JPH0488070A - Water-base ink - Google Patents

Abstract

PURPOSE:To provide a water-base ink composed of a colorant, water and a specific copolymer, having excellent dry resistance of pen tip and dryability of written mark and suitable for recorder, stamp, ink jet recording, etc. CONSTITUTION:The objective water-base ink is composed at least of a colorant (preferably acid dye, direct dye or food dye), water and a copolymer of formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a water-based ink, and more particularly to a water-based ink that is used in writing instruments and has excellent drying resistance of the pen tip.

[Conventional technologies and their problems] Conventionally, in order to improve the drying resistance of water-based ink pen nibs, hygroscopic solvents such as glycol solvents, glycol ether solvents, glycol ether ester solvents, and amine solvents have been used. It has been proposed to use water-soluble organic solvents.

However, when the above-mentioned hygroscopic water-soluble organic solvent is added to improve the drying resistance of the pen tip of water-based ink, a problem arises in that the drying property of the handwriting deteriorates. No additives are known that improve both properties.

[Means for Solving the Problems] The gist of the present invention is a water-based ink comprising at least a coloring material, water, and a copolymer represented by the following general formula (I).

The present invention will be explained in detail below.

As the coloring material, water-soluble dyes and pigments can be used.

Any of acid dyes, direct dyes, food dyes, and basic dyes can be used as the water-soluble dye. In particular, acid dyes,
Direct dyes and food dyes are preferable because they have superior dissolution stability and less toxicity than basic dyes.

An example of a direct dye is described below. Japanol Fast Black D Conch (C, 1, Direct Black 17
), Water Black 100 L (19), Water Black L-200 (19), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black EX (
38), Direct Fast Black Conch (51)
), Kayaras Spragley VGN (71), Kayaras Direct Brilliant Yellow G (C, 1, Direct Yellow 4), Direct Fast Yellow 50L (26), Eisen Primula Niro 100LH (44),
Direct Fast Yellow R (50), Eisen Direct Fast Red F H (C, 1, Direct Red 1), Nippon Fast Scarlet GSX (4
), Direct Fast Eroretsu 1~4BS (Same 2
3), Eisen Direct Rodulin BH (same 31)
, Direct Left Scarlet B (37), Kayaku Direct Scarlet 3B (39), Eisen Primula Pink 2BLH (75), Sumilightlet F3B (
80), Eisen Primula Red 4BH (81),
Kayarasu Spragley BL (83), Kayarasurai 1
~Red F5G (225), Kayaras Light Red F5B (226), Kayaras Light Rose FR (227), Direct Sky Blue 6B (C, 1, Direct Blue 1), Dairef l-Sky Blue 5B (
15), Sumilight Splat Blue BRR Conch (7)
1), Daibogen Turquoise Blue S (86), Water Blue #3 (86), Kayara Turquoise Blue GL (86), Kayara Spragray FF2GL
(106), Kayarasu Supra Turquoise Blue FB
Examples include L (199).

An example of an acidic dye is described below. Acid Blue Black 1.0B (C, 1, Acid Black 1), Nigrosine (C, 2), Suminol Milling Black 8BX (
24), Kayanor Milling Black VLG (24)
6), Suminol Fas 1-Black BR Conch (same 3)
1), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conch (52),
Sumiran Black WA (52), Ranil Black BG
Extra Conch (107), Kayanor Milling Black TLB (109), Suminol Milling Black B (109), Kayanor Milling Blank TL
R (110), Eisen Opal Black New Conch (119), Water Black 187-L (154), Kayaku Acid Brilliant Flavin FF
(C, 1, Acid Yellow 7: 1), Kayashiru Yellow G (17), Xylene Light Yellow 2G140
% (17%), Suminol Leveling Yellow NR (1%)
9) Daiwatatrazine (23), Kayafutatrazine (23), Suminol Fast Yellow R (25)
, Diazid Light Yellow 20P (29), Suminol Milling Yellow ○ (38), Suminol Milling Yellow MR (42), Water Yellow #6 (42), Kayanor Yellow NFG (49), Suminol Knoll Milling Yellow 3G (72), Suminol Fast Yellow G (61), Suminol Milling Yellow G
(78), Kayanor Yellow N5G (110),
Suminol Milling Yellow 4.0200% (141)
, Kayanor Yellow NG (1.35), Kayanor Milling Yellow 50W (127), Kayanor Milling Yellow 6GW (142), Sumitomo Fast Scarlet A (C, 1, Acid Red 8), Kayak Silk Scarlet ( 9), Solar Lupine Extra (14), Daiwa New Kokushin (18), Eisenbonso RH (26), Daiwa Red No. 2 (27), Suminol Leveling Brilliant Red 83B (3)
5), Kayacyl Rubinol 3GS (37), Eisenerythrosin (51), Kayaku Acid Rhodamine FB (52), Suminol Leveling Rubinol 30
P (57), Diazid Alizarin Rubinol F
3G200% (82), Eiseneosin GH (82)
7), Water Pink #2 (92), Eisen Acid Phloxin PB (92), Rose Bengal (92)
4), Kayanor Milinges Scarlet FGW (11
1), Kayanor Millingle Pin 3BW (129),
Sumifall Milling Brilliant Red 3BN Conch (Same 131), Suminol Milling Brilliant Red BS (Same 138), Eisen Opal Pink BH (Same 1)
86), Suminor Milling Brilliant Gide B Conch (249), Kayaku Acid Brilliant Red 3BL (254), Kayaku Acid Brilliant Brilliant Red BL (265), Kayanor Milling Red GW (276), Mitsuiacid Bio Red 1-
6BN (C, 1, Acid Violet 15), Mitsu Acid Violet BN (17), Sumitomo Patent Pure Blue 1), Water Blue #106 (1),
Patent blue A. F (same as 7), water blue #9
(9), Daiwa Blue No. 1 (9), Supranor Blue B (15), Orient Solble Blue OBC (
22), Suminol Leveling Blue 4-GL (22), Suminol Leveling Blue 4-GL (22)
3), Mitsui Nylon Fas 1 to Blue G (same 25),
Kayasil Blue AGG (40), Kayasil Blue BR
(41).

