JP3186354B2 - Aqueous ink composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition for a writing implement containing at least a coloring material, water and a resin.

[0002]

2. Description of the Related Art An ink composition for a general writing instrument uses a dye or a pigment as a coloring material, and dissolves and / or dissolves the coloring material in a solvent.
Or disperse, and, if necessary, add a resin for improving fixability and adjusting viscosity, add a surfactant for improving solubility and dispersion stability, and further add an antiseptic / antifungal agent and the like. I have. Here, the viscosity of the ink composition has been regarded as important because it is closely related to the form of the writing instrument.

[0003] In particular, an aqueous ball-point pen ink composition is used in which an ink having a viscosity of 1 to several centipoise (cps) is impregnated into an ink occluding material such as a fiber converging material. It has a handwriting that is not sharp.

[0004] In the case where the ink is impregnated into the ink occluding body as described above, the remaining amount of the ink is difficult to understand from the external appearance.
To know the remaining ink, increase the viscosity of the ink,
There is a method of storing ink in a transparent container so that the ink itself can hold the ink.

Conventionally, the viscosity of an ink composition has generally been adjusted by adding a resin. In the case of an aqueous ink composition containing water as a solvent for the ink composition, for example, natural arabic gum, tragacanth gum, guar gum, locustobi-
Gum, alginic acid, carrageenan, gelatin, casein, xanthene gum, dextran, semi-synthetic methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, sodium starch glycolate, sodium alginate Propylene glycol alginate, synthetic polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, sodium polyacrylate, carboxyvinyl polymer, polyethylene oxide, copolymer of vinyl acetate and polyvinylpyrrolidone, acrylic resin One or more water-soluble polymers such as alkali metal salts have been used.

[0006]

When the above-mentioned resin is used as a viscosity modifier of an ink composition, the problem that the dye is insolubilized depending on the kind of the dye and the aggregation of the pigment is caused depending on the kind of the pigment. was there. Therefore, it was necessary to further add a solubilizer and a dispersant to the ink composition. In addition, the bonding of the molecules of the added resin is broken due to decay by microorganisms or decomposition due to oxidation, and the function of adjusting the viscosity is not exhibited. As a result, the viscosity of the ink composition decreases over time. was there. Further, when writing is performed on a processed paper having a resin layer formed on the surface of an art paper or the like, there is a problem that repelling occurs in the handwriting and the handwriting width and handwriting density become non-uniform.

When the above-mentioned resin is used as a viscosity modifier of the water-based ballpoint pen ink, the dye is insolubilized depending on the kind of the dye of the coloring material, and the aggregation of the pigment is caused depending on the kind of the pigment of the coloring material. There was a problem that writing became impossible. Therefore, it was necessary to further add a solubilizer and a dispersant to the ink composition. In addition, the bonds of the added resin molecules are broken due to decomposition by microorganisms or decomposition by oxidation, and the function of viscosity adjustment is not exhibited,
As a result, there has been a problem that the viscosity of the ink composition decreases with time, and the ink composition cannot be held in a hollow cylinder. Further, when writing on a processed paper having a resin layer formed on the surface of an art paper or the like, there is a problem that the ball spins or repelling occurs in the handwriting, resulting in uneven handwriting width and handwriting density. Was.

[0008]

Means for Solving the Problems The present invention provides at least:
A coloring material, water, a compound represented by the above general formula (Formula 1) and / or
Alternatively, the gist is an aqueous ink composition comprising a salt thereof.

[0009] The aqueous ink composition of the present invention is preferably an aqueous ink composition.
When used as an ink composition for Lupen, the ink viscosity should be 50 to 2000 cps (less than 600 cps for a standard cone rotor 1 rpm of Tokimec ELD viscometer).
Measured at 600 cps or more, manufactured by Tokimec EL
It is desirable to set it in the range of D-type viscometer ST-type rotor measured at 20 rpm and temperature at 25 ° C.). At this time,
In addition to suppressing the occurrence of brush strokes, the ink becomes ink that can be held by itself in the hollow cylinder, so that the hollow cylinder can be made of a transparent substance to provide a ball pen structure that allows the remaining ink amount to be confirmed. . When the ink viscosity is less than 50 cps, it becomes difficult to hold the ink in the hollow cylinder,
If it is higher than ps, line breaks and dents are likely to appear in the handwriting.

