JPH1067961A - Water base ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water base ink composition capable of writing for a long way while suppressing dripping or blotting of a calligraphy as well possible and preventing wearing of a ball bearing step as well as possible and giving excellent quality of the calligraphy by formulating water-soluble mucopolysaccharides, an amino acid-type betaine and water. SOLUTION: This composition is composed of (A) water-soluble mucopolysaccharides (e.g. gum arabic), (B) an amino acid-type betaine and (C) water. Preferably, 0.01-5wt.% of the component A and 0.01-8wt.% of the component B are mixed into the whole amount of the objective composition. Preferably, 0.1-20wt.% of a coloring agent is used to the whole amount of the composition. In a case of using a pigment as the coloring agent, a dispersant such as a polymer dispersant may be combinedly used and the using amount is preferably 1-20wt.% based on the whole weight of the composition. Other than the component C, various water-soluble organic solvent such as ethylene glycol may be formulated into the ink in order to prevent drying of the ink at a pen point, etc. Preferably, an using amount of the solvent is 5-40wt.% based on the whole weight of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition containing water as a main solvent, and more particularly to a water-based ink composition which is used for a ballpoint pen having a metal tip and has both good handwriting quality and ink dischargeability. It is about things.

[0002]

2. Description of the Related Art A ballpoint pen, unlike a writing implement having a fiber nib or a resin nib, can obtain relatively thin handwriting and has a small change in handwriting width due to abrasion of the nib even after long use. Because of that, it is often used. The aqueous ink composition used for such a ballpoint pen has a viscosity of one to several cp (25 ° C.) and a viscosity of 50 to 30 cp.
000 cp (25 ° C.) is known. Those having 1 to several cp (25 ° C.) are mainly used for ballpoint pens having a structure using a batting as an ink occluding material, and 50 to 30000
The cp (25 ° C.) type is mainly used for a structure in which ink is freely stored in a hollow container such as a cylindrical body.

In particular, a ball-point pen using an aqueous ink composition has a relatively high coefficient of friction of water as a solvent, and therefore the ball seat is likely to be worn by rotation of the ball. As a result, the ink circulation groove in the ballpoint pen tip may be deformed or partially or entirely closed, resulting in insufficient discharge of the ink composition. When deformation or blockage occurs in the ink circulation groove, there is a problem that handwriting is blurred, smooth writing cannot be performed, and the writing distance is shortened. To solve this problem, water-soluble cutting oil such as oxyethylene-oxypropylene copolymer in the ink composition,
Attempts have been made to improve the lubricity of the ink composition by adding a surfactant such as polyoxyethylene alkyl ether, glyceryl fatty acid ester, or polyoxyethylene hardened castor oil as a lubricant.

[0004]

A water-soluble cutting oil such as the oxyethylene-oxypropylene copolymer described above,
Surfactants such as polyoxyethylene alkyl ether, glyceryl fatty acid ester, and polyoxyethylene hardened castor oil have low adhesion to balls and ball seats, and need to be added in large amounts to achieve a sufficient lubricating effect. is there. However, when a large amount of a water-soluble cutting oil such as an oxyethylene-oxypropylene copolymer is added, the ink easily adheres to the outer surface near the tip end of the ballpoint pen tip, and the boss phenomenon easily occurs. Also, if a large amount of a surfactant such as polyoxyethylene alkyl ether, glyceryl fatty acid ester, or polyoxyethylene hardened castor oil is added, the penetrating power of the ink onto the paper surface will be too strong, and the handwriting will spread, The balance of the dissolution system of the ink composition is disrupted, and the ink composition is separated, resulting in shading of the handwriting.
If each of them is used in such an amount that these problems do not occur, the wear of the ball seat is not sufficiently suppressed, and the writing distance is shortened. Particularly, when the diameter of the ball is 0.3 mm or 0.4 mm
When a relatively small diameter is used, the number of rotations of the ball is increased with respect to the writing distance, and the ball is liable to be worn, and a more lubricating effect is expected.

SUMMARY OF THE INVENTION It is an object of the present invention to minimize the wear of a ball seat due to the rotation of a ball while minimizing problems such as blur, blurring of a handwriting, and shading of a handwriting. An object of the present invention is to provide a water-based ink composition capable of ensuring long-distance writing while ensuring good handwriting quality.

[0006]

The gist of the present invention is an aqueous ink composition comprising at least a water-soluble thickening polysaccharide, an amino acid type betaine and water.

