JP3227926B2 - Water-based ink composition for ball pens - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention secures good ink composition dischargeability by minimizing wear of a ball receiving seat due to rotation of a ball and enables a long writing distance. The present invention relates to an aqueous ink composition for ball pens.

[0002]

2. Description of the Related Art A ball pen can obtain relatively fine handwriting and, unlike a writing instrument having a fiber nib or a resin nib, changes in handwriting width due to wear of the nib even after long-term use. It is widely used because it has few. The aqueous ink composition used for such a ball-point pen has a viscosity of one to several cp (25 ° C.) and a viscosity of 50 to 2,000 c.
p (25 ° C.) is known. 1 to several cp (2
(5 ° C.) is mainly used for a ball-point pen having a structure using a batting as an ink occluding material.
C) are mainly used for those having a structure using a hollow cylinder as an ink reservoir.

[0003] The writing mechanism of a ball pen is such that the ink composition attached to the ball surface is transferred to a writing surface such as paper with the rotation of the ball. At this time, an appropriate amount of the ink composition is transferred to the object to be written, and furthermore, in order to prevent bleeding or blurring of the handwriting, the ink composition must have an appropriate viscosity and surface tension, and a high density. It is required that the handwriting is excellent in water resistance and light resistance.

[0004] In particular, a ball pen using an aqueous ink composition has a higher coefficient of friction of water as a solvent than an oil solvent, so that the ball sinks due to abrasion of a ball receiving seat due to rotation of the ball. Is easy to occur. As a result, the ink circulation groove in the ball pen tip is deformed and closed by friction due to the rotation of the ball, and the ejection of the ink composition becomes insufficient. In addition, there is a problem in that the handwriting is blurred, writing cannot be performed smoothly, and the writing distance is shortened. In order to solve this problem, attempts have been made to increase the lubricity of the ink composition by adding a lubricant such as a water-soluble cutting oil such as an oxyethylene-oxypropylene copolymer to the ink composition.

[0005]

As described above, water-soluble cutting oils such as oxyethylene-oxypropylene copolymers, which have been conventionally used as lubricants, are used as a lubricant.
The lubricating effect cannot be fully exhibited due to weak adhesion to the lug seat. As a result, wear of the ball receiving seat was not sufficiently suppressed, and the writing distance was shortened.

An object of the present invention is to provide a ball by rotating the ball.
An object of the present invention is to provide a water-based ink composition for a ball-point pen, which ensures good ink composition dischargeability by minimizing abrasion of a ball receiving seat and enables long-distance writing.

The present invention relates to at least water, a colorant, an alkylolamine salt of coconut oil fatty acid, gum arabic,
Gant gum, guar gum, locust bean gum, kara
Ginan, gelatin, casein, xanthen gum, dex
Strand, semi-synthetic methylcellulose, ethylcellulo
Glucose, hydroxyethyl cellulose, carboxymethyl
Cellulose, sodium alginate, synthetic polyvinyl alcohol
Alcohol, polyvinyl pyrrolidone, polyvinyl meth
Ruether, sodium polyacrylate, polyethylene
Oxide, alkali metal salt of acrylic resin, acrylic
Water selected from copolymers of acid and alkyl methacrylate
The gist of the present invention is a water-based ink composition for a ball pen comprising one or a mixture of two or more soluble polymers .