Mitsui Alizarin Saphyrol SE (43), Suminol Leveling Sky Blue R Extra Conch (6)
2), Mitsui Nylon Fast Sky Blue B (same 78
), Sumitomo brilliant indocyanine 6Bh/c (
83), Sandrancyanin N-6B 350% (9
0), Water Blue #115 (90), Orien 1-Solble Blue BB (93), Sumitomo Brilliant Blue 5G (103), Kayanor Milling Ultra Sky SE (112), Kayanor Milling Cyanine 5R (113), Eisen Opal Blue 20LH (158), Daiwa Guinea Green B (C
．． 1. Acid Green 3), Acid Brilliant Milling Green B (9), Daiwa Green #70 (16), Kayanol Cyanine Green G (25), and Suminol Milling Green G (27).

Most food dyes are included in direct dyes or acid dyes, but an example of food dyes that are not included is Water Yellow #4 (C.1. Food Yellow 3).

These can be used alone or in combination. The amount used is preferably 2 to 20% by weight based on the total amount of the water-based ink.

Pigments include inorganic pigments such as ocher, barium yellow, navy blue, cadmium red, titanium oxide, red iron black, carbon black, azo pigments, phthalocyanine pigments,
Conventionally known pigments include organic pigments such as nitroso pigments, nitro pigments, basic dye pigments, acid dye pigments, vat dye pigments, mordant dye pigments, and natural dye pigments. These can be used alone or in combination. The amount used is 2 to 20% of the total amount of water-based ink.
It is preferable to add % by weight. When using pigments as colorants, it is necessary to use a dispersant from the aspects of dispersibility, stability over time, and workability. Examples include styrene-maleic acid copolymer, styrene-acrylic acid copolymer Polymers, copolymers of hydrophobic monomers and hydrophilic monomers such as styrene-methylthrene-acrylic acid copolymers and/or salts thereof, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, pentaerythritol fatty acids ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether,
Polyoxyethylene phytosterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxyethylene alkyl amine , polyoxyethylene fatty acid amide, nonionic surfactants such as polyoxyethylene alkylphenyl formaldehyde condensates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, N-acylamino acid salts, N-acylmethyl taurine salts, polyoxy Examples include anionic surfactants such as ethylene alkyl ether acetate, alkyl phosphate, and polyoxyethylene alkyl ether phosphate. Dispersants can be used alone or in combination.

The amount used is 0.2 to 20% of the total amount of the water-based ink composition.
．． 0% by weight is preferred.

Water is used as the main solvent, and the amount used is preferably 30 to 80% by weight based on the total amount of the ink.

The copolymer represented by the above general formula (I) is used to improve the drying resistance of water-based inks. A specific example is Jamal 115 (France, Saraton research rupture)
The amount used is 5 to 15% of the total amount of ink.
Weight percent is preferred.

In addition to the ingredients listed above, moisturizing and/or
Alternatively, a water-soluble organic solvent may be used to prevent freezing. Examples include alcohols such as methanol, ethanol, propatool, isopropanol, butanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1.3-butylene gellicol, thiodiglycol, etc. Glycols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate-1~, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, N-methyl-2-pyrrolidone, sorbitol, sorbitan, acetin , glycerin, etc.

These water-soluble organic solvents can be used alone or in combination. The amount used is 1 to 5% of the total amount of water-based ink.
0 Jukei Kikan is preferable.

