JPH05271601A - Water-based ink composition - Google Patents

Abstract

PURPOSE:To obtain a water-based ink composition which is free from a rapid viscosity increase because of its good slow-drying properties and does not emit a strong odor and which neither blots a recorded image on a thermal recording paper or noncarbon paper nor suffers a color change, even when applied on a thermal recording paper, by incorporating a specific compound into a water- based ink. CONSTITUTION:This composition comprises a mixture of a water-based ink containing a colorant and water with at least one member selected from pentaerythritol, trimethylolethane, and trimethylolpropane. In the case where the composition is a dye ink, it is produced by mixing and dissolving the ingredients under stirring. In the case of a pigment ink, the composition can easily be obtained by treating the ingredients with an ordinary dispersion mixer, e.g. a ball mill, for mixing, grinding, and dispersion, or mixing the ingredients with a known stirrer, followed if necessary by the removal of coarse pigment particles by filtration or centrifugal separation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based ink composition having excellent drying resistance suitable for writing instruments, stamps, printing, recorders, printers and the like.

[0002]

2. Description of the Related Art Conventionally, water-based inks mainly contain a colorant and water. On the other hand, writing instruments, specifically fiber, felt, writing instruments using nibs using monofilaments, water-based ball-point pens, fountain pens, capillary writing instruments such as resin nibs, etc. There has been a demand for a water-based ink composition having excellent drying resistance, which does not clog the ink flow passage of the pen tip even when the pen tip is exposed to the air for a long time after being removed from the writing instrument main body. To meet the demand, glycol solvents such as ethylene glycol, propylene glycol and glycerin,
Glycol ether solvent such as ethylene glycol monoethyl ether, glycol ether ester solvent such as ethylene glycol monoethyl ether acetate,
A water-based ink composition is known in which an amine-based solvent such as triethanolamine and a water-soluble organic solvent such as an amide-based solvent such as formamide are included as a hygroscopic agent in a water-based ink to improve drying resistance. ..

Further, in recent years, thermal paper and non-carbon paper have been widely used as recording paper in order to popularize computers and facsimiles and to improve the efficiency of office work. These recording papers generally use leuco dyes, and their coloring mechanism is basically the same, and the lactone ring is opened by contacting a colorless leuco dye and a developer with heat or pressure. A reaction occurs and color develops. Also,
This cleavage reaction is a reversible reaction, and a cyclization reaction easily occurs due to the presence of an electron-withdrawing substance, resulting in colorlessness.

[0004]

The performance of the ink containing the hygroscopic agent, which is used for improving the drying resistance, is not sufficiently satisfactory. These hygroscopic agents have a problem that the hygroscopic agents cannot be added in an amount sufficiently satisfying the drying resistance. In addition, thermal paper and
When writing on Bon paper, there were problems such as discoloration of the paper and erasing characters copied on non-carbon paper.

Specifically, glycol solvents generally have a high viscosity and a high boiling point, so that if used in a large amount, the viscosity of the ink also increases. Therefore, when the ink is used in a writing instrument that requires low viscosity of the ink, it becomes difficult for the ink to flow out and the phenomenon of ink shortage occurs. In addition, the high boiling point makes it difficult for the handwriting to dry. In the case of glycol ether solvent and glycol ether ester solvent, the surface tension is generally low, so if used in a large amount, bleeding of handwriting will occur or ink will penetrate into the back surface of the paper. A phenomenon occurs, and clear handwriting cannot be obtained. Further, the glycol ether type solvent, the glycol ether ester type solvent and the amine type solvent have a peculiar unpleasant odor. Here, the glycol solvent, the glycol ether solvent and the glycol ether ester solvent promote contact between the leuco dye and the developer on the thermal paper to promote the cleavage reaction of the leuco dye. Remains discolored. The amide-based solvent is significantly hydrolyzed, which limits the materials used for the dye and the writing instrument main body. Although the same applies to the amine-based solvent, the phenomenon in which the cyclization reaction of the leuco dye is promoted and the image recorded on the pressure-sensitive paper or the copied characters on the non-carbon paper is erased occurs.