The aqueous ink composition of the present invention can be used as a colorant without limitation for both dyes and pigments conventionally used in aqueous ink compositions. -Lefast Black D Conc (CI Direct Black 17), Water-
Black 100L (19), Water Black L-
200 (19), Water Black # 7 (1)
9), Kayaset Black W9 (19), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black E
X (38), Direct Deep Black (similar to 38), Direct Fast Black Conch (5
1), Kayalas Sprague VGN (71), Kayak Direct Brilliant Ero-G (CI Direct Ero-4), Direct Fast Ero-5GL (2)
6), Eisen Muraero-GCLH (44), Direct Fast Ero-R (50), Eisen 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), Eisen Buri Malabin Conch 2B
LH (75), Sumilight Red F3B (80),
Aizen Burimura Red 4BH (81) Kayasupurarubin BL (83), Kayasu Light Red F5G
(225), Kayasu Light Red F5B (22)
6), Kayalas Light Rose FR (227) 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 (8
6), Kayalaster-Coisble-GL (86), Daiwable-215H (87), Kayalas Scramble-F
F2GL (Id. 106), Kayaras Splashable-FFRL
(Id. 108) Kayasu Splatter-Koizuru-FBL
(1992), Acid Dye Black 10B (CI Acid Black 1), Nigrosine (2), Water Black R455 (2), Water Black R510 (12). 2), Sumino-Lumiring Black 8BX (24), Kayano-Lumiring Black VLG (26), Kayano-Lumiring Black BR
Conch (31), Mitsui Nylon Black GL (5)
2), Aizen Opal Black WH Extra Conch (52), Sumilan Black WA (52), Ranyl Black BG Extra Conch (107), Kayano-
LUMILING BLACK TLB (109), SUMINO-LUMILLING BLACK B (109), KAYANO LUMILING BLACK TLR (110), Eisen Opal Black New Conc (119), Water Black 187
-L (154) Acid Yellow- # 10 (CI Acid Elo-1), Kayaking Acid Brilliant Flavin FF (7: 1), Kayasilero-GG (17),
Xylene Light Ero-2G 140% (17), Sumino-Leveringero-NR (19), Water Yellow # 1 (23), Daiwa-Trazine (25),
Kayaktor-Tradazine (23), Sumino-Lufastero-R (25), Diacido Lightero-2GP (29), Sumino-Lumiringero-O (38), Sumino-Lumiringero-MR (23) 42), Water Yellow # 6 (42), Kayano Luero-NFG (4)
9), Sumino-Lumiringero-3G (Id. 72), Sumino-Lufastero-G (Id. 61), Sumino-Lumiringero-G (Id. 78), Kayano Luero-N5G (Id. 1)
10), 200% of Sumino-Lumiringero-4G (1
41), Kayano Luero-NG (135), Kayano-
Lumilingero-5GW (127), Kayano Lumiling-6GW (142), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (9), SO- Lalvin Extra (14), Daiwa-Kokushin (18), War-
Tar Scarlet (No. 18), Daiwa Red No. 102 (No. 18), Eizen Bonso-RH (No. 26), Daiwa Red No. 2 (No. 27), Sumino-Levering Brilliant Red S3B (No. 35), Kayasil Rubino 3GS (37), Eisenerythrosine (51), Kayak Acid Lo-Damine FB (52), Daiwa Red No. 106 (52), Sumino-Levering Rubinol 3GP
(Id. 57), Diacid Alizarin Rubinol F3G
200% (82), Alizarin Rubinol 5G (8)
3), Aizen Eosin GH (87), Water Red # 2 (87), Daiwa Red 103WB (8)
7), Water Pink # 2 (92), Eisen Acid Phloxine PB (92), Daiwa Red No. 104 (92), Rose Bengal (94), Kayano Milling Scarlet FGW (111) ), Kayano Lumiring Rubin 3BW (129), Sumino-Lumiring Brilliant Red 3BN Conch (131), Sumino-Lumiring Brilliant Red BS (138), Aizen Opal Pink BH (186), Sumino-L Brilliant Red B Conc (249), Kayak Acid Brilliant Red 3BL (254), Kayak Acid Brilliant Red BL (265), Kayano-Milling Red GW (276), Mitsui Acid Violet 6BN (CI Acid). Violet 1
5), Mitsuiacid Violet BN (17), Water Violet # 1 (49), Water Violet # 5 (49), Daiwa Purple No. 1 (49), Violet L10 (49) ), Sumitomo Patentable-VX (CI Acid Bull-1), Water
Bull # 106 (1), Patent Bull-AF (7), Waterable # 9 (9), Daiwa Blue No. 1 (9), Bull L20 (9), Sprano Rubles-
B (15), Waterable # 116 (15),
Orient Soluble-OBC (22), Orient Soluble-OBX (22), Suminole Leveling Bull-4GL (23), Mitsui Nylon Fast Bull-G (25), Kayasil Bull-AGG (4)
0), Kayasil Bull-BR (41), Mitsui Alizarin Safirolle SE (43), Sumino-Rel Leveling Skible-R Extra Conch (62), Mitsui Nylon Fast Skible-R (78), Sumitomo Brilliant indocyanine 6Bh / e (83), Sandran cyanine N-6B 350% (90), Waterable # 115 (90), Waterable # 10
5 (90), Orient Soluble-OBB (9)
3), Spranolucyanine 7BF (100), Sumitomobrilliant-5G (103), Acid Bull (103), Asilane Brilliant-FFR
(Id. 104), Kayano-Lumiring Ultra Sky SE
(No. 112), Kayano-Lumiring Cyanine 5R (No. 1)
13), Aizen opalcyanine 2GLH (15
8), Daiwa Guinea Green B (CI Acid Green 3), Acid Brilliant Milling Green (No. 9), Daiwa Green # 70 (No. 16), Kayanor Cyaning Green G (No. 25) ), Sumino-Luminating Green G (27), Water Orange # 17 (C.I.
I. Acid dyes such as Acid Orange 56), food dyes such as Water Yellow # 2 (CI Foodro-3), malachite green (C.I. 42000), Victoria Bull-FB ( CI44045), methyl violet FN (CI42535), rhodamine F
4G (CI45160), Rhodamine 6GCP
(CI. 45160) and the like.