As the colorant, any of the dyes and pigments conventionally used in aqueous ink compositions can be used without limitation, and specific examples thereof include Japan Nolfast Black D-conc (C.I. Direct Black 17), Water Black 100L (19), Water Black L-200 (19), Water Black # 7 (19), Kayaset Black W9 (1)
9), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black EX (38), Direct Deep Black (38 similar products), Direct Fast Black Conc. 51), Kayalas Sprague VGN (7)
1), kayak direct brilliant erotic-G (C.I.
I. Direct erotic-4) Direct fast erotic-5
GL (26), Aizen Brimuraro-GCLH (44), Direct Fast Ero-R (50), Aizen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX
(4), Direct Fast Scarlet 4BS (23), Eisen Direct Durin BH (31),
Direct Scarlet B (37), Kayak Direct Scarlet 3B (39), Eisenbri Mlavin Conch 2BLH (75), Sumilite Red F3B
(80), Eisen Burimura Red 4BH (81)
Kayalas Sprarubin BL (83), Kayalas Light Red F5G (225), Kayalas Light Red F5
B (226), Kayaras Light Rose FR (22)
7) Direct Skible-6B (CI Direct Bull-1), Direct Skible-5B (15),
Benzo Brilliant Skible-8GS (41), Sumilite Scramble-BRR Conc (71), Dybo Genta Coizable-S (86), Waterable # 3 (86), Kayalaster Direct dyes such as Koyzable-GL (86), Daiwable-215H (87), Kayasurupuru-FF2GL (106), Kayasurupuru-FFRL (108) Kayasusupurata Koizuru-FBL (199) And Acid Bull-Black 10B (CI Acid Black 1),
Nigrosine (2), Water Black R455 (2), Water Black R510 (2), Sumino
Lumi Ring Black 8BX (24), Kaya Lumi Ring Black VLG (26), Kaya Lumi Ring Black BR Conc (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conc (44) 52), Sumilan Black WA (5
2), Ranyl Black BG Extra Conc (10
7), Kayano-milling black TLB (10
9), Sumino-Lumiring Black B (109), Kayano Milling Black TLR (110), Aizen Opal Black New Conc (119), Wo
Tar Black 187-L (154) Acid Yellow-
# 10 (CI Acid Ero-1), Kayak Acid Brilliant Flavin FF (7: 1), Kayasilero-GG (17), Xylene Light Ero-2G 140%
(No. 17), Sumino-Le Levelingero-NR (No. 1)
9), Water Yellow # 1 (23), Daiwater
Torazine (25), kayaker torazine (23),
Sumino-Lufastero-R (25) Diacid Lightero-2GP (29), Sumino-Lumiringero-O (38), Sumino-Lumilingero-MR (4)
2), Water Yellow # 6 (42), Kayanor Luero-NFG (49), Sumino-Lumiringero-3
G (72), Sumino-Rufastero-G (6)
1), Sumino-Lumiringero-G (Id. 78), Kayano Luero-N5G (Id. 110), Sumino-Lumiringero-4G 200% (Id. 141), Kayano Luero-NG
(135), Kayano-Lumiringero-5GW (1)
27), Kayano Lumilingero-6GW (14)
2), Sumitomo fast scarlet A (CI acid red 8), kayak silk scarlet (9),
Solar Rubin Extra (14), Daiwan-Kokushin (18), Water Scarlet (1)
8), Daiwa Red No. 102 (18), Eisenbonso-RH (26), Daiwa Red 2 (27), Sumino-Levering Brilliant Red S3B (35),
Kayasil rubinol 3GS (37), Aizen erythrosine (51), kayak acid rhodamine FB (52), Daiwa red No. 106 (52), Sumino-levelling rubinol 3GP (57), die Acid Alizarin Rubinol F3G 200% (82), Alizarin Rubinol 5G (83), Aizen Eosin GH
(No. 87), Water Red # 2 (No. 87), Daiwa Red 103WB (No. 87), Water Pink # 2 (No. 92), Eisen Acid Phloxine PB (No. 92),
Daiwa Red No. 104 (92), Rose Bengal (9)
4), Kayano milling scarlet FGW (11
1), Kayano Lumiling Rubin 3BW (129),
Sumino-Lumiring Brilliant Red 3BN Conc (131), Sumino-Lumiring Brilliant Red BS (138), Aizen Opal Pink BH (1)
86), Sumino-Lubrilliant Red B Conch (2
49), Kayak Acid Brilliant Red 3BL (254), Kayak Acid Brilliant Red BL (265), Kayano Lumiling Red GW (27).
6), Mitsui Acid Violet 6BN (CI Acid Violet 15), Mitsui Acid Violet BN (17), Water Violet # 1 (4)
9), Water Violet # 5 (49), Daiwa Purple No. 1 (49), Ink Violet L10 (4)
9), Sumitomo Patentable-VX (CI Acid Bull-1), Waterable # 106 (1), Patent Bull-AF (7), Waterable
# 9 (9), Daiwa Blue No. 1 (9), Inkable
L20 (9), Spranol R-B (15), Waterable # 116 (15), Orient Soluble-OBC (22), Orient Soluble
OBX (22), Sumino-Levelling Bull-4GL
(23), Mitsui Nylon Fast Bull-G (2)
5), Kayasil Bull-AGG (40), Kayasil Bull-BR (41), Mitsui Alizarin Safilol SE
(No. 43), Sumino-Leveling Skible-R Extra Conch (No. 62), Mitsui Nylon Fast Skible-R (No. 78), Sumitomobrilliant Indocyanine 6Bh / e (No. 83), Sandran cyanine N-
6B350% (90), Waterable # 115
(90), Waterable # 105 (90), Orient Soluble OBB (93), Sprano
Lucianin 7BF (100), Sumitomobrilliant Blue-5G (103), Acid Bull (10)
3), Asilane Brilliant Bull-FFR (10
4), Kayano-Lumiring Ultra Sky SE (11)
2), Kayano-milling cyanine 5R (113);
Aizen Opal Cyanine 2GLH (158), Daiwa Guinea Green B (CI Acid Green 3) Acid Brilliant Milling Green (9), Daiwa Green # 70 (16), Cyanol Culinary Green −
G (25), Sumino-milling green G (2)
7), acid dyes such as Water Orange # 17 (CI Acid Orange 56), Water Yellow # 2
(CI Foodero-3), Food Yellow No. 5 (C.I.
I. Foodello-3) Red No. 3 for Food (CI Food Red 14), Blue No. 2 for Food (CI Acid Bull-74), Green No. 2 for Food (CI Acid Gris) Food dyes, such as malachite green (C.I.4)
2000), Victoria Bull-FB (CI. 4404).
5), methyl violet FN (C.I.
5), Rhodamine F4G (C.I. 45160),
There are basic dyes such as Damin 6GCP (C.I. 45160).

