JP2946747B2 - Aqueous ink composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an aqueous ink composition in which the occurrence of blur is minimized. More specifically, the present invention relates to a water-based ink composition that hardly causes blurring immediately after being assembled as a writing instrument or after being stored for a long time.

(Problems to be Solved by Conventional Techniques and Inventions) Conventionally, aqueous inks mainly include a colorant, a water-soluble organic solvent, and water. This water-based ink is often used on a daily basis because, when written on paper, the bleeding is small and a high-density handwriting is obtained.

However, when this water-based ink is used by filling it into a writing instrument main body such as a ball-point pen and a needle pen, there has been a problem that ink is less discharged from a pen tip and handwriting is blurred. Blurring occurs when the writing ink is filled in the writing implement body (in the case of the so-called "raw ink type" writing implement, the ink cartridge is set in the writing implement main body), and after the writing implement has been assembled, it occurs in a short period of time or stored for a long time. Some occur later, and the cause is not clear.

Various proposals have been made to prevent the occurrence of blurring. For example, using a large amount of a surfactant to prevent generation in a short period of time, using a water-soluble silicone resin to prevent generation after long-term storage, and using a large amount of a water-soluble organic solvent for a short period of time Or after storage for a long period of time.

However, the above proposal was by no means sufficient to prevent the occurrence of blurring.

An object of the present invention is to provide a water-based ink composition that hardly causes blurring immediately after being assembled as a writing instrument or after being stored for a long time.

(Means for Solving the Problems) The present invention relates to an aqueous ink composition comprising at least a coloring material, a water-soluble organic solvent and water, wherein (iso) ascorbic acid and / or a derivative thereof and an anodic ketone group are formed. A water-based ink composition comprising:

 Hereinafter, the present invention will be described in detail.

As the coloring material, any of dyes and pigments can be used. As the dye, any of an acid dye, a direct dye, a basic dye and the like can be used, but it is preferable to use an acid dye and a direct dye. An example is given below.

As direct dyes, Japananol Fast Black D
Conch (CI Direct Black 17), Water Black 100L (19), Water Black L-200 (1)
9), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black EX (38), Direct 4st Blank Conch (51), Kayara Splupray VGN (71), Kayaras Direct Pretty Yellow G (CI Direct Yellow 4), Direct Fast Yellow 5GL (26), Eizen Primula Yellow GCLH (44), Direct Fast Yellow R (50), Eizen Direct Fast Red
FH (CI Direct Red 1), Nippon Fast Scarlet GSX (4), Direct Fast Scarlet 4BS (23), Eisen Direct Lodulin BH
(31), Direct Scarlet B (37), Kayak Direct Scarlet 3B (39), Aizen Prism Pink 2BLH (75), Sumilight Red F3B (8)
0), Aizen Primula Red 4BH (81), Kayalas Sprarubin BL (83), Kayalas Light Red 5G (22)
5), Kayasu Light Red F5B (226), Kayasu Light Rose FR (227), Direct Sky Blue 6B
(CI Direct Blue 1), Direct Sky Blue
5B (15), Sumilight Supra Blue BRR Conch (7
1), Daibogen Turquoise Blue S (86), Water Blue # 3 (86), Kayara Star Turquoise Blue
GL (86), Kayalas Supra Blue FF2GL (106), Kayaras Splatter Koizu Blue FBL (199) and the like.