As the pigment, Special Blac is used.
k 6, S170, S610, 5, 5, 4,
A, 550, 35, 250, 100, Prin
tex150T, U, V, 140U, 140
V, 95, 90, 85, 80, 75, 5
5, 45, P, XE2, L6, L, 30
0, 30, 30, 35, 25, 200, A,
G (above, manufactured by Degussa Japan Co., Ltd.), # 2400
B, # 2350, # 2300, # 2200B, # 100
0, # 950, # 900, # 850, # MCF88, M
A600, MA100, MA7, MA11, # 50, #
52, # 45, # 44, # 40, # 33, # 32, # 3
0, CF9, # 20B, # 4000B (Mitsubishi Chemical Industries, Ltd.), MONARCH 1300, 110
0, 1000, 900, 880, 800, 7
00, MOGUL L, REGAL 400R, 66
0R, 500R, 330R, 300R, 99
R, ELFTEX 8, 12 and BLACK PEAR
LS 2000 (above, Cabot Co. LTD, USA)
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 black such as tex 975, 900, and SC (all manufactured by Colombian Carbon Japan Co., Ltd.);
A-10, same 10P, same 15, same 20, same 30, same 3
5, 60, 80, 90, KR-310, 38
0, 460, 480 (Titanium Industry Co., Ltd.
Inorganic pigments such as titanium oxide such as P25 (manufactured by Nippon Aerosil Co., Ltd.), black iron oxide, yellow iron oxide, red iron oxide, ultramarine, cobalt blue, chrome green, and chromium oxide; Hansaero-10G; Same 5G, Same 3G, Same 4, Same G
R, same A, benzidine erotic, permanent erotic NC
G, tartrazine lake, quinoline erotic, sudane 1, permanent orange, indasrene brilliant orange GN, permanent brown FG, para brown, permanent red 4R, fire red, brilliant oka -Min BS, pyrazolone red, lake red C, quinacridone red, brilliant cumin 6
B, Bold-5B, Thioindigo Red, Fast Violet B, Dioxane Violet, Alkaline-
Organic pigments such as lake, phthalocyanine blue, indigo, acid green lake, phthalocyanine line, etc.
BS-605, BS-607 (Toyo Aluminum Co., Ltd.)
Bronze Powder-P-555, P-777 (above, manufactured by Nakajima Metal Foil Industry Co., Ltd.), Bronze Powder-3L
5 and 3L7 (above, manufactured by Fukuda Metal Foil Industry Co., Ltd.). In addition, inorganic fluorescent pigments such as zinc sulfide, zinc silicate, zinc cadmium sulfate, calcium sulfide, strontium sulfide, calcium tungstate, and other known organic fluorescent pigments may be used. The above-mentioned coloring agents can be used alone or in combination with other coloring agents. The amount of the coloring agent used varies depending on the color tone and the like, but is preferably 0.5 to 20% by weight based on the total amount of the aqueous composition.

