JPH10195363A - Water-base ink for ballpoint - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To prevent the occurrence of ink spots, to reduce wear of a ball receiving seat due to ball rotation, and to prevent ball sinking as much as possible. SOLUTION: An aqueous ink for a ballpoint pen to which polyoxyethylene styrenated phenyl ether is added.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention suppresses the occurrence of ink spots and minimizes abrasion of a ball receiving seat caused by rotation of a ball of a ballpoint pen tip, thereby ensuring good ink dischargeability. And a water-based ink that enables a long writing distance.

[0002]

2. Description of the Related Art In a writing mechanism of a ball pen, ink attached to the ball surface is transferred to a writing surface such as paper as the ball rotates. At this time, an appropriate amount of ink is transferred to the object to be scribed,
In order to prevent blurring, the ink is required to have an appropriate viscosity and surface tension, and to be a handwriting having a high concentration and excellent water resistance and light resistance.

In particular, ball pens using water-based inks are:
Because the coefficient of friction of water, which is a solvent, is larger than that of an oily solvent,
The ball sinks easily due to the wear of the ball receiving seat due to the rotation of the ball. 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,
Insufficient ink ejection. 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, a water-soluble cutting oil such as oxyethylene-oxypropylene copolymer or a surfactant such as polyoxyethylene alkyl ether, glyceryl fatty acid ester, or polyoxyethylene hardened castor oil is used as a lubricant in the ink. Attempts have been made to increase the lubricity of the ink by adding it as an additive.

[0004]

As described above, water-soluble cutting oils such as oxyethylene-oxypropylene copolymers, polyoxyethylene alkyl ethers, glyceryl fatty acid esters, etc., which have been conventionally used as lubricants, are not mentioned. Since the adhesion to the ball and the ball seat is weak, it is necessary to add a relatively large amount in order to sufficiently exert the lubricating effect. However, if the added amount is too large, the viscosity, surface tension, etc., decrease, and the ink ejected to the entire ball spreads, and the ink that has not been transferred from the ball to the paper surface is scraped off by the small tip of the ball pen tip. It easily adheres to the outer surface near the fore edge, causing problems such as ink spots. When used in an area where problems such as ink bottling do not occur, abrasion of the ball seat is not sufficiently suppressed, resulting in a short writing distance.

SUMMARY OF THE INVENTION It is an object of the present invention to suppress the occurrence of ink bottling and to minimize the abrasion of a ball receiving seat due to the rotation of the ball, thereby ensuring good ink dischargeability, and allowing long-distance writing. An object of the present invention is to provide a water-based ink for ball pens, which makes it possible to achieve the above.

[0006]

The gist of the present invention is an aqueous ink comprising at least a colorant, water, and polyoxyethylene styrenated phenyl ether.

As the coloring agent, any of the dyes and pigments conventionally used in aqueous inks can be used without limitation, and specific examples thereof include Japan Nolfast Black D-conc (CI Direct). Black 1
7), Water Black 100L (19), Water
Tar 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) Food Red No. 3 (CI Food Red 14), Food Blue No. 2 (CI Acid Bull-74), Food Green No. 2 (CI Acid Gris) Food dyes such as malachite green (C.I.
2000), Victoria Bull-FB (C.I.
5), methyl violet FN (C.I.
5), Rhodamine F4G (CI. 45160),
There are basic dyes such as Damin 6GCP (C.I. 45160).

As the pigment, conventionally known pigments can be used.
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 used varies depending on the color tone and the like, but is 0.1 to 2 with respect to the total amount of the aqueous composition.
0% by weight is preferred.