[0006]

The present inventors have conducted various studies to solve the above-mentioned conventional problems, and as a result, when a water-based ink contains a certain substance, the drying resistance is good. It is possible to obtain an excellent water-based ink that does not cause a sharp rise in viscosity or generate a strong odor, does not erase recorded images and handwriting on thermal paper or non-carbon paper, and does not discolor handwriting even on thermal paper. The inventors have found the present invention and completed the present invention. That is, the gist of the present invention is an aqueous ink composition comprising a colorant, water, and one or a mixture of two or more selected from pentaerythritol, trimethylolethane, or trimethylolpropane.

The present invention will be described in detail below. Pentaerythritol or trimethylol-the essence of the present invention
Luethane or trimethylolpropane is used as a desiccant, and can be used alone or in a mixture, and the amount thereof is 0.0 to the total amount of ink.
1 to 15.0% by weight is preferable.

As the colorant, dyes and pigments conventionally used in water-based inks can be used without any limitation. Specific examples of the dyes include Japanol Just Black D Conc (C.I. Direct black 1
7), Water Black 100L (Same as 19), Water
Water Black L-200 (19 same), Water Black # 7 (19 same), Kayaset Black W9 (1 same)
9), Direct Fast Black B (22 same), Direct Fast Black AB (32 same), Direct Deep Black EX (38 same), Direct Deep Black (38 similar product), Direct Fast Black Conc (the same) 51), Kayarus Supra Ray VGN (7
1), Kayak Direct Brilliant Elo-G (C.
I. Direct erotic-4) Direct fast erotic-5
GL (same as 26), Aizen Blumurao-GCLH (same as 44), Direct Fast Elo-R (same as 50), Aizen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX
(Same as 4), Direct Fast Scarlet 4BS (Same as 23), Eisen Direct Durin BH (Same as 31),
Direact Scarlet B (37), Kayak Direct Scarlet 3B (39), Eisenburi Mullabin Conc 2BLH (75), Sumilite Red F3B
(Same 80), Eisenbrimura Red 4BH (Same 81)
Kayaras Sprarubin BL (83), Kayaras Light Red F5G (225), Kayaras Light Red F5
B (same 226), Kayaras Light Rose FR (same 22)
7) Direct Sky Bull-6B (CI Direct Bull-1), Direct Sky Bull-5B (15),
Benzo Brilliant Skyble-8GS (41 same), Sumilite Sprable-BRR Conc (71 same), Divergent Cosble-S (86 same), Waterable- # 3 (86 same), Kaya Raster Direct dyes such as Koisable-GL (86), Daiwable-215H (87), Kayaras Spruble-FF2GL (106), Kayaras Spruble-FFRL (108), Kayaras Splata-Koisuru-FBL (199) Or Acid Bull-Black 10B (CI Acid Black 1),
Nigrosine (same 2), Water Black R455 (same 2), Water Black R510 (same 2), Sumino-
Lumi Ring Black 8BX (same 24), Kayano-Lumi Ring Black VLG (same 26), Kayano-Milling Black BR Conc (same 31), Mitsui Nylon Black GL (same 52), Aizen Opal Black WH Extra Conc (same) 52), Sumilan Black WA (5
2), Ranil Black BG Extra Conc (10
7), Kayano-Rumiring Black TLB (10
9), Sumi-no-milling black B (same as 109), Kayano-milling black TLR (same as 110), Aizen Opal Black New Conc (same as 119), W
Turquoise 187-L (154) Acid Yellow
# 10 (CI Acid Ero-1), Kayak Acid Brilliant Flavin FF (7: 1), Kayasilero-GG (17), Xylene Light Ero-2G 140%
(Ibid. 17), Sumino Le Leveling Elo-NR (Ibid. 1
9), Water Yellow # 1 (23), Daiwa
Tolazine (same 25), Kayaktorrazine (same 23),
Sumi-no-Fast Elo-R (same as 25), Diacid Light Ero-2GP (same as 29), Sumi-no-Milling Elo-O (same as 38), Sumi-no-Milling Elo-MR (same as 4)
2), Water Yellow # 6 (42), Kayano Luero-NFG (49), Sumino Lumiringero-3