Further, in the case of a pigment ink composition, using an aqueous ink composition base in which a pigment is dispersed in an aqueous medium is advantageous in producing a pigment ink composition. Specifically, Fuji. SP. Black. 8031, 81
19, 8167, 8276, 8381, 840
6, Fuji. SP. Red. 5096, 5111,
5193, 5220, Fuji. SP. Borde
aux. 5500, Fuji. SP. Blue. 606
2, 6133, 6134, Fuji. SP. Gre
en. 7051, Fuji. SP. Yellow. 40
60, Fuji. SP. Violet. 9011, Fu
ji. SP. Pink. 9524, 9527, Fuj
i. SP. Orange. 534, FUji. SP. B
rown. 3074 (all manufactured by Fuji Dye Co., Ltd.), Em
acol. Black. CN, Emacol. Blu
e. FBB, FB, KR, Emacol. Green
n. LXB, Emacol. Violet. BL, Em
acol. Brown. 3101, Emacol. Ca
rmmine. FB, Emacol. Red. BS, E
macol. Orange. R, Emacol. Yel
low. FD, ibid. IRN, 3601, FGN, GN, GG, F5G, F7G, 10GN, 1
0G, Sndye. Super. Black. K, C, Sandye. Super. Gray. B, San
dye. Super. Brown. SB, FRL, RR, Sandye. Super. Green. L5
G, GXB, Sandye. Super. Nayv
y. Blue. HRL, GLL, HB, FBL-
H, FBL-160, FBB, Sandye. Su
per. Violet. BL. H / C, BL, San
dye. Super. Bordeaux. FR, San
dye. Super. Pink. FBL, F5B, S
andye. Super. Rubine. FR, San
dye. super. Carmmine. FB, San
dye. Super. Red. FFG, RR, B
S, Sadye. Super. Orange. FL, R, BO, Sandye. Gold. Yellow.
5GR, R, 3R, Sandye. Ywllow.
GG, F3R, IRC, FGN, GN, GR
S, GSR-130, GSN-130, GSN,
10GN (above, manufactured by Sanyo Dyeing Co., Ltd.), Rio. Fa
st. Black. Fx. 8012, 8313, 8
169, Rio. Fast. Red. Fx. 8209,
8172, Rio. Fast. Red. S. Fx. 8
315, 8316, Rio. Fast. Blue. F
x. 8170, Rio. Fast. Blue. FX. 8
170, Rio. Fast. Blue. S. Fx. 83
12, Rio. Fast. Green. S. Fx. 83
14 (manufactured by Toyo Ink Composition Co., Ltd.), NKW-2
101, 2102, 2103, 2104, 21
05, 2106, 2107, 2108, 211
7, 2127, 2137, 2167, 2101
P, 2102P, 2103P, 2104P, 2
105P, 2106P, 2107P, 2301,
2302, 2303, 2304, 2305, 2306, 2307, 2308, 2317, 2
327, 2337, 2367, 2108P, 21
17P, 2127P, 2137P, 2167P,
3002, 3003, 3004, 3005, 3007, 3077, 3008, 3402, 3
404, 3405, 3407, 3408, 34
77, 3602, 3603, 3604, 360
5, 3607, 3677, 3608, 370
2, 3703, 3704, 3705, 377
7, 3708 (all manufactured by Nippon Fluorescence Co., Ltd.); 1000F series (manufactured by Toyo Soda Co., Ltd.)
Shinroihi Color Base SW-11, SW-12,
SW-13, SW-14, SW-15, SW-
16, SW-17, SW-27, SW-37,
SW-47, SW-18, and SW-07 (all manufactured by Shinloich Co., Ltd.) and the like, and these can be used alone or in combination of two or more.
Further, dyes, pigments, and dispersed pigments can be used in combination.

The solvent is essentially water, and various organic solvents can be used in addition to water. As the organic solvent, specifically, ethanol, methanol, 1-propanol,
2-propanol, 1,3-propanediol, 2-methyl-2,4-pentaneddiol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol
2-phenoxyethanol, 2-benzyloxyethanol, 2- (2-methoxyethoxy) ethanol,
2- (2-ethoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol
Butoxyethoxy) ethanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol and the like.

Further, since the compound represented by the above general formula (Formula 1) has an emulsifying action, xylene, toluene,
Hydrocarbons such as cyclohexane, ethers such as anisole, dibenzyl ether, 1,2-diethoxyethane, 1,2-dibutoxyethane, methyl ethyl ketone, 2-pentanone, 2-hexanone, methyl isobutyl ketone Organic solvents such as ketones such as diisobutyl ketone and esters such as ethyl acetate and butyl acetate can also be used in small amounts. One or more of the above organic solvents are used.
It can be used in combination of more than one species.

As the resin for thickening the ink composition, a substance represented by the general formula (1) and / or a salt thereof can be used.