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, when a pigment is used as a coloring material, using an aqueous ink base in which the pigment is dispersed in an aqueous medium is advantageous in producing a pigment ink. In particular,
Fuji SP Black 8031, 8119,
8167, 8276, 8381, 8406, F
uji SP Red 5096, 5111, 51
93, 5220, Fuji SP Bordeaux
5500, FujiSP Blue 6062, 6
133, 6134, Fuji SP Green 7
051, Fuji SP Yellow 4060, F
uji SPBiolet 9011, Fuji SP
Pink 9524, Pink 9527, Fuji SP
Orange 534, FUji SP Brown
3074 (all manufactured by Fuji Dye Co., Ltd.), Emacol
Black CN, Emacol Blue FBB,
Same FB, Same KR, Emacol Green LXB,
Emacol Violet BL, Emacol B
rown 3101, Emacol Carmmine
FB, Emacol Red BS, Emacol
Orange R, Emacol Yellow F
D, IRN, 3601, FGN, GN, G
G, F5G, F7G, 10GN, 10G, Sa
ndye Super Black K, C, San
Dye Super Gray B, Sandy S
upper Brown SB, FRL, RR, Sa
ndye Super Green L5G, GX
B, Sandy Super Navy Blue
HRL, GLL, HB, FBL-H, FBL-
160, same FBB, Sandy Super Vio
let BL H / C, same BL, Sandy Sup
er BordeauxFR, Sandy Suppe
r Pink FBL, F5B, SandySup
er Rubine FR, Sandy super
Carmmine FB, Sandy Super
Red FFG, RR, BS, Sandy S
upper Orange FL, same R, same BO, San
DyeGold Yellow 5GR, R, 3
R, Sandye YwllowGG, F3R, I
RC, FGN, GN, GRS, GSR-13
0, the same GSN-130, the same GSN, the same 10GN (or more,
Sanyo Dyeing Co., Ltd.), Rio Fast Black
Fx 8012, 8313, 8169, RioFa
st Red Fx 8209, 8172, Rio
Fast RedS Fx 8315, 8316, R
io Fast Blue Fx 8170, Rio
Fast Blue FX 8170, Rio Fas
t Blue S Fx 8312, Rio Fast
Green S Fx 8314 (manufactured by Toyo Ink Co., Ltd.), NKW-2101, 2102, 210
3, 2104, 2105, 2106, 210
7, 2108, 2117, 2127, 213
7, 2167, 2101P, 2102P, 21
03P, 2104P, 2105P, 2106P,
2107P, 2108P, 2117P, 212
7P, 2137P, 2167P, NKW-300
2, 3003, 3004, 3005, 300
7, 3077, 3008, 3402, 340
4, 3405, 3407, 3408, 347
7, 3602, 3603, 3604, 360
5, 3607, 3677, 3608, 370
2, 3703, 3704, 3705, 377
7, 3708, 6013, 6038, 6559
(The above products are manufactured by Nippon Fluorescent Co., Ltd.)
0F series (manufactured by Toyo Soda Co., Ltd.), Victoria Ero G-11, G-20, Victoria Orange G-
16, G-21, Victoria Red G-19, G
-22, Victoria Pink G-17, Victoria G-23, Victoria Green G-18, Victoria G-24, Victoria Bull G-15, Victoria G-25
And the like, and these may be one type or two types.
More than one kind can be selected and used together.

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, for example, prevention of ink drying at a pen tip, low temperature It is used for the purpose of preventing ink freezing. Specifically, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,3-butylene glycol, thiodiethylene glycol, and glycerin And ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2
-Pyrrolidone and the like can be used, and 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.

The polyoxyethylene styrenated phenyl ether may be used after being mixed with the ink solvent in advance, or may be added after mixing other components of the ink. The addition amount is not unique because it may be affected by the type of the colorant and the surfactant of the ink, but the addition of 0.1% by weight or less diminishes the effect on other inks, and If the addition is more than 0.1% by weight, the compatibility with other inks becomes unstable, resulting in separation of the components in the ink.
Is preferred. As an example, the polyoxyethylene styrenated phenyl ether has an ethylene oxide addition number of 8 mol such as polyoxyethylene monostyrenated phenyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tristyrenated phenyl ether and the like. , 12 mol, 13 mol, 15 mol, 20 mol, etc. The optimal ethylene oxide addition number is not unique because it may be affected by the type of ink solvent, the colorant, the resin, and the type of surfactant. Since the hydrophilicity becomes too weak and the compatibility with other inks becomes unstable, and the components in the ink are separated, the ethylene oxide addition number is usually preferably 8 mol or more.