Conventionally known pigments can be used as the pigment.
As specific examples, SpecialBlack 6 and S
170, S610, 5, 5, 4, 4A, 550,
35, 250, 100, Printex 150
T, U, V, 140U, 140V, 95, 90, 85, 80, 75, 55, 45, 45, P, XE2, L6, L, 300 30, 30, 35, 25, 200, A, G (all manufactured by Degussa Japan KK), # 2400B, # 235
0, # 2300, # 2200B, # 1000, # 95
0, # 900, # 850, # MCF88, MA600,
MA100, MA7, MA11, # 50, # 52, # 4
5, # 44, # 40, # 33, # 32, # 30, CF
9, # 20B, # 4000B (Mitsubishi Chemical Industries, Ltd.), MONARCH 1300, 1100,
1000, 900, 880, 800, 70
0, MOGULL, REGAL 400R, 660
R, 500R, 330R, 300R, 99R,
ELFTEX 8, 12 and BLACK PEARLS
2000 (above, USA, Cabot Co. Ltd.
Manufactured), Raven7000, 5750, 5250,
5000, 3500, 2000, 1500, 1255, 1250, 1200, 1170, 1
060, 1040, 1035, 1020, 10
00, 890H, 890, 850, 790, 780, 760, 500, 450, 430, 420, 410, 22, 22, 16, 14, and 825
Oil Beads, H20, C, Conduc
carbon blacks such as tex 975, 900, and SC (all manufactured by Colombian Carbon Japan Co., Ltd.);
KA-10, 10P, 15, 15, 20, 30, 3
5, 60, 80, 90, KR-310, 38
0, 460, 480 (Titanium Industry Co., Ltd.
Titanium oxides such as P25 (manufactured by Nippon Aerosil Co., Ltd.), BS-605, and 607 (manufactured by Toyo Aluminum Co., Ltd.), Bronze Powder P-555, and P-77
7 (manufactured by Nakajima Metal Foil Industry Co., Ltd.), Bronze Powder-3L5, 3L7 (above manufactured by Fukuda Metal Foil Industry Co., Ltd.)
Metal powder pigments, such as black iron oxide, yellow iron oxide, red iron oxide, ultramarine, navy blue, cobalt blue, and chrome grease.
Inorganic pigments such as chromium oxide, Hansaero-10G,
5G, 3G, 4, GR, A, Benzidine erotic, permanent erotic-NCG, tartrazine lake,
Quinoline erotic, sdarn 1, permanent orange,
Indus Ren Brilliant Orange GN, Permanent Brown FG, Para Brown, Permanent Red 4
R, Fire Red, Brilliant Carmine BS, Pyrazolone Red, Lake Red C, Quinacridone Red, Brilliant Carmine 6B, Bold-5B, Thioindigo Red, Fast Violet B, Dioxane Violet, Alkaline Bull Lake And organic pigments such as phthalocyanine blue, indigo, acid green lake and phthalocyanine line. Also,
In addition, inorganic fluorescent pigments such as zinc sulfide, zinc silicate, cadmium zinc sulfate, calcium sulfide, strontium sulfide, calcium tungstate, and other known organic fluorescent pigments can be used. The above-mentioned coloring agent can be used alone or in combination with another. The amount of the coloring agent varies depending on the color tone and the like, but the amount is 0.1 to 2 with respect to the total amount of the aqueous composition.
0% by weight is preferred.