The ink composition of the present invention can be obtained by mixing and stirring a coloring material, which is an essential component, water and a compound represented by the above general formula (Chemical Formula 1). Further, if necessary, a coloring machine may be used, and the coloring material may be classified by filtration and centrifugation. As the writing means, as the type of the pen tip, there can be used a writing instrument such as a pen-type writing instrument, a writing brush, an air brush, a ball pen, a fiber convergent pen tip, and a synthetic resin pen tip. In particular, when used for a ball-point pen, it is preferable from the viewpoints of the display of the remaining ink amount, the ink color, and the quality of handwriting.

Further, if necessary, a resin can be added in order to make the coloring material adhere to the writing surface. This resin is made of natural gum arabic, tragacanth gum, guar
Gum, locust bean gum, alginic acid, carrageenan, gelatin, casein, xanthen gum, dextran, semi-synthetic methylcellulose, ethylcellulose,
Hydroxyethyl cellulose, carboxymethyl cellulose, sodium starch glycolate, sodium alginate, propylene glycol alginate,
Mix one or more water-soluble polymers such as synthetic polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyethylene oxide, copolymers of vinyl acetate and polyvinyl pyrrolidone, and alkali metal salts of acrylic resins. Can be used. Since some of these resins cause insolubilization of the dye in the ink composition and aggregation of the dispersed pigment, it is necessary to change the type of the resin to be added depending on the type of the dye pigment.

In addition to the above, various polymer dispersants and surfactants can be used. For example, as a polymer dispersant, natural rubbers such as gum arabic and gum tragacanth; glucosides such as saponin; cellulose derivatives such as methylcellulose, carboxycellulose and hydroxymethylcellulose; and ligninsulfonic acid Salt, natural polymer such as shellac, polyacrylate, salt of styrene-acrylic acid copolymer, salt of vinylnaphthalene-maleic acid copolymer, β
Anionic polymers such as salts of naphthalenesulfonic acid formalin condensate, phosphates, and polyvinyl alcohol;
Nonionic polymers such as polyvinylpyrrolidone and polyethylene glycol are exemplified. As surfactants, fatty acid salts, higher alcohol sulfate salts,
Liquid fatty acid sulfates, anionic surfactants such as alkyl allyl sulfonates, polyoxyethylene alkyl ethers, sorbitan alkyl esters,
Nonionic surfactants such as polyoxyethylene sorbitan alkyl esters are included.

Further, in order to suppress the outflow inhibition of the ink composition in the ink passage of the writing implement 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 ethylenediaminetetraacetate for preventing corrosion of the metal, and oleic acid as a solubilizer are used. Such fatty acids can also be added as appropriate.

[0021]

The aqueous ink composition of the present invention having the compound represented by the above general formula (Formula 1) and / or a salt thereof as an essential component has a stable viscosity over time without causing precipitation of dyes and aggregation of pigments. The reason why it is possible to write uniformly on a processed paper having a resin layer formed on the surface of an art paper or the like when incorporated in various writing instruments while maintaining the above is considered as follows.

The compound represented by the above general formula (Chemical Formula 1) exists in the form of a filament that has shrunk in a coil shape and overlapped in a layer shape in a dry state, and hydrates and swells in a state of being dispersed in an aqueous ink. It exhibits a thickening effect. Further, when an alkali metal is added, the carboxyl group in the molecule is dissociated and swells further due to its electric repulsion. Therefore, when added to the aqueous ink composition, even a small amount shows a remarkable thickening action. In addition, since the molecule has a hydrophilic portion and a lipophilic portion and functions as a surfactant, it does not cause dye insolubilization or pigment aggregation even when added to an aqueous ink composition. Further, since there is a lipophilic part in the molecule, it is possible to write evenly on coated paper having strong lipophilicity. Further, the compound represented by the above general formula used in the present invention is resistant to hydrolysis and oxidation and does not assist the growth of microorganisms, so that it has good stability over time.

[0023]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples. In Examples and Comparative Examples, "parts" means "parts by weight".
Is shown.

The conditions for measuring the viscosity of each ink composition are 50
The value of less than cps is measured with a standard cone rotor at 10 rpm of an ELD viscometer manufactured by Tokimec Co., Ltd.
The value of less than 0 cps is measured with a standard cone rotor at 1 rpm of an ELD type viscometer manufactured by Tokimec Co., Ltd.
For less than 500 cps, measured with a Tokimec ELD viscometer ST-type rotor at 20 rpm. For more than 500 cps, Tokimec ELD viscometer ST-type rotor.
It was measured at 10 rpm. The temperature during the measurement was 25 ° C.