G (72), Sumino Le Fastello-G (6)
1), Sumino-Rumi Ringero-G (same as 78), Kayano Ruero-N5G (same as 110), Sumino-Rumi Ringero-4G 200% (same as 141), Kayano-Ruelo-NG
(135), Kayano-Rumi Ringero-5GW (1)
27), Kayano-Rumi Ringero-6GW (14)
2), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (Same 9),
Solar Rubin Extra (14), Daiwa New Coxine (18), Water Scarlet (1)
8), Daiwa Red No. 102 (No. 18), Eisenbonso-RH (No. 26), Daiwa Red No. 2 (No. 27), Sumino Le Leveling Brilliant Red S3B (No. 35),
Kayasil Rubinol 3GS (37), Eisen Erythrosine (51), Kayaqua Acid Rho-Damine FB (52), Daiwa Red No. 106 (52), Sumino Lebeling Rubinol 3GP (57), Dai Acid Alizarin Rubinol F3G 200% (82), Alizarin Rubinol 5G (83), Eisen Eosin GH
(Id. 87), Water Red # 2 (Id. 87), Daiwa Red 103WB (Id. 87), Water Pink # 2 (Id. 92), Aizen Acid Phloxine PB (Id. 92),
Daiwa Red No. 104 (92), Rose Bengal (9)
4), Kayano Milling Scarlet FGW (11
1), Kayano-Rumi Ring Rubin 3BW (same as 129),
Sumino-Milling Brilliant Red 3BN Conc (131), Sumino-Milling Brilliant Red BS (138), Aizen Opal Pink BH (1)
86), Sumino-Lubrilliant Red B Conc (2)
49), Kayak Acid Brilliant Red 3BL (254), Kayak Acid Brilliant Red BL (265), and Kayano Lumiring Red GW (27)
6), Mitsui Acid Violet 6BN (C.I. Acid Violet 15), Mitsui Acid Violet BN (17), Water Violet # 1 (4)
9), Water Violet # 5 (49), Daiwa Purple No. 1 (49), Ink Violet L10 (4)
9), Sumitomo Patent Pure-VX (CI Acid Bull-1), Water Bull- # 106 (Same 1), Patent Bull-AF (Same 7), Water Bull-
# 9 (Same 9), Daiwa Blue No. 1 (Same 9), Ink Bull-
L20 (same 9), Spranol Ruble-B (same 15), Water Bull- # 116 (same 15), Orient Solble Bull-OBC (same 22), Orient Solble Bull-
OBX (22), Sumino Le Leveling Bull-4GL
(23), Mitsui Nylon Fast Bull-G (2)
5), Kayasil Bull-AGG (40 for the same), Kayasil Bull-BR (41 for the same), Mitsui Alizarin Safiroll SE
(Id. 43), Sumino Le Leveling Skyble-R Extra Conc (Id. 62), Mitsui Nylon Fast Skiable-R (Id. 78), Sumitomo Brilliant Indocyanine 6Bh / e (Id. 83), Sandlancyanin N-
6B 350% (same 90), waterable # 115
(Id. 90), Water Bullet # 105 (Id. 90), Orient Solble Bull-OBB (Id. 93), Sprano-
Lucyanin 7BF (100 same), Sumitomo Brilliant Bull-5G (103 same), Acid Bull- (10 same)
3), Asilane Brilliant Bull-FFR (10
4), Kayano-Rumiring Ultra Sky SE (11
2), Kaya-no-milling cyanine 5R (same 113),
Eisen opalcyanine 2GLH (158), Daiwa Guinea Green B (CI Acid Green 3), Acid Brilliant Milling Green (9), Daiwa Green # 70 (16), Kayano Lucyaning Green −
G (Same 25), Sumino-Milling Green G (Same 2)
7), acid dyes such as water orange # 17 (C.I. acid orange 56), water yellow # 2
(C.I. Foodero-3) and other food dyes, Malachite Green (C.I. 42000), Victoria Bull
FB (CI44045), methyl violet FN
(C.I. 42535), Rhodamin F4G (C.I.
45160), Rhodamine 6GCP (C.I. 4516).
There are basic dyes such as 0) and the like, and as the pigments, azo pigments, condensed polyazo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, perinone pigments. Pigments, organic pigments such as perylene pigments, inorganic pigments such as titanium oxide, iron oxide and carbon black, and inorganic fluorescent materials such as zinc sulfide, zinc silicate, cadmium zinc sulfate, calcium sulfide, strontium sulfide and calcium tungstate. Examples include pigments and other known organic fluorescent pigments. The above-mentioned colorants can be used alone or in combination with others, and the amount thereof is preferably 0.5 to 15% by weight with respect to the total amount of the ink, although it varies depending on the color tone and the like.