As the colorant, any of the dyes and pigments conventionally used in aqueous ink compositions can be used without limitation. Specific examples of the dye include Japanol Fast 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 Conch (51), Kaya Rath Sprague VGN (7
1), Kayak Direct Brilliant Yellow G (C.I.
I. Direct erotic-4) Direct fast yellow 5
GL (26), Aizen Brimura Yellow GCLH (44), Direct Fast Yellow 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), Aizen Murabin Conch 2BLH (75), Sumilight Red F3B
(80), Eisen Burimura Red 4BH (81)
Kayalas Sprarubin BL (83), Kayalas Light Red F5G (225), Kayalas Light Red F5
B (226), Kayasu Light Rose FR (22)
7) Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (15),
Benzo Brilliant Sky Blue 8GS (41), Sumilite Supra Blue BRR Conc (71), Diebogen Turquoise Blue S (86), Water Blue # 3 (86), Kayara Star Coy Blue GL (86), Direct dyes such as Daiwa Blue 215H (87), Kayalas Supra Blue FF2GL (106), Kayaras Supra Blue FFRL (108), Kayaras Splatter Turquoise Blue FBL (199) and Acid Blue Black 10B (C.I. I. Acid Black 1),
Nigrosine (2), Water Black R455 (2), Water Black R510 (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (26), Kayanol Milling Black BR Conc (2) 31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conc (52), Sumilan Black WA (5)
2), Ranyl Black BG Extra Conc (10
7), Kayanol Milling Black TLB (10
9), Suminol Milling Black B (109), Kayanol Milling Black TLR (110), Aizen Opal Black New Conc (119), Water Black 187-L (154) Acid Yellow # 10 (CI) Acid Yellow 1), Kayak Acid Brilliant Flavin FF (7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140%
(17), Suminol Leveling Yellow NR (1)
9), Water Yellow # 1 (23), Daiwa Torazine (25), Kayaktor Trazine (23),
Suminol Fast Yellow R (25) Diacid Light Yellow 2GP (29), Suminol Milling Yellow O (38), Suminol Milling Yellow MR (4)
2), Water Yellow # 6 (42), Kayanol Yellow NFG (49), Suminol Milling Yellow 3
G (72), Suminol Fast Yellow G (6)
1), Suminol Milling Yellow G (78), Kayanol Yellow N5G (110), Suminol Milling Yellow 4G 200% (141), Kayanol Yellow NG
(135), Kayanol Milling Yellow 5GW (1
27), Kayanol Milling Yellow 6GW (14
2), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (9),
Solar Rubin Extra (14), Daiwa New Koksin (18), Water Scarlet (1)
8), Daiwa Red No. 102 (18), Eisen Bonso-RH (26), Daiwa Red 2 (27), Suminol Leveling Brilliant Red S3B (35),
Kayasil rubinol 3GS (37), Aizen erythrosine (51), kayak acid rhodamine FB (52), Daiwa red No. 106 (52), Suminol leveling rubinol 3GP (57), Diacid alizarin rubi Nord F3G 200% (82), Alizarin Rubinol 5G (83), Eizen Eosin GH
(87), Water Red # 2 (87), Daiwa Red 103WB (87), Water Pink # 2 (92), Eisen Acid Phloxine PB (92),
Daiwa Red No. 104 (92), Rose Bengal (9)
4), Kayanol milling scarlet FGW (11
1), Kayanol Milling Rubin 3BW (129)
Suminol Milling Brilliant Red 3BN Conc (131), Suminol Milling Brilliant Red BS (138), Aizen Opal Pink BH (1)
86), Suminol Brilliant Red B Conch (2
49), Kayak Acid Brilliant Red 3BL (254), Kayak Acid Brilliant Red BL (265), Kayanol Milling Red GW (27)
6), Mitsuiacid Violet 6BN (CI Acid Violet 15), Mitsuiacid Violet BN (17), Water Violet # 1 (4)
9), Water Violet # 5 (49), Daiwa Purple No. 1 (49), Ink Violet L10 (4)