Example 1 Purified water 17.5 parts Ethylene glycol 10.0 parts Glycerin 20.0 parts NKW-2105 (pigment dispersion, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 40.0 parts Proxel GXL (1. 2-Benzothiazalin-3-one, manufactured by ICI, UK 0.2 parts PEMULEN TR-1 2% aqueous solution (compound represented by the above formula 1, BF Goodrich, USA) 12.0 parts 25 0.3% aqueous sodium hydroxide solution 0.3 parts of the above components were mixed except for a 25% aqueous sodium hydroxide solution, stirred for 1 hour, and then added with a 25% aqueous sodium hydroxide solution to obtain a 1600 cps yellow ink several times.

Example 2 Purified water 23.5 parts Propylene glycol 10.0 parts Glycerin 15.0 parts NKW-2117 (pigment dispersion, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 40.0 parts Proxel GXL 0.2 Part PEMULEN TR-2 2% aqueous solution (compound represented by the above formula 1, BF Goodrich, USA) 11.0 parts 25% lithium hydroxide aqueous solution 0.3 part 25% water in each of the above components A mixture other than the aqueous lithium oxide solution was mixed and stirred for 1 hour, and then a 25% aqueous lithium hydroxide solution was added to obtain a pink ink having a viscosity of 1100 cps.

Example 3 Purified water 46.8 parts Water Black # 100L (CI Direct Black 19, manufactured by Orient Chemical Industry Co., Ltd.) 30.0 parts Ethylene glycol 13.0 parts Dehydroacetic acid Sodium 0.2 part 2% aqueous solution of the compound represented by the following general formula (Chemical Formula 2) 10.0 parts The above components are mixed, heated to 40 to 50 ° C, stirred for 1 hour, and then filtered to obtain a viscosity of 60 cps. Of black ink was obtained.

[0028]

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Example 4 73.7 parts of purified water Aizen Eosin GHC (CI Acid Red 87, manufactured by Hodogaya Chemical Industry Co., Ltd.) 5.0 parts Water Orange # 17 (CI Acid Orange) 56, manufactured by Orient Chemical Industry Co., Ltd.) 1.0 part Diethylene glycol 10.0 parts Proxel GXL 0.2 parts 2% aqueous solution of the compound represented by the following general formula (Chemical Formula 3) 10.0 parts 25% 0.1 part of aqueous sodium hydroxide solution
After stirring for an hour, a 25% aqueous sodium hydroxide solution was added to obtain a red ink having a viscosity of 150 cps.

[0030]

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Example 5 Purified water 72.42 parts Lodamine 6 GCP (CI Basic Red 1, manufactured by Sumitomo Chemical Co., Ltd.) 0.3 parts Glycerin 2.0 parts Polyethylene glycol # 400 10 0.0 part Proxel GXL 0.2 part 2% aqueous solution of the compound represented by the following general formula (Formula 4) 15.0 parts Triethanolamine 0.08 part Mix all of the above components except for triethanolamine and mix for 1 hour After stirring, triethanolamine was added to obtain a pink fluorescent ink having a viscosity of 600 cps.

[0032]

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Example 6 40.95 parts of purified water NKW-3007 (aqueous fluorescent ink base, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 40.0 parts Waterable # 9 (CI Acid Bull-9, 0.8 parts Glycerin 8.0 parts Proxel GXL 0.2 parts 2% aqueous solution of the compound represented by the following general formula (Chemical Formula 5) 10.0 parts Triethanolamine 0.05 parts Other than triethanolamine in each of the above components was mixed and stirred for 1 hour, and then triethanolamine was added to obtain a yellow-green fluorescent ink having a viscosity of 250 cps.

[0034]

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Example 7 Purified water 70.22 parts Ethylene glycol 15.0 parts MA100 (carbon black, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 8.0 parts Joncryl J61j (styrene-acrylic acid copolymer) 2.5 parts Proxel XL-2 (1.2-benzoisothiazolin-3-one, manufactured by ICI Japan) 0.2 part The following general formula (Chemical Formula 6) ) 2% aqueous solution of the compound represented by the following formula: 4.0 parts 2-amino-2-methyl-1.3-propanediol 0.08 part Of the above components, represented by the above general formula (Chemical Formula 1) A compound and a compound other than 2-amino-2-methyl-1.3-propanediol were blended and dispersed in a commercially available sand mill for 4 hours to obtain a 2% aqueous solution of the compound represented by the above general formula (Chemical Formula 1). After adding and stirring for 1 hour, 2- Amino-2-methyl-1,3-propanediol - to obtain a black ink having a viscosity 60cps those stirring was further added Le 0.5 hours with the removal of coarse particles by centrifugation.