When a pigment is used as the coloring agent,
Although it is preferable to use a dispersant in combination, there is no limitation as the dispersant, which is conventionally used as a water-soluble or water-soluble resin or a pigment dispersant such as an anionic or nonionic surfactant. Can be used.

Further, in the case of pigment ink, it is advantageous in the production of pigment ink to use an aqueous ink base in which a pigment is dispersed in an aqueous medium. Specifically, Fuji. S
P. Black. 8031, 8119, 8167,
8276, 8381, 8406, Fuji. S
P. Red. 5096, 5111, 5193, 5
220, Fuji. SP. Bordeaux. 550
0, Fuji. SP. Blue. 6062 and 613
3, 6134, Fuji. SP. Green. 705
1, Fuji. SP. Yellow. 4060, Fuj
i. SP. Violet. 9011, Fuji. SP.
Pink. 9524 and 9527, Fuji. SP. O
range. 534, FUji. SP. Brown. Three
074 (all manufactured by Fuji Dye Co., Ltd.), Emacol. B
rack. CN, Emacol. Blue. FBB, FB, KR, Emacol. Green. LXB, E
macol. Violet. BL, Emacol. Br
own. 3101, Emacol. Carmine.
FB, Emacol. Red. BS, Emacol. O
range. R, Emacol. Yellow. FD,
same. IRN, 3601, FGN, GN, GG,
Same F5G, same F7G, same 10GN, same 10G, Sndy
e. Super. Black. K, C, Sandy
e. Super. Gray. B, Sandye. Sup
er. Brown. SB, FRL, RR, Sand
ye. Super. Green. L5G, GXB, S
andye. Super. Nayvy. Blue. HR
L, GLL, HB, FBL-H, FBL-16
0, same FBB, Sandye. Super. Viole
t. BL. H / C, same BL, Sandye. Supe
r. Bordeaux. FR, Sandye. Supe
r. Pink. FBL, F5B, Sandye. Su
per. Rubine. FR, Sandye. supe
r. Carmine. FB, Sandye. Supe
r. Red. FFG, RR, BS, Sadie. S
upper. Orange. FL, same R, same BO, San
dye. Gold. Yellow. 5GR, same R, same 3
R, Sandye. Ywlow. GG, same F3R, same IRC, same FGN, same GN, same GRS, same GSR-13
0, the same GSN-130, the same GSN, the same 10GN (above,
Sanyo Dye Co., Ltd., Rio. Fast. Black.
Fx. 8012, 8313, 8169, Rio. F
ast. Red. Fx. 8209, 8172, Ri
o. Fast. Red. S. Fx. 8315 and 831
6, Rio. Fast. Blue. Fx. 8170, R
io. Fast. Blue. FX. 8170, Rio.
Fast. Blue. S. Fx. 8312, Rio. F
ast. Green. S. Fx. 8314 (above, manufactured by Toyo Ink Co., Ltd.), NKW. 3002, 3003, 3004, 3005, 3007, 3077, 3
008, 3402, 3404, 3405, 34
07, ibid 3408, ibid 3477, ibid 3602, ibid 360
3, 3604, 3605, 3607, 367
7, 3608, 3702, 3703, 370
4, ibid. 3705, ibid. 3777, ibid. 3708, (manufactured by Nippon Fluorescent Co., Ltd.), Cosmokara-S. 1000F series
(Manufactured by Toyo Soda Co., Ltd.) and the like,
These are used alone or in combination of two or more.