Furthermore, there are various kinds of preservatives, anti-mold agents, anti-rust agents and anti-foaming agents to prevent corrosion of metal parts, and the above-mentioned surfactants to improve ink penetration into the writing surface and discharge from writing instruments. It is also possible to select and use additives as appropriate.

This water-based ink is prepared by mixing and stirring using a commonly known stirrer when dyes are used as colorants, and by mixing and dispersing using commonly known dispersing machines when using pigments. It can be easily obtained by

[Function] The copolymer represented by the above general formula (I) has a strong hydrogen bonding force in an aqueous solution, and prevents evaporation of the solvent in the ink. Therefore, since the evaporation of the solvent (particularly water) from the surface of the pen nib is suppressed, the pen nib has excellent drying resistance.

[Example] The present invention will be explained in more detail with reference to Examples below. In the Examples, "1 part" means "part by weight."

Tsubasa-V Water Red #2 2.0 parts (C, I
, Acid Red 1ku87, manufactured by Orient Chemical Industry ■) Water Pink #2 3.0 parts (C, I
, Acid Red 92, manufactured by Orient Chemical Industry ■) Ethylene glycol 20.0 parts Germal 115 8.0 parts Nikkor NP-
100.1 parts (surfactant, polyoxyethylene nonylphenyl ether, manufactured by Nikko Chemicals) Broxel XL2
0.2 parts (preservative, 1,2benzisothiazolin=3-one, manufactured by ICI Japan) Water 66.
7 parts Each of the above components was stirred for 2 hours to obtain an aqueous red ink.

Tsubaki 11-λ- Water Blue #116 5.0 parts (C, I
, Acid Blue 15, manufactured by Orien J~Kagaku Kogyo ■) Ethylene glycol 25°0 parts Germal 115 10.0 parts Nitsukol NP-
100.1 part Broxel XL2 0.2 part water
59.7 parts A water-based blue ink was obtained using the same ingredients as in Example 1.

Tian Yong J Special Blank Nα4 7.0 parts (carbon black, manufactured by Degusosa Japan ■) Nilacol PBC
-341.0 parts (dispersant, polyoxyethylene (20 moles) polyoxypropylene (4 moles) cetyl ether, Nikko Chemicals ■
) Ethylene glycol 10.0 parts Glycerin 6.0 parts Germal 115
7. ○Part Broxel XL2
0.2 parts water
61.8 parts Among the above ingredients, the total amount of Special Black Nα4 and Niracol PBC-34 was mixed with 15% of water, and the mixture was dispersed by passing it through a 3-roll mill 5 times. The solution was added to the mixture, and the mixture was further stirred for 1 hour to obtain a water-based black ink.

Arrow 4 - Water Blank #7 4. ．． 0 copies (C,
I, Direct Black 19, Orient Chemical Industry■
) Ethylene glycol 15.0 parts Thiodiglycol 10.0 parts Germal 1] 5
10.0 parts (two copies) L/NP-10
0.1 part Broxel XL2 0.2 part water
60.7 parts Water-based black ink using the same ingredients as in Example 1! 4
! )is.

Comparative Example] Water Red #2 2. O part Water Pink #2 3.0 parts ethylene glycol 20. O part Ninocol Nl? -100
, 1 part Broxel XL2 0.2 parts water
74.7 parts Aqueous black ink was obtained using the same ingredients as in Example 1.

Shakukyosha Water Blue #116 5.0 parts Ethylene glycol 35.0 parts Nikkor NP-
100.1 part Broxel XL2 0.2 part water
59.7 parts A water-based blue ink was obtained using the same ingredients as in Example 2.

Le Kasa Koshu Special Black N (I47, 0 parts Nikkor PBC-341, 0 parts ethylene glycol 10.0 parts Glycerin 6.0 parts Broxel XL2
0.2 parts water
68.8 parts of each of the above ingredients Example 3
Aqueous black ink was obtained in the same manner as above.

[Effects of the Invention] The water-based inks obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were applied to a writing instrument (S 520,
(manufactured by Pentel ■) was filled with 1.9 g, and a test was conducted. The results are shown in Table 1.

Pen tip dryness resistance test: At a temperature of 18°C and a humidity of 65%, the writing instrument is left with the cap removed, and handwriting is performed on high-quality paper.The time until force scratches appear in the handwriting (unit: : day) was measured.

Handwriting drying test: Handwriting was performed on high-quality paper, and high-quality paper with a load of 500 g was placed over the handwriting, and the time (unit: 2 seconds) until ink transfer stopped occurring was determined.

As shown in Table 1 above, the present invention is a water-based ink with excellent pen tip drying resistance and handwriting drying properties, and can be used not only for writing instruments, but also for recorders, stamps, inkjet recording, etc. is also available.

Claims (1)

[Claims] A water-based ink comprising at least a colorant, water, and a copolymer represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I)