Various additives and surfactants can be used in the aqueous ink for ball-point pens of the present invention, if necessary, in addition to the above components. Examples include antioxidants, ultraviolet absorbers, rust inhibitors, writability, various surfactants used for improving brushability, such as fatty acid salts, higher alcohol sulfate salts, fatty acid sulfate salts, Anionic surfactants such as alkyl allyl sulfonates, decaglycerin fatty acid ester, hexaglycerin fatty acid ester, polyoxyethylene alkyl ethers, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxy Ethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether
Nonionic surfactants such as ter and polyoxyethylene hydrogenated castor oil; amphoteric surfactants such as imidazoline and betaine;

Further, natural gum arabic, tragacanth gum, guar gum, locust bean gum, natural gum arabic, gum tragacanth, guar gum, etc.
Alginic acid, carrageenan, gelatin, casein, xanthan gum, dextran, semi-synthetic methylcellulo-
, Ethylcellulose, hydroxyethylcellulose,
Thickening polysaccharides such as carboxymethyl cellulose, sodium starch glycolate, sodium alginate, propylene glycol alginate, hydroxypropylated guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic acid Water-soluble polymers such as sodium, carboxyvinyl polymer, polyethylene oxide, copolymers of vinyl acetate and polyvinylpyrrolidone, alkali metal salts of acrylic resins, and copolymers of acrylic acid and alkyl methacrylate may also be used in combination. it can.

Further, in order to suppress the outflow inhibition of the ink in the ink passage of the writing instrument due to the generation of mold, sodium dehydroacetate and 1,2-benzothiazaline-3 are used.
Preservatives and fungicides such as -one and sodium benzoate may be added in appropriate amounts.

Further, in the case of a writing instrument which uses a metal in a portion that comes into contact with the ink, a corrosion inhibitor such as benzotriazole or ethylenediaminetetraacetic acid for preventing corrosion of the metal, or a solubilizer such as oleic acid. Fatty acids can also be added.

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

[0018]

The following is the reason why a water-based ball-point pen which ensures good ink ejection by minimizing wear of the ball receiving seat due to the rotation of the ball and enables long-distance writing can be obtained is as follows. It is thought to be. Many surfactants have the property of forming a multimolecular layer on the metal surface and physically adsorbing them, and polyoxyethylene styrenated phenyl ether has similar properties, but polyoxyethylene styrenated phenyl ether has several properties. Since it has a benzene ring, a hydroxyl group and an ether group, its properties become stronger. When writing with a ball-point pen, when the ball starts to rotate, the polymolecular layer of polyoxyethylene styrenated phenyl ether physically adsorbed on a metal surface such as nickel-white or stainless steel, which is the material of the ball-point tip, forms a ball and a ball seat. The ball receives frictional resistance due to the rotation of the ball while being sucked, and is dragged in the direction of rotation of the ball. Here, the polymolecular layer of polyoxyethylene styrenated phenyl ether has a strong attraction force to the ball and the ball seat. Further, a plurality of benzene rings arranged in parallel act like grease or lubricating oil, and reduce frictional resistance applied to the multimolecular layer. As a result, the multi-layer does not readily separate from the metal surface in the ballpoint pen tip, causing inter-layer misalignment within the multi-layer. As the ball further rotates, the polyoxyethylene styrenated phenyl ether multi-layer receives greater frictional resistance, and cannot dissipate the frictional resistance due to misalignment between the layers in the multi-layer. Is done. By repeating such "shift" and "ejection" of the multi-layer,
Most of the frictional resistance can be absorbed. As a result, the addition of polyoxyethylene styrenated phenyl ether reduces the frictional resistance between the ball and the ball seat and reduces the wear of the ball seat. In addition, polyoxyethylene styrenated phenyl ether is easily compatible with inks such as dyes, pigments, thickeners, resins, and various additives due to its multiple benzene rings and hydroxyl and ether groups arranged in parallel. Since the tension is kept high enough not to impair the writing ability, the ink does not unnecessarily spread on the ball surface, and therefore the ink does not adhere to the vicinity of the tip of the tip of the ballpoint pen and ink spots do not occur.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. The viscosity of each ink in the examples and comparative examples is less than 50 cp and the standard viscosity of an ELD type viscometer manufactured by Tokimec Co., Ltd.
Measured at 10 rpm, 50 cp or more and less than 600 cp measured with a Tokimec ELD viscometer standard controller-1 rpm, and 600 cp or more and less than 2000 cp with an ELD viscometer ST ro made by Tokimec. T-20
It was measured at rpm. The temperature during the measurement was 25 ° C.
In each of the examples, “parts” means “parts by weight”.