9), Sumitomo Patent Pure Blue VX (CI Acid Blue 1), Water Blue # 106 (1), Patent Blue AF (7), Water Blue # 9 (9), Daiwa Blue 1 ( 9), Ink Blue L20 (9), Spranol Blue B (15), Water Blue # 116 (15), Orient Soluble Blue OBC (22), Orient Soluble Blue OBX (22), Suminol Leveling Blue 4GL
(23), Mitsui Nylon Fast Blue G (2)
5), Kayasil Blue AGG (40), Kayasil Blue BR (41), Mitsui Alizarin Safirol SE
(43), Suminol Leveling Sky Blue R Extra Conch (62), Mitsui Nylon Fast Sky Blue R (78), Sumitomobrilliant Indocyanine 6Bh / e (83), Sandran cyanine N-
6B350% (90), Water Blue # 115
(90), Water Blue # 105 (90), Orient Soluble Blue OBB (93), Spranol Cyanine 7BF (100), Sumitomobrilliant Blue 5G (103), Acid Blue (10)
3), Asilane brilliant blue FFR (10
4), Kayanol Milling Ultra Sky SE (11
2), Kayanol milling cyanine 5R (113);
Eisen Opal Cyanine 2GLH (158), Daiwa Guinea Green B (CI Acid Green 3) Acid Brilliant Milling Green (9), Daiwa Green # 70 (16), Kayanol Cyanine Green G (25), Suminol Milling Green G (2
7), acid dyes such as water orange # 17 (CI acid orange 56), water yellow # 2
(C.I. Food Yellow 3), Food Yellow No. 5 (C.I.
I. Food Yellow 3) Food Red No. 3 (CI Food Red 14), Food Blue 2 (CI Acid Blue 74), Food Green 2 (CI Acid Green 5), etc. Food dye, malachite green (CI.4
2000), Victoria Blue FB (CI. 4404)
5), methyl violet FN (C.I.
5), basic dyes such as rhodamine F4G (CI. 45160) and rhodamine 6GCP (CI. 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 oxide such as P25 (manufactured by Nippon Aerosil Co., Ltd.), BS-605, and 607 (manufactured by Toyo Aluminum Co., Ltd.), and bronze powders P-555 and P-77.
7 (above, 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, chrome green, chromium oxide and other inorganic pigments, Hansa Yellow 10G,
5G, 3G, 4, GR, A, Benzidine Yellow, Permanent Yellow NCG, Tartrazine Lake,
Quinoline yellow, Sudanese 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, Bordeaux 5B, Thioindigo Red, Fast Violet B, Dioxane Violet, Alkaline Blue Lake, Phthalocyanine Blue, Indigo, Acid Green Lake, Organic pigments such as phthalocyanine green are exemplified. 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. Natural polymer such as gum arabic and tragacanth, glucosides such as saponin, cellulose derivatives such as methylcellulose, carboxycellulose and hydroxymethylcellulose, natural polymers such as ligninsulfonate and shellac, as polymer dispersants. Acrylic acid salt, styrene-acrylic acid copolymer salt, vinyl naphthalene
Maleic acid copolymer salts, β-naphthalenesulfonic acid formalin condensate sodium salts, phosphates, and the like, and anionic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene glycol, and the like. Can be As surfactants, alkyl sulfates, polyoxyethylene alkyl ether sulfates, N-acyl amino acids and salts thereof, N-acylmethyl taurine salts, polyoxyethylene alkyl ether acetates, alkyl sulfocarboxylates, α- Anionic surfactants such as olefin sulfonates, alkyl phosphates and polyoxyethylene alkyl ether phosphates; nonionics such as polyoxyethylene alkyl ethers, sorbitan alkyl esters, and polyoxyethylene sorbitan alkyl esters Surfactants.
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.