In addition to the above essential components, various anions or penetrants such as nonionic surfactants are added to the total amount of the ink in order to add a wetting action to the ink to make the ink outflow during writing smooth. 0.01 to 5% by weight, and sodium dehydroacetate and 1.2-benzothiazoline-in order to prevent ink outflow inhibition due to the generation of mold.
Preservatives and fungicides such as 3-one and sodium benzoate may be added in appropriate amounts. Further, when a metal is used in a portion of the writing instrument that comes into contact with the ink, a corrosion inhibitor such as benzotriazole or ethylenediaminetetraacetic acid salt can be appropriately added to prevent corrosion of the metal.

As a method for producing the water-based ink composition of the present invention, in the case of dye ink, the above components are mixed and stirred to be dissolved. In the case of a pigment ink, the above components are mixed and milled with an ordinary disperser, for example, a ball mill, a roll mill, a sand mill, a flow mill, a dyno mill, an atizer, or the like.
When dispersing or using the above-mentioned aqueous ink base as a colorant, each component is stirred and mixed with a known stirrer, and further, if necessary, coarse particles of the pigment are obtained by a method such as filtration and centrifugation. It can be easily obtained by removing.

[0013]

The reason why the water-based ink according to the present invention is excellent in drying resistance and does not erase the recorded image and the handwriting on the thermal paper or the non-carbon paper or does not discolor the handwriting is presumed as follows. .. Pentaerythritol, trimethylolpropane, and trimethylolethane have a large number of hydroxyl groups in the molecule and therefore have a strong hydrogen bonding force. This hydrogen bonding force suppresses evaporation of water at the pen tip,
Prevent dryness. In addition, pentaerythritol, trimethylolpropane, and trimethylolethane are
Since it is a crystalline solid at room temperature, in writing, it solidifies due to the evaporation of water, and does not affect the leuco dye or developer used in thermal paper or non-carbon paper, causing discoloration of the paper. It is considered that the handwriting is not discolored and the recorded image is not erased.

[0014]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but "parts" simply means "parts by weight".

Example 1 Water 87.8 parts Eisen Eosin GHC (CI. Acid Red 87, Hodogaya Chemical Co., Ltd.) 8.0 parts Trimethylolpropane 4.0 parts Proxel GXL (1.2-benzothiazalin-3) -ON, manufactured by ICI, UK) 0.2 parts The above components were mixed, heated to 40 to 50 ° C, stirred for 1 hour, and then filtered to obtain a red ink.

Example 2 Water 97.3 parts Rhodamine 6GCP (CI. Basic Red 1, manufactured by Sumitomo Chemical Co., Ltd.) 0.3 parts Trimethylolethane 2.5 parts Sodium dehydroacetate 0.2 parts The respective components were mixed and stirred for 2 hours, and then filtered to obtain a pink fluorescent ink.

Example 3 Water 96.0 parts Orient Solble Bull-OBX (CI Acid Bull-22, manufactured by Orient Chemical Industry Co., Ltd.) 1.2 parts Water Bull- # 9 (CI. Acid Bull-9, manufactured by Orient Chemical Industry Co., Ltd.) 0.8 part Pentaerythritol 1.8 parts Sodium dehydroacetate 0.2 part The above components were mixed and stirred for 2 hours to obtain a blue ink. ..