Hereinafter, the present invention will be described in detail with reference to Examples, but the term "parts" indicates parts by weight. Example 1 Polyvinylpyrrolidone (thickener) 7.0 parts Xanthan gum (thickener) 0.5 parts NKW-2105 (yellow aqueous pigment base, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 45.0 parts Proxel GXL (preservative) 0.1 parts Polyoxyethylene distyrenated phenyl ether 6.0 parts Water 41.4 parts Components other than xanthan gum in each of the above components were mixed with a stirrer.
After mixing and stirring for a period of time, xanthan gum was added and the mixture was stirred again for 3 hours to obtain a yellow aqueous ink having a viscosity of 1080 cp.

Example 2 NKW-6559 (black aqueous pigment base, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 40.0 parts Hydroxypropylated guar gum (thickener) 0.5 part Polyoxyethylene nonyl phenyl ether (pigment) Dispersant) 1.0 part Proxel GXL (preservative, manufactured by ICI Japan) 0.1 part Polyoxyethylene monostyrenated phenyl ether 5.0 parts Water 53.4 parts Other than hydroxypropylated guar gum in each of the above components After mixing and stirring the components for 1 hour with a stirrer, hydroxypropylated guar gum was added and stirred again for 3 hours to obtain a black aqueous ink having a viscosity of 380 cp.

Example 3 Daiwa Red No. 104 (Dye, manufactured by Daiwa Chemical Industry Co., Ltd.) 5.0 parts Xanthan gum (thickener) 0.5 part Joncryl J-61 (styrene acrylic resin, Johnson Polymer Co., Ltd.) 1.0 part PEMULEN TR-1 (copolymer of acrylic acid and alkyl methacrylate, manufactured by BF Goodrich) 1.0 part Polyoxyethylene tristyrenated phenyl ether 0.5 part Water 91.7 parts 25 % Sodium hydroxide aqueous solution 0.3 part Xanthan gum, PEMULEN, 25%
After mixing and stirring other than the aqueous sodium hydroxide solution with a stirrer for 3 hours, xanthan gum was added and stirred again for 1 hour,
Thereafter, PEMULEN was added and the mixture was stirred for 30 minutes.
p red water-based ink was obtained.

Example 4 Phthalocyanine Blue 8.0 parts Propylene glycol 7.0 parts Propylene glycol alginate (water-soluble thickening polysaccharide) 1.2 parts Sodium dehydroacetate (preservative) 0.2 parts Polyoxy Ethylene sorbitan fatty acid ester (dispersant) 1.0 part Polyoxyethylene tristyrenated phenyl ether 1.2 parts Water 81.4 parts Components other than propylene glycol alginate in the above components were mixed and stirred for 4 hours in a ball mill. Propylene glycol alginate was added and dispersed again for 2 hours to obtain a 0.65 μm membrane filter.
Coarse particles were removed using (Advantech Toyo Co., Ltd.) to obtain a blue aqueous ink having a viscosity of 980 cp.