Furthermore, in the case of pigment inks, it is advantageous in the production of pigment inks 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 Pigment 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, 601
3, 6038, 6559 (The above are from Nippon Fluorescence Co., Ltd.)
Co., Ltd.), Cosmo Color S 1000F Series (manufactured by Toyo Soda Co., Ltd.), Victoria Yellow G-11, G-2
0, 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 (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 example, prevention of ink drying at a pen tip, It is used for the purpose of preventing freezing of the ink in the above. Specifically, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,3-butylene glycol, thiodiethylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, etc. 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 composition.

The amino acid type betaine is used to suppress wear of the ball seat. The amount used is preferably from 0.01 to 8.0% by weight based on the total amount of the ink composition. In particular, when a higher lubrication effect is required, such as when using a small-diameter ball, besides increasing the amount used,
It is effective to use it with a conventionally used lubricant. Amino acid type betaine is an amino acid such as alanine, glycine, etc.
A betaine such as alkyl glycine, acyl alanine, dialkylaminoethyl glycine, or alkylamidopropyl glycine is shown, and the alkyl group has 1 to 22 carbon atoms. Specific examples of the amino acid type betaine include SWANO
L AM-3130N, SWANOL AM-301
(Nikko Chemicals Co., Ltd.), Lipomin LA (Lion Co., Ltd.), Nissan Anon BF, Nissan Anon BL, Nissan Anon LG, Nissan Anon B
DF-R (all manufactured by NOF Corporation), Levon 2000
(Above, manufactured by Sanyo Chemical Industry Co., Ltd.), Obazoline BC, Obazoline LB, Obazoline CAB, Obazoline LAB,
Obazoline 516, Obazoline 516S, Obazoline B
(The above are manufactured by Toho Chemical Industry Co., Ltd.), Amphitol 20B
S, Amphitol 24B, Amphitol 86B (above,
Kao Corporation).

[0013] The water-soluble thickening polysaccharide increases the viscosity of the entire ink composition to stabilize the dispersion of the coloring material and the like, or to prevent ink leakage, and suppresses wear of the ball seat together with the amino acid type betaine. Is used to The amount used is 0.01 to the total amount of the ink composition.
~ 5.0 wt% is preferred. Specifically, natural gum arabic, tragacanth gum, guar gum, locust bean gum, alginic acid, carrageenan, gelatin, casein, xanthen gum, dextran, semi-synthetic methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium starch glycolate , Sodium alginate, propylene glycol alginate, hydroxypropylated guar gum and the like. One or more of these water-soluble thickening polysaccharides can be selected and used in combination.

In addition to these water-soluble thickening polysaccharides, polyvinyl alcohol, polyvinylpyrrolidone, and the like for adjusting the viscosity of the ink composition or for stabilizing the dispersion of the coloring material and the like.
Water-soluble polymers such as polyvinyl methyl ether, sodium polyacrylate, carboxyvinyl polymer, polyethylene oxide, copolymer of vinyl acetate and polyvinylpyrrolidone, alkali metal salt of acrylic resin, and copolymer of acrylic acid and alkyl methacrylate You can also.

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 and sodium benzoate is used. An appropriate amount of a fungicide can be added.

Further, in the case of a writing instrument using a metal in a portion which comes into contact with the ink composition, a corrosion inhibitor such as benzotriazole or ethylenediaminetetraacetic acid for preventing corrosion of the metal, or a solubilizing agent such as oleic acid. 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 or an aqueous pigment base is used as a coloring material, the mixture is stirred and mixed by a stirrer such as a turbo mixer. When a pigment is used as a coloring material, a ball mill, a sand grinder, a speed line mill, a roll mill, or the like is used. Can be easily obtained by mixing and grinding with a dispersing machine.

[0018]

The reason why amino acid betaine and the water-soluble thickening polysaccharide are effective in suppressing the wear of the ball seat is speculated as follows. In amino acid-type betaine, a part of the charged site forms a hydrogen bond with the hydroxyl group of the water-soluble thickening polysaccharide, or binds by attracting an electron pair of an oxygen atom, and also bonds with the water-soluble thickening polysaccharide. The missing portion is compatible with metals such as nickel silver and stainless steel used for the ballpoint pen tip. As a result, an adhesion layer of the amino acid type betaine-water-soluble thickening polysaccharide is formed on the metal surface of the ball seat.

The water-soluble thickening polysaccharide contained in the adhesion layer of the amino acid type betaine-water-soluble thickening polysaccharide is generally a huge molecule, and is intricately entangled, associated, etc., and present in the ink composition. Therefore, the entire adhesion layer is thick and large enough to receive the frictional resistance between the ball and the ball receiving seat. When the ball starts to rotate, the adhesion layer shifts in the direction of rotation of the ball with the amino acid type betaine portion attached to the ball seat, and absorbs frictional resistance between the ball and the ball seat. When the ball further rotates, the amino acid type betaine separates from the ball receiving seat, and the adhesive layer is discharged. By repeating such displacement and ejection, the adhesion layer absorbs most of the frictional resistance and acts as a lubricant.As a result, the abrasion resistance between the ball and the ball seat is reduced, and the wear of the ball seat is reduced. It is thought to be less. As described above, since the adhesion layer has a great effect on suppressing abrasion of the ball seat, it is not necessary to add a large amount of the amino acid type betaine and the water-soluble thickening polysaccharide. Therefore, ink spots, blurring of handwriting, shading of handwriting, etc. No problem occurs.