Here, when a pigment is used as a colorant,
It is preferable to use a dispersant in combination, and examples of the dispersant include water-soluble or water-soluble resins conventionally used generally and those used as pigment dispersants such as anionic or nonionic surfactants. Then, as a polymer dispersant, natural gums such as gum arabic and tragacanth, glucosides such as saponin, cellulose derivatives such as methylcellulose, carboxycellulose and hydroxymethylcellulose, lignin sulfonate , Natural polymers such as shellac, polyacrylates, styrene-acrylic acid copolymer salts, vinylnaphthalene-
Anionic polymers such as salts of maleic acid copolymers, sodium salts and phosphates of β-naphthalenesulfonic acid formalin condensates, and nonionic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene glycol. Molecules. As surfactants, alkyl sulfates, polyoxyethylene alkyl ether sulfates, N-acyl amino acids and salts thereof, N-acylmethyl taurine salts, polyoxyethylene alkyl ether acetate salts, alkyl sulfocarboxylic acids Anionic surfactants such as salts, α-olefin sulfonates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl ethers, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl Examples include nonionic surfactants such as esters.
One or two or more of these can be selected and used in combination. The amount used is 1-2 based on the total amount of the aqueous composition.
0% by weight is preferred.

Further, in the case of a pigment ink, it is advantageous in the production of a pigment ink to use an aqueous ink base in which a pigment is dispersed in an aqueous medium. Specifically, Fuji S
PBlack 8031, 8119, 8167, 8276, 8381, 8406, Fuji SP
Red 5096, 5111, 5193, 522
0, Fuji SP Bordeaux 5500, F
uji SP Blue 6062, 6133, 6
134, Fuji SP Green 7051, Fu
ji SP Yellow 4060, Fuji SP
Violet 9011, Fuji SP Pink
9524, 9527, FujiSP Orange
534, FUji SP Brown 3074 (all manufactured by Fuji Dye Co., Ltd.), Emacol Black
CN, Emacol Blue FBB, FB, K
R, Emacol Green LXB, Emacol
Violet BL, Emacol Brown 3
101, EmacolCarmmine FB, Ema
col Red BS, Emacol Orange
R, Emacol Yellow FD, IRN, 3601, FGN, GN, GG, F5G, F
7G, 10GN, 10G, Sandy Suppe
r Black K, C, Sandye Super
Gray B, Sandy Super Brow
n SB, same FRL, same RR, Sandy Suppe
r Green L5G, GXB, Sandy S
upper Navy Blue HRL, GLL, HB, FBL-H, FBL-160, FBB, S
andy Super Violet BLH / C,
BL, Sandy Super Bordeaux
FR, Sandye Super Pink FB
L, F5B, Sandy SuperRubine
FR, Sandye super Carmine
FB, Sandy Super Red FFG,
Same RR, Same BS, SandySuper Orange
e FL, R, BO, Sandye Gold Y
yellow 5GR, same R, same 3R, Sandye Y
wllow GG, F3R, IRC, FGN, GN, GRS, GSR-130, GSN-13
0, the same GSN, the same 10GN (above, Sanyo Dyeing Co., Ltd.)
Manufactured), Rio FastBlack Fx 8012,
8313, 8169, Rio FastRed F
x 8209, 8172, Rio Fast Red
S Fx8315, 8316, Rio Fast
Blue Fx 8170, RioFast Blue
FX 8170, Rio Fast Blue S
FX 8312, Rio Fast Green S
Fx 8314 (all manufactured by Toyo Ink Co., Ltd.), NKW
-2101, 2102, 2103, 2104, 2105, 2106, 2107, 2108, 2
117, 2127, 2137, 2167, 21
01P, 2102P, 2103P, 2104P,
2105P, 2106P, 2107P, 210
8P, 2117P, 2127P, 2137P, 2167P, NKW-3002, 3003, 300
4, 3005, 3007, 3077, 300
8, 3402, 3404, 3405, 340
7, 3408, 3377, 3602, 360