Acid dyes include Acid Blue Black 10B (C.
I. Acid Black 1), Nigrosine (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (26), Suminol Fast Black B
R Conch (31), Mitsui Nylon Black GL (5
2), Eisen Opal Black WH Extra Conch (52), Sumilan Black WA (52), Ranil Black BG Extra Conch (107), Kayanol Milling Black TLB (109), Suminol Milling Black B
(109), Kayanol Milling Black TLR (11)
0), Eisen Opal Black New Conch (11
9), Water Black 187-L (154), Kayak Acid Brilliant Flavin FF (CI Acid Yellow 7:
1), Kayasil Yellow GG (17), Xylene Light Yellow 2G140% (17), Suminol Leveling Yellow NR
(19), Daiwa Tarazin (23), Kayaktor Trazine (23), Suminol Fast Yellow R (2)
5), Diacid Light Yellow 2GP (29), Suminol Milling Yellow O (38), Suminol Milling Yellow MR (42), Water Yellow # 6 (42), Kayanol Yellow NFG (49) , Suminol Milling Yellow 3G
(No. 72), Suminol Fast Yellow G (No. 61), Suminol Milling Yellow G (No. 78), Kayanol Yellow N5
G (110), Sumino Milling Yellow 4G 200% (14)
1), Kayanol Yellow NG (135), Kayanol Milling Yellow 5GW (127), Kayanol Milling 6GW (14)
2), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayaksil Scarlet (9), Solar Rubin Extra (14), Daiwa Nyukokushin (18), Aizen Bon Saw RH (26), Daiwa Red 2
No. (No. 27), Suminol Leveling Brilliant Red
S3B (35), Kayasil Lubinol 3GS (37), Eisenerythrosine (51), Kayaquaid Rhodamine 4B
(52), Suminol Leveling Binol 3GP (5
7), Diacid Alizarin Rubinol F3B 200% (8
2), Eisen Eosin GH (87), Water Pink # 2 (92), Eisen Acid Phloxine PB (9)
2), Rose Bengal (94), Kayanol milling scarlet FGW (111), Kayanol milling rubin 3B
W (129), Sumino All Milling Brilliant Red
3BN Conch (131), Suminol Milling Brilliant Red BS (138), Eisen Opal Pink BH (18)
6), Suminol Milling Brilliant Red B Conch (249), Kayak Acid Brilliant Red 3BL (Id.)
254), kayak acid brilliant brilliant red BL
(265), Kayanol Milling Red GW (276), Mitsui Acid Violet 6BN (CI Acid Violet 15), Mitsui Acid Violet BN (17), Sumitomo Patent Pure Blue VX (CI Acid Blue 1), Water Blue # 106 (1), Patent Blue AF (7), Water Blue # 9 (9), Daiwa Blue No. 1 (9), Spranol Blue B (15), Orient Soluble Blue OBC (22) , Suminol Leveling Blue 4GL (23), Mitsui Nylon Fast Blue G (25), 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 B (78), Mist Mobile Brilliant Indocyanine
6Bh / c (83), Sandran cyanine N-6B350% (9
0), Water Blue # 115 (90), Orient Soluble Blue OBB (93), Sumitomo Brilliant Blue 5
G (103), Kayanol Milling Ultra Sky SE (103)
112), Kayanol Milling Cyanine 5R (113), Eisen Opal Blue 2GLH (158), Daiwa Guinea Green B (CI Acid Green 3), Acid Brilliant Milling Green B (9), Daiwa Green # 70
(No. 16), Kayanol Cyanine Green G (No. 25), Suminol Milling Green G (No. 27) and the like.

Pigments are azo pigments, nitroso pigments, nitro pigments,
Organic pigments such as basic dye pigments, acid dye pigments, vat dye pigments, mordant dye pigments and natural dye pigments, ocher, barium yellow, navy blue, cadmium red, barium sulfate, titanium oxide, valves Inorganic pigments such as patterns, iron black, and carbon black.

These coloring materials can be used alone or in combination. The amount used is based on the total amount of the aqueous ink composition.
0.5 to 20% by weight is preferred.

The water-soluble organic solvent is used mainly for the purpose of preventing freezing at a constant temperature and keeping moisture. Specific examples include ethylene glycol, propylene glycol, thiodiglycol, glycerin, polyethylene glycol and the like. The amount used is preferably from 10 to 30% by weight based on the total amount of the aqueous ink composition.

The (iso) ascorbic acid and its derivative and the substance having an enol ketone group are used in combination so as not to cause blurring immediately after assembling as a writing instrument or after long-term storage.

In addition to ascorbic acid and isoascorbic acid (erythorbic acid), examples of ascorbic acid derivatives include magnesium ascorbic acid phosphate and disodium ascorbic acid sulfate.

Examples of the substance having an enol ketone group include acetoacetanilide, acetoacetoortho toluide, acetoacetoxy lide, and 3-methyl-1-phenyl-5.
-Pyrazolone, 1-phenyl-5-pyrazolone-3-carboxylic acid, 3-methyl-1-phenyl-5-pyrazolone-6'-sulfonic acid, and the like.

The amount of each of these is preferably 0.2 to 3.0% by weight based on the total amount of the aqueous ink composition.

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

In addition, antiseptic and antifungal agents, rust inhibitors for preventing metal corrosion,
It is also possible to add a water-soluble polymer for viscosity extension.

When a pigment is used as the colorant, it is necessary to use a dispersant in terms of dispersibility, stability over time, and the like. For example, styrene-maleic acid copolymer, styrene-
A copolymer of a hydrophobic monomer and a hydrophilic monomer such as an acrylic acid copolymer and a styrene-methylstyrene-acrylic acid copolymer, and / or a salt thereof, and various surfactants may be used.

When a dye is used as a coloring material, the ink according to the present invention can be obtained by mixing and stirring the above essential components with a conventionally known stirrer to uniformly dissolve it. When a pigment is used as the colorant, the pigment can be obtained by mixing and dispersing with a conventionally known dispersing machine.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples. In the examples and comparative examples, “parts” simply indicates “parts by weight”.