[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
The value of less than cp is measured with a standard cone rotor 10 rpm of ELD type viscometer manufactured by Tokimec Co., Ltd.
The value of less than p is measured with a standard cone rotor at 1 rpm of an ELD viscometer manufactured by Tokimec Co., Ltd.
A value of less than p was measured with a Tokimec ELD viscometer ST rotor at 20 rpm, and a value of 2,000 cp or more was measured with a Tokimec ELD viscometer ST rotor at 2.5 rpm. The temperature during the measurement was 25 ° C. In each of the examples, “parts” means “parts by weight”.

Example 1 NKW-2105 (yellow aqueous pigment base, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 45.0 parts Hydroxypropylated guar gum (water-soluble thickening polysaccharide) 0.5 part Lipomin LA (amino acid type betaine, 1.0 part Proxel GXL (preservative, manufactured by ICI Japan) 0.1 part Water 53.4 parts Components other than guar gum in each of the above components were mixed and stirred for 1 hour with a stirrer. Thereafter, hydroxypropylated guar gum was added and stirred again for 3 hours to obtain a yellow aqueous ink composition having a viscosity of 380 cp.

Example 2 Daiwa Red No. 104 (Dye, manufactured by Daiwa Chemical Industry Co., Ltd.) 0.5 part Xanthan gum (water-soluble thickening polysaccharide) 1.8 parts Hydroxypropyl cellulose (water-soluble thickening polysaccharide) 1 2.0 parts Levon 2000 (amino acid type betaine, manufactured by Sanyo Kasei Kogyo Co., Ltd.) 2.0 parts Water 95.7 parts After mixing and stirring components other than xanthan gum and hydroxypropyl cellulose in the above components for 1 hour with a stirrer. ,
Xanthan gum and hydroxypropyl cellulose were added, and the mixture was stirred again for 3 hours to obtain a red aqueous ink composition having a viscosity of 1950 cp.

Example 3 NKW-6559 (black aqueous pigment base, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 40.0 parts Xanthan gum (water-soluble thickening polysaccharide) 0.5 part Anone BL (amino acid type betaine, Nippon Oil & Fat) 2.0 parts Anon LG (amino acid type betaine, manufactured by NOF CORPORATION) 1.5 parts Joncryl J-61 (styrene acrylic resin, manufactured by Johnson Polymer Co., Ltd.) 1.0 part PEMULEN TR- 1 (copolymer of acrylic acid and alkyl methacrylate, manufactured by BFGoodrich) 0.4 part Water 54.3 parts 25% aqueous sodium hydroxide 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, the mixture was stirred for 30 minutes, and a 25% aqueous sodium hydroxide solution was added thereto, and the viscosity was 550 cp.
Was obtained.

Example 4 Phthalocyanine Blue 8.0 parts Ethylene glycol 7.0 parts Propylene glycol alginate (water-soluble thickening polysaccharide) 1.0 part Amphitol 86B (amino acid type betaine, manufactured by Kao Corporation) 0.8 Part Sodium dehydroacetate (preservative) 0.2 part Water 3.0 parts After mixing and stirring components other than propylene glycol alginate in the above components for 4 hours in a ball mill, propylene glycol alginate is added and dispersed again for 2 hours. After removing coarse particles with a 0.65 μm membrane filter (manufactured by Advantech Toyo Co., Ltd.), a blue aqueous ink composition having a viscosity of 895 cp was obtained.

Example 5 Rhodamine 6 GCP (CI Basic Red 1, manufactured by Sumitomo Chemical Co., Ltd.) 0.2 parts Carboxymethyl cellulose (water-soluble thickening polysaccharide) 0.3 parts Levon 2000 1.2 parts Lipomin LA 0.5 part Copolymer of methyl vinyl ether and maleic anhydride (thickener) 0.2 part Water 97.0 parts The above components were mixed and stirred for 3 hours with a stirrer to give a viscosity of 50.
A purple aqueous ink composition of 7 cp was obtained.

Example 6 MA100 (carbon black, manufactured by Mitsubishi Kasei Kogyo KK) 8.0 parts Carboxymethyl hydroxypropylated guar gum (water-soluble thickening polysaccharide) 1.5 parts Carrageenan (water-soluble thickening polysaccharide) 0.2 parts Obazoline LB (amino acid type betaine, manufactured by Toho Chemical Industry Co., Ltd.) 4.0 parts NP-20 (polyoxyethylene nonylphenyl ether, manufactured by Nikko Chemicals Co., Ltd.) 2.0 parts Sodium benzoate 0. 4 parts Propylene glycol 5.0 parts Water 80.9 parts After mixing and stirring the above components in a ball mill for 3 hours other than carboxymethylhydroxypropylated guar gum and carrageenan, add carboxymethylhydroxypropylated gargam and carrageenan and add again. Performed a dispersion treatment for 2 hours and prepared a black aqueous ink composition having a viscosity of 2018 cp. It was obtained.