Example 5 MA100 (carbon black, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 10.0 parts Carboxymethyl hydroxypropylated guar gum (thickener) 1.5 parts Poly N-vinylacetamide (thickener) 0.3 parts OP-20 (polyoxyethylene octyl phenyl ether, manufactured by Nikko Chemicals Co., Ltd.) 2.0 parts Sodium benzoate (preservative) 0.5 parts Polyoxyethylene distyrenated phenyl ether 2.2 parts Propylene Glycol 5.0 parts Water 78.5 parts Components other than carboxymethylhydroxypropylated gum gum and poly N-vinylacetamide in the above components are mixed and stirred for 3 hours in a ball mill, and then carboxymethylhydroxypropylated gum gum is Poly-N-vinylacetamide was added thereto, and the mixture was dispersed again for 2 hours.
Was obtained.

Comparative Example 1 A yellow ink was obtained in the same manner as in Example 1, except that the same amount of polyoxyethylene oleyl ether was used instead of removing polyoxyethylene distyrenated phenyl ether.

Comparative Example 2 A black ink was obtained in the same manner as in Example 2 except that the same amount of polyoxyethylene hydrogenated castor oil was added instead of removing polyoxyethylene monostyrenated phenyl ether.

Comparative Example 3 A red ink was obtained in the same manner as in Example 3, except that the same amount of polyoxyethylene oleyl ether was used instead of removing polyoxyethylene tristyrenated phenyl ether.

Comparative Example 4 A blue ink was obtained in the same manner as in Example 4 except that the same amount of polyoxyethylene hydrogenated castor oil was added instead of removing polyoxyethylene tristyrenated phenyl ether.

Comparative Example 5 A black ink was obtained in the same manner as in Example 5, except that the same amount of polyoxyethylene sorbite tetraoleate was added instead of removing polyoxyethylene distyrenated phenyl ether.

As described above, the water-based inks obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were used as hollow hollow cylinders made of polypropylene in which a nickel-white ball pen tip (ball material: cemented carbide) was connected at one end. 0.8g into a transparent ink container
The writing distance and the amount of ball sink were tested. The results are shown in Tables 1 and 2.

Writing distance: Using a rotation type continuous spiral writing tester (writing tester MODEL TS-4C-20 manufactured by Seiki Kogyo Kenkyusho) at a writing speed of 7 cm / sec and a load of 100.
g, the writing distance was measured until the ink was not discharged after continuous writing at a writing angle of 70 °. (However, Examples 1 to
In No. 5, all the filled inks have been used. In Comparative Examples 1 to 4, 20% of the filled ink remained, but no ink was ejected.)

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

Ink bot number measurement test; writing angle 70 °,
After drawing a spiral of 1000 m on high-quality paper at a writing speed of 7 cm / sec, the handwriting was written by Scale Lupe (Tokai Sangyo Co., Ltd.)
And the number of ink spots on the spiral handwriting was counted.

As for the ink botts, 0.25 pieces each having a short diameter of 2 mm and a long diameter of 5 m, 0.50 pieces smaller than those specified by JIS, and 1 piece each having the same size as those specified by JIS. The number was measured as 1.00 and the sum was taken as the number of ink spots.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

As described above in detail, the water-based ink according to the present invention can also suppress the occurrence of ink bottling and can reduce the wear of the ball receiving seat due to the rotation of the ball.
The intended purpose of minimizing sun sinking can be sufficiently achieved. Thus, the original long writing distance corresponding to the amount of the filled ink is realized.

Claims (1)

[Claims] An aqueous ink for a ballpoint pen, comprising at least a colorant, water and polyoxyethylenestyrenated phenyl ether.