW-2108 (previously described) 42.00 parts by weight GANEX P-904LC (previously described) 0.30 parts by weight Alkathylan (previously described) 0.39 parts by weight ion-exchanged water 35.21 parts by weight ethylene glycol 5 .50 parts by weight Glycerin 4.00 parts by weight Proxel GXL (previously described) 0.30 parts by weight PO-20 (previously described) 3.00 parts by weight BYK-035 (previously described) 0.30 parts by weight AKP-20 (previously described) 50 parts by weight Among the above components, Pearl Glaze MRB-100RF, GANEX P-904LC, ion-exchanged water, ethylene glycol and glycerin are mixed and stirred, and then Lumicol NKW-2108, Proxel GXL, PO-20 and BYK- 035, AKP-20 and Alkathylan were added and stirred for 1 hour with a homogenizer. A glittering water-based ink composition was obtained.

(Comparative Example 1)
TITANIX JR-800 (previously described) 10.00 parts by weight Ropaque OP-62 (previously described) 38.00 parts by weight Jonkrill 60J (previously described) 4.00 parts by weight Kelzan AR (previously described) 0.60 parts by weight ion-exchanged water 33. 30 parts by weight ethylene glycol 5.50 parts by weight glycerin 4.50 parts by weight Proxel GXL (previously described) 0.30 parts by weight PO-20 (previously described) 3.00 parts by weight BYK-035 (previously described) 0.30 parts by weight AKP- 20 (described above) 0.50 parts by weight Of the above components, TITANIX JR-800, Jonkrill 60J, 23.93 parts by weight of ion-exchanged water, ethylene glycol and glycerin are mixed and stirred, and dispersed in a bead mill for 1 hour. The body was made. Next, Ropaque OP-62, Proxel GXL, PO-20, BYK-035 and AKP-20 were added and mixed and stirred for 30 minutes. Further, Kelzan AR and 9.4 parts by weight of ion-exchanged water were mixed, and a Kelzan AR aqueous solution obtained by stirring for 1 hour was added, followed by stirring for 1 hour with a homogenizer to obtain a white aqueous ink composition.

(Comparative Example 2)
Type R-780 (previously described) 16.00 parts by weight GANEX P-904LC (previously described) 0.30 parts by weight Alkathylan (previously described) 0.40 parts by weight Jonkrill 60J (previously described) 8.00 parts by weight ion-exchanged water 61. 20 parts by weight ethylene glycol 5.50 parts by weight glycerin 4.50 parts by weight Proxel GXL (previously described) 0.30 parts by weight PO-20 (previously described) 3.00 parts by weight BYK-035 (previously described) 0.30 parts by weight AKP- 20 (above) 0.50 parts by weight Of the above components, TYPEKE R-780, GANEX P-904LC, Jonkrill 60J, ion-exchanged water, ethylene glycol and glycerin are mixed and stirred, and dispersed in a bead mill for 1 hour. The body was made. Next, Proxel GXL, PO-20, BYK-035, AKP-20 and Alkathylan were added and stirred with a homogenizer for 1 hour to obtain a white aqueous ink composition.

(Comparative Example 3)
TITANIX JR-800 (previously described) 10.00 parts by weight Ropaque OP-62 (previously described) 55.00 parts by weight Jonkrill 60J (previously described) 4.00 parts by weight Kelzan AR (previously described) 0.60 parts by weight ion-exchanged water 15. 80 parts by weight ethylene glycol 5.50 parts by weight glycerin 4.50 parts by weight Proxel GXL (previously described) 0.30 parts by weight PO-20 (previously described) 3.00 parts by weight BYK-035 (previously described) 0.30 parts by weight AKP- 20 (mentioned above) 0.50 parts by weight KF-96H-10000cs (methyl silicone oil, manufactured by Shin-Etsu Silicone Co., Ltd.)
0.50 parts by weight Among the above components, TITANIX JR-800, Jonkrill 60J, 6.40 parts by weight of ion-exchanged water, ethylene glycol and glycerin were mixed and stirred, and dispersed in a bead mill for 1 hour to prepare a pigment dispersion. . Next, Ropaque OP-62, Proxel GXL, PO-20, BYK-035, AKP-20 and KF-96H-10000cs were added and mixed and stirred for 30 minutes. Further, Kelzan AR and 9.40 parts by weight of ion-exchanged water were mixed, and a Kelzan AR aqueous solution obtained by stirring for 1 hour was added, followed by stirring for 1 hour with a homogenizer to obtain a white aqueous ink composition.

(Comparative Example 4)
Typaque R-780 (previously described) 16.00 parts by weight Ropaque OP-62 (previously described) 40.00 parts by weight Jonkrill 60J (previously described) 4.00 parts by weight Kelzan AR (previously described) 0.60 parts by weight ion-exchanged water 20. 30 parts by weight ethylene glycol 5.50 parts by weight glycerin 4.50 parts by weight Proxel GXL (previously described) 0.30 parts by weight PO-20 (previously described) 3.00 parts by weight BYK-035 (previously described) 0.30 parts by weight AKP- 20 (described above) 0.50 parts by weight Unilube DGP-700 (polyoxypropylene diglyceryl ether, NOF Corporation)
5.00 parts by weight Of the above components, TYPEQUE R-780, Jonkrill 60J, 10.90 parts by weight of ion-exchanged water, ethylene glycol and glycerin are mixed and stirred, and dispersed in a bead mill for 1 hour to obtain a pigment dispersion. Produced. Next, Ropaque OP-62, Proxel GXL, PO-20, BYK-035, AKP-20 and Unilube DGP-700 were added and mixed and stirred for 30 minutes. Further, Kelzan AR and 9.40 parts by weight of ion-exchanged water were mixed, and a Kelzan AR aqueous solution obtained by stirring for 1 hour was added, followed by stirring for 1 hour with a homogenizer to obtain a white aqueous ink composition.