Example 7 Kronos KR380 (manufactured by Titanium Industry Co., Ltd.) 30.0 parts Xanthan gum 0.4 parts SWANOL AM-3130N 7.0 parts Joncryl J61J (ammonium salt of styrene-acrylate copolymer, Johnson Polymer Co., Ltd.) 10.0 parts Water 42.6 parts Ethylene glycol 5.0 parts Glycerin 5.0 parts Among the above components, components other than xanthan gum are mixed,
After performing a dispersion treatment in a ball mill for 24 hours, xanthan gum was added and the mixture was stirred for 1 hour, and the viscosity was 12,000 cps.
A white aqueous ink composition (E-type viscometer, st rotor, 1 rpm, 25 ° C.) was obtained.

Comparative Example 1 A yellow aqueous ink composition having a viscosity of 475 cp was obtained in the same manner as in Example 1 except that the amount of polyoxyethylene oleyl ether was added except for Lipomin LA of Example 1.

Comparative Example 2 A red aqueous ink composition having a viscosity of 1870 cp was obtained in the same manner as in Example 3 except that the amount of polyoxyethylene hardened castor oil was added except for Levon 2000 of Example 2.

Comparative Example 3 A black aqueous ink composition having a viscosity of 316 cp was obtained in the same manner as in Example 4 except that the amount of sodium polyacrylate was added except for the xanthan gum of Example 3.

Comparative Example 4 A blue aqueous ink having a viscosity of 1025 cp was prepared in the same manner as in Example 4 except that enazicol CNS (imidazoline type betaine, manufactured by Lion Corporation) was added in the same amount except for Amphitol 86B of Example 4. A composition was obtained.

Comparative Example 5 Except for the carboxymethylcellulose of Example 5, except that the copolymer of methyl vinyl ether and maleic anhydride was added in the same amount, the viscosity was 365 cp.
Of a blue water-based ink composition was obtained.

Comparative Example 6 Except for adding the amount of polyoxyethylene sorbite tetraoleate except for the ovazoline LB of Example 6,
A black aqueous ink composition having a viscosity of 2200 cp was obtained in the same manner as in Example 2.

Comparative Example 7 Except for SWANOL AM-3130N of Example 7, except that polyoxyethylene octyl phenyl ether was added in the same amount, the viscosity was 11,000.
A white aqueous ink composition of cp was obtained.

As described above, the aqueous ink compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 7 are made of hollow polypropylene pipes having one end connected with a nickel-white ballpoint pen tip (ball material: cemented carbide). 0.8 g in a transparent ink container (K105 refill for Pentel)
Filling, writing distance, ball sinking amount, dent, handwriting bleeding,
The handwriting was tested for shading. The results are shown in Tables 1 and 2.

Writing distance: Using a rotating 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
7 used all of the filled ink composition, while Comparative Examples 1 to 4 had 20% of the filled ink composition remaining, but did not discharge ink. ) 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 was measured using a tool microscope (digital small measuring microscope, MODEL STM).
-DH Olympus Optical Co., Ltd.) was used to measure the length from the tip of the ballpoint pen tip to the tip of the ball. Bote: In the above-mentioned writing test, the number of boulders in 100 m of the initial handwriting was visually measured. In addition, in the length of about 3mm,
A portion having a handwriting width 1.5 to 2.0 times the normal width was measured as a dent. Bleeding of handwriting: In the above-described writing test, the largest handwriting width was measured, and it was visually determined whether or not the boundary of the handwriting at that location was unclear (whether the handwriting was blurred). Boundary is unclear ... × Boundary is clear ... ○ Shading of handwriting: initial handwriting 100 m in the above writing test
A portion having a low handwriting density was visually determined, and the length was measured.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

As described above in detail, the water-based ink composition according to the present invention can be used for ink spotting, handwriting bleeding,
As long as problems such as separation of the ink composition do not occur, wear of the ball seat due to rotation of the ball can be reduced, and the desired object of preventing ball sinking as much as possible can be sufficiently achieved. Thus, the original long writing distance corresponding to the amount of the filled ink is realized.

Claims (1)

[Claims] 1. An aqueous ink composition comprising at least a water-soluble thickening polysaccharide, an amino acid type betaine and water.