3, 3604, 3605, 3607, 367
7, 3608, 3702, 3703, 370
4, 3705, 3777, 3708 (all manufactured by Nippon Fluorescence Co., Ltd.), Cosmokara-S 1000F series
(Toyo Soda Co., Ltd.), Victoria Ero-G-1
1, G-20, Victoria Orange G-16, G
-21, Victoria Red G-19, Victoria G-22, Victoria Pink G-17, Victoria G-23, Victoria Green G-18, Victoria G-24, Victoria Bull G
-15 and G-25 (all manufactured by Mikuni Pigment Co., Ltd.), and these can be used alone or in combination of two or more.

As the solvent, various water-soluble organic solvents can be used in addition to water, which is an essential condition. These solvents have various qualities as an aqueous ink composition for ball pens, for example, ink drying with a pen tip. It is used for the purpose of preventing ink freezing at low temperatures. Specifically, ethylene glycol, diethylene glycol, triethylene glycol
Propylene glycol, polyethylene glycol,
1,3-butylene glycol, thiodiethylene glycol
And glycols such as glycerol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and 2-pyrrolidone. These can be used alone or in combination of two or more. Further, the use amount thereof is preferably 5 to 40% by weight based on the total amount of the ink composition.

Alkylamine salts of coconut oil fatty acids are used to suppress wear of the ball seat. The amount used is 0.1 to the total amount of the ink composition.
8.0% by weight is preferred. Specifically, coconut oil fatty acids are obtained by heating oils and fats obtained from coconut meat with water,
Shows a mixture of volatile fatty acids and water-soluble fatty acids obtained by hydrolysis, such as saturated fatty acids include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachiic acid, Unsaturated fatty acids include hexadecenoic acid, oleic acid, linoleic acid and the like. The composition ratio of each fatty acid differs depending on the hydrolysis method and accuracy of the fat or oil. Examples of coconut oil fatty acids commercially available on the market include Lunac L-50, L
Unac L-55 (all manufactured by Kao Corporation), coconut oil fatty acid 200, and coconut oil fatty acid 300 (all manufactured by Miyoshi Oil & Fat Co., Ltd.). Examples of alkylamines include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, aminoethylethanolamine, N-methyl-N, N-diethanol-
Ruamine, N-methylethanolamine, 2-amino-
2-methyl-1, 3-propanediol and the like. Specific examples of the alkylamine salt of coconut oil fatty acid include Toho-CT (manufactured by Toho Chemical Industry Co., Ltd.) and Lost Nine # 108DK (manufactured by Ito Oil Co., Ltd.).

Alkylamine of coconut oil fatty acid is stirred with the above-mentioned alkylolamine or an aqueous solution thereof while heating at room temperature or, if necessary, adding an equivalent of coconutyl fatty acid to the alkylolamine. It is obtained by stirring for about 60 minutes. Alkylamine salt of coconut oil fatty acid may be added in advance into a salt in the ink composition, but coconut oil fatty acid and alkylolamine are separately added to the ink composition to form a salt. good. However, when they are added separately, the mixing order may be restricted depending on the composition of the ink composition.