Example 1 Water Red # 2 2.0 parts (CI Acid Red 87, Orient Chemical Co., Ltd.)
Water Pink # 2 3.0 parts (CI Acid Red 92, Orient Chemical Co., Ltd.)
20.0 parts of ethylene glycol L-(+)-ascorbic acid 1.0 part 0.5 parts of acetoacetanilide Nichol NP-10 0.1 parts (surfactant, polyoxyethylene nonylphenyl ether, Nikko Chemicals Co., Ltd.) 0.2 parts of Proxel XL2 ( Preservative, 1,2-benzisothiazolin-3-one, I
CI Japan Co., Ltd.) 0.1 parts of sodium hydroxide 73.1 parts of water The above components were stirred for 2 hours to obtain an aqueous red ink.

Example 2 5.0 parts of water blue # 116 (CI Acid Blue 15; manufactured by Orient Chemical Co., Ltd.) Glycerin 15.0 parts Ethylene glycol 5.0 parts Nikkor VC-SS 0.3 parts (Vitamin derivatives, disodium ascorbate sulfate disodium salt, sunlight Chemicals Co., Ltd.) Acetoacetanilide 2.0 parts Nikkor NP-10 0.1 parts Proxel XL2 0.2 parts Water 72.4 parts The above components were used in the same manner as in Example 1 to obtain an aqueous blue ink.

Example 3 7.0 parts of special black No. 4 (carbon black, manufactured by Degussa Japan Co., Ltd.) 1.0 part of Nikkor PBC-34 (dispersant, polyoxyethylene (20 mol) polyoxypropyl (4 mol) ethyl ether, Nikko Chemicals Co., Ltd.) Propylene glycol 15.0 parts L-(+)-ascorbic acid 1.0 part Acetoacetoxy ride 0.5 parts Proxel XL2 0.2 parts Water 75.3 parts Special black No. 4 and Nikkor among the above components
The total amount of PBC34 and 15 parts of water were mixed, and the mixture was passed through a three-roll mill five times, and the remaining total amount was mixed and uniformly dissolved, and further stirred for 1 hour to obtain an aqueous black color. An ink was obtained.

Example 4 Water Black # 7 4.0 parts (CI Direct Black 19, manufactured by Orient Chemical Industry Co., Ltd.) Ethylene glycol 10.0 parts Ethioglycol 4.0 parts Urea 7.0 parts L-(+)-ascorbic acid 2.0 parts 1-phenyl-5- Pyrazolone-3-carboxylic acid 0.3 parts Triethanolamine 2.0 parts Nikkor NP-10 0.1 parts Proxel XL2 0.2 parts Water 70.4 parts The same ingredients as in Example 1 were used to obtain an aqueous black ink.

Comparative Example 1 Water Red # 2 2.0 parts Water Pink # 2 3.0 parts Ethylene glycol 21.5 parts Nikkor NP-10 0.1 parts Proxel XL2 0.2 parts Water 73.2 parts The same ingredients as in Example 1 were used to obtain an aqueous red ink.

Comparative Example 2 Water Blue # 116 5.0 parts Glycerin 15.0 parts Ethylene glycol 5.0 parts Nikkor NP-10 0.1 parts Proxel XL2 0.2 parts Silicone X-22-611 2.3 parts (water-soluble silicone resin, Shin-Etsu Chemical Co., Ltd.) Water 72.4 parts The above components were made in the same manner as in Example 1 to obtain an aqueous blue ink.

Comparative Example 3 Special Black No.4 7.0 parts Nikkor PBC-34 2.0 parts Propylene glycol 15.5 parts Proxel XL2 0.2 parts Water 75.3 parts The above components were made in the same manner as in Example 3 to obtain an aqueous black ink.

Comparative Example 4 Water Black # 7 4.0 parts Ethylene glycol 10.0 parts Thiodiglycol 4.0 parts Urea 9.3 parts Nikkor NP-10 0.1 parts Proxel XL2 0.2 parts Water 72.4 parts The above components were prepared in the same manner as in Example 1 to obtain an aqueous black ink. Was.

(Effect of the Invention) 2.6 g of the aqueous ink composition obtained in each of Examples 1 to 4 and Comparative Examples 1 to 4 was put on a commercially available ballpoint pen type writing implement for aqueous ink (Ball Pentel R50, manufactured by Pentel Co., Ltd.).
It was filled and tested for blurring.

 Table 1 shows the results.

Blurring test: Ten writing instruments each filled with the aqueous ink compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were assembled, left for a predetermined period of time with the cap kept on, and then written. The presence or absence was checked.

 Initial: After one day at room temperature.

 After aging: After leaving at room temperature for 3 months.

As described above, the water-based ink composition according to the present invention is an excellent water-based ink composition that is hardly blurred immediately after being assembled as a writing instrument or after being stored for a long time. In addition, it can be very suitably used not only for writing instruments used alone such as ballpoint pens and needle pens but also for writing instruments used for recorders, mechanical drawings and the like.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C09D 11/16-11/18

Claims (1)

(57) [Claims] An aqueous ink composition comprising at least a coloring material, a water-soluble organic solvent and water, characterized in that it contains (iso) ascorbic acid and / or a derivative thereof and a substance having an enol ketone group. -Based ink composition.