Example 4 Water 59.0 parts NKW-3007 (fluorescent water-based ink base, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 40.0 parts Pentaerythritol 2.2 parts Proxail GXL 0.2 parts Each of the above The components were mixed and stirred for 2 hours to obtain a yellow fluorescent aqueous pigment ink.

Example 5 Water 82.6 parts Carbon black 13.0 parts Demol N (sodium salt of formalin condensate of naphthalene sulfonate, manufactured by Kao Corporation) 1.0 part Neugen-P (nonionic activity) Agent, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. 0.2 parts Trimethyl ethane 1.0 part Pentaerythritol 2.0 parts Proxel GXL 0.2 parts Mixing and dispersing treatment of the above components in a ball mill for 24 hours After that, a black ink was obtained by filtering.

Comparative Example 1 A red ink was obtained in the same manner as in Example 1, except that propylene glycol was used instead of trimethylolpropane in Example 1.

Comparative Example 2 A red ink was prepared in the same manner as in Example 1 except that 25.0 parts of propylene glycol was used instead of trimethylolpropane in Example 1 to reduce a large amount of water. Obtained.

Comparative Example 3 Pink was prepared in the same manner as in Example 2 except that 8.0 parts of ethylene glycol monoethyl ether was used in place of the trimethylolethane of Example 2 to reduce a large amount of water. A colored fluorescent ink was obtained.

Comparative Example 4 Yellow fluorescent aqueous solution was prepared in the same manner as in Example 4 except that 5.0 parts of dimethylformamide was used in place of the pentaerythritol of Example 4 to reduce a large amount of water. A pigment ink was obtained.

[0024]

【The invention's effect】

Test 1 The inks obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were filled in a commercially available fiber nib pen (Pentel Sign Pen S520, manufactured by Pentel Co., Ltd.), and an art paper (special / art post) was filled. N
o. 122, made by Hokuetsu Paper Mills Co., Ltd., and the state of handwriting was visually judged.

Test 2 The inks obtained in Examples 1-5 and Comparative Examples 1-4 were tested 1
The same fiber nib as that used in 1. was filled, the cap was removed, and it was left in the air, and every 24 hours until 1 hour, and thereafter every 1 day, the writing paper A (JIS, P320).
It was handwritten on 1) and the time until the occurrence of blurring was measured.

Test 3 The inks obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were used as commercially available underline fiber pen nibs (Pentel Signal S).
510, manufactured by Pentel Co., Ltd., and evaluated for discoloration with thermal paper and erasability with non-carbon paper. (Example 5
Is a black ink, so discoloration on thermal paper and erasability on non-carbon paper are not judged.)

Handwriting State From Test 1, the handwriting state was visually judged. ◯: No bleeding and good handwriting dryness Δ: Little bleeding, but handwriting does not dry forever ×: Severe bleeding resistance From the drying resistance test 2, the time until scratches were generated on the handwriting was measured. Discoloration of thermal paper From Test 3, writing was done on the thermal paper, and the discoloration of the handwriting was visually judged. ◯: No discoloration ×: Discoloration Decoloration of non-carbon paper From Test 3, writing was performed in an underline shape on the characters copied on the non-carbon paper, and the erasure of the copied characters was visually judged. ○: Handwriting is not erased ×: Handwriting is erased

[0028]

[Table 1]

As described above, the water-based ink of the present invention does not have an unpleasant odor, is excellent in drying resistance at the pen tip of a writing instrument,
In addition, it has good handwriting quality and does not discolor on thermal paper or non-carbon paper, and erases images recorded on these thermal paper or non-carbon paper or images copied on non-carbon paper. It is something that cannot be lost.

Claims (1)

[Claims] 1. A coloring agent, water, pentaerythritol,
A water-based ink composition comprising one or a mixture of two or more selected from trimethylolethane or trimethylolpropane.