Examples of the water-soluble polymer include natural gum arabic, tragacanth gum, guar gum locust bean gum, carrageenan, gelatin, casein, xanthen gum, dextran, semi-synthetic methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and carboxyl.
Simethyl cellulose , sodium alginate, synthetic polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, sodium polyacrylate, polyethylene oxide, alkali metal salts of acrylic resins,
One type of copolymer of acrylic acid and alkyl methacrylate
Alternatively, two or more kinds are selected and used in combination .

Further, in order to prevent the ink composition from flowing out of the ink passage of the writing instrument due to the generation of mold, the antiseptic such as sodium dehydroacetate, 1,2-benzothiazalin-3-one, sodium benzoate and the like are used. An appropriate amount of a fungicide can be added.

Further, in the case of a writing instrument using a metal in a portion that comes into contact with the ink composition, an anticorrosive such as benzotriazole and ethylenediaminetetraacetic acid for preventing corrosion of the metal, and oleic acid as a solubilizer are used. Such fatty acids can also be added.

In producing the ink composition of the present invention, various conventionally known methods can be employed. For example, when a dye is used as a coloring material, a turbo mixer is used.
When a pigment is used as a coloring material, the mixture can be easily obtained by mixing and grinding using a disperser such as a ball mill, a sand grinder, a speed line mill, or a roll mill. Can be

[0019]

The reason why the alkylamine salt of coconut oil fatty acid is effective in suppressing the wear of the ball seat is presumed as follows. That is, the alcohol amine salt of coconut oil fatty acid has a larger adhesive force to metals such as nickel silver and stainless steel used for ball pen tips than conventional lubricants, so that the metal surface of the ball receiving seat is It forms a strong molecular film of the alkylamine salt of coconut fatty acid. As a result of this adhesion film acting as a lubricant between the ball and the ball receiving seat, the wear resistance between the ball and the ball receiving seat is reduced, and the wear of the ball receiving seat is reduced. Is reduced. Therefore,
Discharge of the ink composition is stabilized, and a long writing distance commensurate with the amount of ink can be realized.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. The viscosity of each ink composition in Examples and Comparative Examples was 50
Less than cp is the standard coke of ELD type viscometer manufactured by Tokimec Co., Ltd.
Measured at 10rpm of rotor, 50cp or more and 600c
The value of less than p is measured with an ELD viscometer standard controller 1 rpm from Tokimec Co., Ltd.
The value less than p was measured with an ELD viscometer ST rotor 20 rpm manufactured by Tokimec. The temperature during the measurement was 25 ° C. In addition, in each embodiment, "parts" means "parts by weight".
Represents

Example 1 MA100 (carbon black, manufactured by Mitsubishi Kasei Co., Ltd.) 8.0 parts John Krill (dispersant, manufactured by Johnson Polymer Co., Ltd.) 4.0 parts Gar gum (thickener) 0.5 parts Propylene glycol 18.0 parts Glycerin 15.0 parts Toho-CT (lubricant, alkanolamine salt of coconut oil fatty acid, manufactured by Toho Chemical Industry Co., Ltd.) 1.0 part Proxel XL- 2 (preservative, manufactured by ICI Japan Co., Ltd.) 0.1 part Water 53.4 parts Components other than the guar gum in each of the above components were mixed and dispersed in a ball mill for 48 hours. The gum was added and the dispersion treatment was performed again for 5 hours, and coarse particles were removed with a 0.65 μm membrane filter (manufactured by Advantech Toyo) to obtain a black aqueous ink composition having a viscosity of 280 cp.

Example 2 Fuji S. P. Black 8031 (black aqueous pigment base, manufactured by Fuji Dye Co., Ltd.) 30.0 parts Ethylene glycol 15.0 parts Glycerin 8.0 parts Lunac L-55 (coconut oil fatty acid, manufactured by Kao Corporation) 0 0.3 parts Triethanolamine 0.2 parts Proxel GXL (preservative, manufactured by ICI Japan Co., Ltd.) 0.2 parts Water 45.5 parts Carboxymethylhydroxypropylated guar gum (thickener) 0.8 parts For each component, Lunac L-55 and triethanolamine are first mixed and stirred with a stirrer, salted, mixed and stirred with other components, and coarsely filtered with a 0.65 μm membrane filter (manufactured by Advantech Toyo). The particles were removed to obtain a black aqueous ink composition having a viscosity of 1950 cp.