[0036]

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Example 8 58.75 parts of purified water 15.0 parts of propylene glycol 6.0 parts of quinacridone red (CI Pigment Red 112) 6.0 parts of SMA Resin 1440 (styrene-maleic acid copolymer 27%, USA) ARCO Chemical Co. LTD) 10.0 parts Proxel XL-2 0.2 parts 2% aqueous solution of the compound represented by the following general formula (Chemical Formula 7) 10.0 parts 2-amino-2-methyl-1.3 -Propanediol 0.05 part A commercially available Dyno containing a compound other than the compound represented by the above general formula (Chemical Formula 1) and 2-amino-2-methyl-1.3-propanediol, among the above components. -Dispersion treatment with a mill for 4 hours, addition of the compound represented by the above general formula (Chemical Formula 1), and stirring for 1 hour, followed by 2-amino-2-methyl-1.3-propanediol. Viscosity 300c what was further stirred for 0.5 hours with the addition of cycle by removal of coarse particles were centrifuged
ps red ink was obtained.

[0038]

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Example 9 Purified water 46.6 parts 10% aqueous sodium hydroxide solution 0.2 parts Diethylene glycol 10.0 parts Fuji. S. P. Blue 6062 (blue aqueous pigment base, manufactured by Fuji Dye Co., Ltd.) 25.0 parts Proxel XL-2 0.2 parts 2% aqueous solution of the compound represented by the following general formula (Formula 8) 18.0 parts The components were blended, mixed and stirred for 12 hours, and then filtered to obtain a blue ink having a viscosity of 1800 cps.

[0040]

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Example 10 Purified water 76.79 parts Propylene glycol 15.0 parts Quinacridone red (CI Pigment Red 11) 6.0 parts SMA Resin 1440 10.0 parts Proxel XL-2 0.2 parts 2.0 parts of a 2% aqueous solution of the compound represented by the general formula (Chemical formula 9) 2.0 parts 2-amino-2-methyl-1,3-propanediol 0.01 part The above general formula (Chemical formula 1) And 2-amino-2-methyl-1,3-propanedio-
And a dispersion treatment with a commercially available Dyno-Mill for 4 hours, adding the compound represented by the above general formula (Chemical Formula 1), stirring for 1 hour, and then adding 2-amino-2-methyl-1,3- After adding propanediol and stirring for 0.5 hour, coarse particles were removed by centrifugation, and the viscosity was 40 cps.
Red ink was obtained.

[0042]

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Example 11 56.7 parts of purified water 15.0 parts of propylene glycol 6.0 parts of quinacridone red 10.0 parts of SMA Resin 1440 10.0 parts 0.2 parts of Proxel XL-2 The following general formula (Formula 10) 2% aqueous solution of the compound represented by the formula: 22.0 parts 2-amino-2-methyl-1,3-propanediol 0.1 part Among the above components, the compound represented by the above general formula (Chemical Formula 1) and 2- Amino-2-methyl-1,3-propanedio-
And a dispersion treatment with a commercially available Dyno-Mill for 4 hours, adding the compound represented by the above general formula (Chemical Formula 1), stirring for 1 hour, and then adding 2-amino-2-methyl-1,3- After adding propanediol and stirring for 0.5 hour, coarse particles were removed by centrifugation, and the viscosity was 2500 c.
ps red ink was obtained.

[0044]

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Example 12 Purified water 51.8 parts Water Black # 100L 30.0 parts Ethylene glycol 13.0 parts Sodium dehydroacetate 0.2 part Compound represented by the following general formula (Chemical Formula 11) 5.0 parts of a 2% aqueous solution of the above components The above components were mixed, heated to 40 to 50 ° C., stirred for 1 hour, and then filtered to obtain a black ink having a viscosity of 10 cps.

[0046]

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Example 13 Purified water 58.7 parts Aizen Eosin GHC (CI Acid Red 87, manufactured by Hodogaya Chemical Industry Co., Ltd.) 5.0 parts Water orange # 17 1.0 part Diethylene glycol 10.0 parts Proxel GXL 0.2 parts 2% aqueous solution of the compound represented by the following general formula (Formula 12) 25.0 parts 25% aqueous sodium hydroxide solution 0.1 parts Other than 25% sodium hydroxide in each of the above components And mix
After stirring for an hour, a 25% aqueous sodium hydroxide solution was added to obtain a red ink having a viscosity of 6000 cps.

[0048]

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Comparative Example 1 Compound 2 of the compound represented by the above general formula (Formula 1) of Example 1
% Aqueous solution instead of carboxymethyl cellulose (CMC
Daicel 1205, manufactured by Daicel Chemical Industries, Ltd.)
A black ink having a viscosity of 60 cps was obtained in the same manner except that 0 part was used and water was changed to 51.8 parts.