(Comparative Example 5)
Typaque R-780-2 (previously described) 21.00 parts by weight Ropaque OP-62 (previously described) 30.00 parts by weight Jonkrill 60J (previously described) 4.00 parts by weight Kelzan AR (previously described) 0.60 parts by weight ion-exchanged water 29.80 parts by weight Ethylene glycol 5.50 parts by weight Glycerin 4.50 parts by weight Proxel GXL (previously described) 0.30 parts by weight PO-20 (previously described) 3.00 parts by weight BYK-035 (previously described) 0.30 parts by weight AKP-20 (described above) 0.40 parts by weight Potassium hydroquinonesulfonate (manufactured by Samsung Chemical Co., Ltd.) 0.10 parts by weight Triethanolamine 0.50 parts by weight
Among the above components, Tyco R-780-2, Jonkrill 60J, 20.40 parts by weight of ion-exchanged water, ethylene glycol and glycerin were mixed and stirred, and dispersed with a bead mill for 1 hour to prepare a pigment dispersion. Next, Ropaque OP-62, Proxel GXL, PO-20, BYK-035, AKP-20, potassium hydroquinonesulfonate and triethanolamine were added and mixed and stirred for 30 minutes. Further, Kelzan AR and 9.40 parts by weight of ion-exchanged water were mixed, and a Kelzan AR aqueous solution obtained by stirring for 1 hour was added, followed by stirring for 1 hour with a homogenizer to obtain a white aqueous ink composition.

(Creation of test sample)
The ink compositions of Examples 1 to 9 and Comparative Examples 1 to 5 described above were applied to an ink containing tube of an aqueous ballpoint pen (K108-W, ball diameter 0.8 mm, manufactured by Pentel Co., Ltd.) having a ball diameter of 0.8 mm. Filled and used as a test ballpoint pen sample.

(Ink adhesion confirmation test on the inner wall of the ink container)
A test writing instrument having a ball diameter of 0.8 mm prepared using the ink compositions of Examples 1 to 9 and Comparative Examples 1 to 5 was used as a commercially available spiral writing tester (MODEL TS-4C-20, Seiki Industrial Research Institute). Whether or not the remaining ink level can be confirmed by writing continuously until the ink runs out on JIS P3201 writing paper A, and writing at a writing speed of 7 cm / sec, a writing angle of 70 degrees, and a writing load of 100 g. Evaluation was based on the following criteria. Subsequently, as a writing condition when the writing speed is high and the ink consumption is fast, writing is performed at a writing speed of 10 cm / sec, a writing angle of 70 degrees, and a writing load of 100 g, and writing is continuously performed until the ink disappears on JIS P3201 writing paper A. Whether the remaining amount of ink could be confirmed was evaluated based on the following criteria. The results are listed in Table 1.

◎: No ink adheres to the ink receiving tube ○: There is a slight amount of ink adhering to the ink receiving tube, but the remaining amount of ink can be clearly confirmed △: There is ink adhering to a part of the ink containing tube, but the remaining amount of ink is Can be confirmed ×: Ink adheres to the entire ink storage tube, and the remaining amount of ink cannot be confirmed.

  The water-based ink composition for ballpoint pens of Examples 1 to 9 includes at least a high specific gravity pigment, resin particles, 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- Since it contains at least one α-olefin selected from octene and 1-nonene and a copolymer of vinyl pyrrolidone, the whole ink is improved and the whole ink is collected as the ink is consumed by writing. As a result, the ink does not remain on the inner wall of the ink containing tube, and ink adhesion to the inner wall of the ink containing tube can be prevented.

On the other hand, Comparative Example 1 has at least one α- selected from 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene. Since the copolymer of olefin and vinylpyrrolidone is not included, and Comparative Example 2 does not include resin particles, the entire ink is not well-organized, and the ink remains on the inner wall of the ink storage tube. Ink adhesion to the ink could not be prevented. In Comparative Examples 3, 4, and 5, at least one α-olefin selected from 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-nonene. Modified vinyl oil instead of a copolymer of vinyl pyrrolidone, ether polyol obtained by addition polymerization of propylene oxide to diglycerin, hydroquinonesulfonic acid and / or salt for ink, triethanolamine, Although used, the effect of preventing ink adhesion to the high specific gravity pigment was not sufficient, and ink remained on the inner wall of the ink containing tube.

  As described above in detail, the water-based ink for ballpoint pens of the present invention has no ink contamination on the inner wall of the ink storage tube (even if the amount of ink discharged is large), and the water-based ink for ballpoint pens can clearly see the remaining amount of ink. The present invention relates to an ink composition.

Claims (3)

  At least one α- selected from at least a high specific gravity pigment, resin particles, 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene. A water-based ink composition for ballpoint pens containing an olefin and a copolymer of vinylpyrrolidone. The water-based ink composition for a ballpoint pen according to claim 1, wherein the high specific gravity pigment is titanium oxide. The water-based ink composition for ballpoint pens according to claim 2, wherein the titanium oxide has an oil absorption of 29 g / 100 g.