Example 3 NKW-2117 (pink aqueous pigment base, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 45.0 parts Glycerin 10.0 parts Propylene glycol 15.0 parts Proxel GXL 0.2 parts E-CT 0.5 part Water 28.6 parts PEMULEN TR-1 (copolymer of acrylic acid and alkyl methacrylate, manufactured by BFGoodrich) 0.4 part 25% aqueous sodium hydroxide 0.3 part After mixing and stirring the components other than the 25% aqueous sodium hydroxide solution with a stirrer for 3 hours, the 25% aqueous sodium hydroxide solution was added to obtain a fluorescent pink aqueous ink composition having a viscosity of 1800 cp.

Example 4 Phthalocyanine Blue 8.0 parts Joncryl 8.0 parts Ethylene glycol 15.0 parts Glycerin 5.0 parts Water 62.6 parts Lunac L-50 0.7 parts Diethanolamine 0.0 parts 4 parts Carboxymethyl hydroxypropylated guar gum (thickener) 0.3 parts Lunc L-50 and diethanolamine in each of the above components were first mixed and stirred with a stirrer to form a salt, and then carboxymethylhydroxypropylated. The mixture was mixed and stirred with components other than guar gum and subjected to a dispersion treatment in a ball mill for 48 hours.
Thereafter, carboxymethylhydroxypropylated guar gum was added, and the mixture was dispersed again for 5 hours. Coarse particles were removed with a 0.65 μm membrane filter (manufactured by Advantech Toyo Co., Ltd.), and a blue aqueous ink composition having a viscosity of 295 cp was obtained. I got

Example 5 Victoria Blue G-15 (blue aqueous pigment base, manufactured by Mikuni Pigment Co., Ltd.) 50.0 parts Rhodamine 6GCP (CI Basic Red 1, manufactured by Sumitomo Chemical Co., Ltd.) 0.1 part Glycerin 12.0 parts Propylene glycol 18.0 parts Proxel XL-2 0.2 parts Coconut oil fatty acid 200 (coconut fatty acid, manufactured by Miyoshi Oil & Fat Co., Ltd.) 1.3 parts 2-amino-2-methyl- 1,3 -0.7 parts of propanediol 16.8 parts of water CMC- Daicel # 2000 (carboxymethylcellulose, manufactured by Daicel Chemical Industries, Ltd.) 1.0 part 200 parts of coconut oil fatty acid, 2-amino-2-me
Chill-1,3-propanediol, CMC-Daicel #
Mix and stir for 1 hour with a stirrer except for 2000.
Gini palm oil fatty acid 200, 2-amino-2-methyl-
Add 1,3-propanediol and mix for 1 hour
And add CMC-Daicel # 2000 and mix for 3 hours
Aqueous purple ink with viscosity of 1050 cp by stirring
A product was obtained.

Comparative Example 1 NKW-3005 (Yellow aqueous pigment base, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 40.0 parts Glycerin 8.0 parts Propylene glycol 15.0 parts Proxel GXL 0.2 parts Toho CT 0.3 parts Lost Nine # 108DK (Lubricant, manufactured by Ito Oil Co., Ltd.) 0.3 parts Water 36.2 parts The above components were mixed and stirred with a stirrer for 3 hours, and the viscosity was 7 cp.
Of a fluorescent yellow aqueous ink composition was obtained.

COMPARATIVE EXAMPLE 2 Except for the Toho CT of Example 1, the same amount of water was added.
Outside, black water having a viscosity of 275 cp was made in the same manner as in Example 1.
A water-soluble ink composition was obtained.

Comparative Example 3 Lunac L-55 of Example 2
Same as Example 3 except that water was added in that amount except for
To obtain a black aqueous ink composition having a viscosity of 1900 cp.
Was.