Comparative Example 2 Compound 2 of the compound represented by the above general formula (Chemical Formula 1) of Example 2
% Aqueous solution instead of carrageenan (Genubisco CSW
0.6 parts of Sanshin Co., Ltd.) and 8 parts of purified water
A red ink having a viscosity of 300 cps was obtained in the same manner except that 3.1 parts were used.

Comparative Example 3 Compound 2 of the general formula (Chemical Formula 1) of Example 1
A black ink having a viscosity of 4 cps was obtained in the same manner except that purified water was used in place of the aqueous solution.

Comparative Example 4 The compound 2 of Example 1 represented by the above general formula (Chemical Formula 1)
% Aqueous solution instead of carboxymethyl cellulose (CMC
1. Daicel 1205, manufactured by Daicel Chemical Industries, Ltd.)
A black ink having a viscosity of 10 cps was obtained in the same manner except that 0 part was used.

Comparative Example 5 The compound 2 of Example 5 represented by the above general formula (Chemical Formula 1)
% Aqueous solution instead of carboxymethyl cellulose (CMC
Daicel 1350, manufactured by Daicel Chemical Industries, Ltd.)
A black ink having a viscosity of 300 cps was obtained in the same manner except that 0 part was used and purified water was changed to 73.22 parts.

Tables 1, 2 and 3 show the results of the following tests 1 to 5 performed on the inks of Examples 1 to 13 and Comparative Examples 1 to 5. Test 1: Dissolution Stability (Dye Ink) and Dispersion Stability (Pigment Ink) After placing the ink in a glass bottle and sealing, leaving it at room temperature for one month, the ink was filtered with a membrane filter (0.3 μm,
The condition was visually evaluated by instillation into Toyo Roshi Kaisha, Ltd.). ○: no residue ×: residue

Test 2: Fixing property to processed paper Each ink was applied to a writing implement (Brush No. 0, XZBS)
-0, manufactured by Pentel Co., Ltd.)
SY PLOTTER PAPER Hewlett-Packard Co., USA), 10 cm, 10 lines were written, and the state of the handwriting was visually judged. ：: Handwriting with uniform line width and / or density ×: Handwriting with repelling and uneven line width and / or density

Test 3: Writing line Each ink was assembled into an aqueous ballpoint pen (using parts made by Pentel Co., Ltd.), and 10 lines of 10 cm were written on high-quality paper (JIS P3201 writing paper). The number of bosses was measured visually. ○: 0 to 2 Δ: 3 to 15 ×: 16 or more

Test 4: Viscosity stability over time After ink was put in a glass bottle and sealed, and allowed to stand at 50 ° C. for 3 months, the viscosity was measured, and the viscosity reduction rate ((original viscosity−viscosity after aging) × 100 / (Original viscosity). (Viscosity measurement conditions less than 600 cps are ELD manufactured by Tokimec Co., Ltd.
Measured with a viscometer at 1 rpm.
Tokimec ELD viscometer ST rotor 20rpm
Measured in m. (Temperature 25 ° C) ○: 0 to 10% △: 11 to 60% ×: 61% or more

Test 5: Ink Retention in a Cylinder Ink was placed in a polypropylene pipe having an inner diameter of 3 mm, and a ball-point pen tip (ball diameter: 0.6 mm, manufactured by Pentel Co., Ltd.) was attached. The ink was kept downward for 30 minutes, and the state of ink leakage was visually determined. ○: No leakage △: Slight leakage ×: Leakage

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

As described above, the water-based ink of the present invention comprises at least the coloring material, water and the compound represented by the above general formula (1) and / or a salt thereof. It is possible to obtain a desirable viscosity without causing the handwriting, and it is difficult for handwriting to be disturbed such that the handwriting width and handwriting density become nonuniform even on the processed paper as if a resin layer was formed on the surface, and the viscosity over time A stable handwriting with little change can be obtained.

In addition, it is possible to keep the ink in a good condition without being influenced by the kind of the coloring material, especially as a ballpoint ink.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-60-181178 (JP, A) JP-A-61-60768 (JP, A) JP-A-62-27479 (JP, A) JP-A-53-178 59537 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 11/00-11/20

Claims (2)

(57) [Claims] An aqueous ink composition comprising at least a coloring material, water, a compound represented by the following general formula (Formula 1) and / or a salt thereof. 2. The aqueous ink composition having an ink viscosity of 5
2. The water-based ink composition for ball pens according to claim 1, wherein the water-soluble ink composition has a temperature in the range of 0 to 2000 cps (25 [deg.] C.). Embedded image