COMPARATIVE EXAMPLE 4 Except for the Toho CT of Example 3, the same amount of water was added.
The outside is made in the same manner as in Example 4, and has a pink color having a viscosity of 1750 cp.
An aqueous ink composition was obtained.

Comparative Example 5 Fuji S.I. P. Black 8031 30.0 parts Newpol 50HB-5100 (water-soluble cutting oil, manufactured by Sanyo Chemical Industries, Ltd.) 1.5 parts Propylene glycol 12.0 parts Glycerin 5.0 parts Proxel GXL 0.2 parts CMC-Daicel = 2000 2.0 parts Water 49.3 parts The above components were mixed and stirred for 3 hours with a stirrer to give a viscosity of 19
A 50 cp black aqueous ink composition was obtained.

Comparative Example 6 Fuji S.I. P. Black 8031 30.0 parts Unilube 70DP-950B (water-soluble cutting oil, manufactured by NOF Corporation) 0.1 part Glycerin 10.0 parts Proxel GXL 0.2 parts CMC-Daicel = 2000 2.0 parts Water 57. 7 parts The above ingredients were mixed and stirred with a stirrer for 3 hours to give
A black aqueous ink composition of 80 cp was obtained.

Comparative Example 7 C.I. I. Acid Black 2 10.0 parts Propylene glycol 20.0 parts Glycerin 5.0 parts Proxel GXL 0.1 parts Water 64.9 parts The above components are mixed and stirred with a stirrer for 3 hours to have a viscosity of 5.6.
cp of a black aqueous ink composition was obtained.

The above results were obtained in Examples 1 to 4 and Comparative Examples 1 to 6.
The water-based ink composition for ballpoint pens
Tip (ball material: cemented carbide) connected to one end
Transparent ink storage tube consisting of a polypropylene hollow shaft cylinder
0.8 g, and obtained in Example 5 and Comparative Example 7.
A commercially available water-based metal ball with an ink occluding material
Pen (Super Ball BH16, Pentel Co., Ltd.)
Fill 2.5g, write distance and ball sink amount respectively
Was tested. The results are shown in Tables 1 and 2.

Writing distance: Rotating continuous spiral writing tester (brush
Tester Model TS-4C-20 Seiki Industrial Research Institute
Writing speed: 7 cm / sec, load: 100
g, ink is not ejected by continuous writing at a writing angle of 70 °
The writing distance until it became exhausted was measured. (However, Examples 1 to
In No. 4, all the filled ink compositions were used.
In Comparative Examples 2 to 4, 20% of the filled ink composition remains.
But did not eject ink)

Ball sinking amount: In the above writing test,
Ball protrusion length before writing and ball after 500m continuous writing
The difference from the protrusion length was defined as the ball sinking amount. In addition, ball protrusion
The length is a tool microscope (digital small measuring microscope MOD)
EL STM-DH manufactured by Olympus Optical Co., Ltd.)
The length from the tip of the ballpoint pen tip to the tip of the ball
Was measured.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

As described in detail above, the present invention
Such a water-based ink composition for a ball-point pen is prepared by rotating a ball.
Wear of the ball seat is reduced, and ball sinking is minimized.
That the intended purpose of prevention can be fully achieved.
is there. Therefore, when filled into a ballpoint pen,
Achieving the original long writing distance corresponding to the amount of ink
It is.

[0039]

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 11/00-11/20

Claims (1)

(57) [Claims] At least water, a coloring agent, an alkylolamine salt of a coconut oil fatty acid, gum arabic and tragagantoga
Mu, guar gum, locust bean gum, carrageen
, Gelatin, casein, xanthen gum, dextra
, Semi-synthetic methylcellulose, ethylcellulose,
Hydroxyethyl cellulose, carboxymethyl cellulose
Source, sodium alginate, synthetic polyvinyl alcohol
Cole, polyvinylpyrrolidone, polyvinylmethylate
Ter, sodium polyacrylate, polyethylene oxa
And alkali metal salts of acrylic resin, acrylic acid and
High water solubility selected from alkyl methacrylate copolymer
An aqueous ink composition for ball-pen comprising one or a mixture of two or more molecules .