JP2002129070A - Oil-based ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-based ink using a 1-4C aliphatic alcohol as a solvent, which is excellent in fixing a handwriting and, also, capable of exhibiting a clear handwriting without involving uneven color. SOLUTION: The oil-based ink contains, essentially, an oil-soluble dye, a 1-4C aliphatic alcohol, a resin and an ethylene oxide adduct to acetylenediol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitably used for writing implements, recorders and jet printers, and has a non-absorptive surface which has excellent fixability of handwriting and has a vivid color tone without color unevenness. Which relates to an oil-based ink.

[0002]

2. Description of the Related Art Conventionally, an oil-based ink used for a quick-drying marking pen or the like mainly contains an oil-soluble dye, an oil-soluble resin, and a solvent. Oil-based inks can write better not only on ink-absorbing surfaces such as paper and cloth, but also on non-ink-absorbing surfaces such as glass, metal, and plastic, compared to water-based inks that contain water-soluble dyes and water. is there. As a solvent for the oil-based ink, toluene having a high dissolving power for an oil-soluble dye,
Aromatic hydrocarbons such as xylene and glycol ethers such as ethylene glycol monomethyl ale and ethylene glycol monoethyl ether are used. However, the above-mentioned solvents have a problem of safety to the human body such as high odor and toxicity, and in recent years, aliphatic alcohols having 4 or less carbon atoms, which have low odor and toxicity, particularly ethyl alcohol having high safety are used as solvents for oil-based inks. Is required.

[0003]

However, an oil-based ink using a lower aliphatic alcohol having 4 or less carbon atoms as a solvent may cause handwriting to drop due to contact with an object or friction.
There is a problem that the fixing property of the handwriting on the non-absorbing surface is poor. In order to solve this problem, it is conceivable to add a large amount of resin in order to improve the fixing effect, but when a large amount of resin is added, the ink becomes high in viscosity, and when used in a writing instrument, etc. In consideration of the decrease in ink ejection from the pen tip, the amount of addition is limited, and sufficient fixability has not been obtained. In addition, depending on the dye used, there is a problem in that the handwriting when writing on the non-absorbing surface is affected by the surface state of the non-absorbing surface and becomes non-uniform or causes a density difference.

[0004]

The gist of the present invention is to provide an oil-based ink containing at least an oil-soluble dye, an aliphatic alcohol having 4 or less carbon atoms, a resin, and an ethylene oxide adduct of acetylene diol. Things.

The details will be described below. The oil-soluble dye used in the oil-based ink of the present invention is used as a colorant, and a dye soluble in an aliphatic alcohol having 4 or less carbon atoms can be used. Examples thereof include an oil-soluble fluorescent dye, an oil dye, a salt-forming type oil-soluble dye, a metal-containing complex dye, and a basic dye. Specifically, NKS-1001 and 100
3, 1004, 1005, 1006, 100
7, 1010, 1008, 1018, MPI-5
01 · C, 502, 503 · C, 504 · C, 505 · C, 506 · C, 507 · C, 508 ·
C (above, manufactured by Nippon Fluorescent Chemical Co., Ltd.), Oil Yellow 1
01, 107, oil pink 312, oil brown BB, GR, oil green BG, oil blue 61
3, BOS, oil black HBB, 860, B
S, Balifast Yellow 1101, 1105, 3
108, 4120, Balifast Orange 2210,
3209, 3210, Balifast Red 130
6, 1308, 1355, 1360, 230
3, 2320, 3304, 3306, 332
0, Balifast Pink 2310N, Balifast Brown 2402, Balifast 3405, Balifast Green 15
01, Balifast Blue 1603, 1605, 1
607, 1631, 2606, 2610, 26
20, Varifast Violet 1701, 170
2, Varifast Black 1802, 1807, 3
804, 3806, 3808, 3810, 38
20, 3830, Spirit Red 102, OSY Yellow RY, ROB-B, MVB3, SP Blue 10
5 (all manufactured by Orient Chemical Industry Co., Ltd.), Aizen Spiron Yellow 3RH, GRLH Special, C-
2GH, C-GNH, Eisenspiron Orange 2R
H, GRH Conch Special, Aizen Spiron Red GEH, BEH, GRLH Special, CG
H, C-BH, Eisenspiron Violet RH,
C-RH, Aizen Spiron Brown BH Conch, ARH, Aizen Spiron Mahogany RH, Aizen Spiron Blue GNH, 2BNH, C-RH, BPN
H, Eisen Spiron Green C-GH, 3GNH Special, S.I. B. N. Orange 703, S.P. B. N.
Violet 510, 521; P. T. Orange 6, S.I. P. T. Blue 111, SOT pink 1, SO
T Blue 4, SOT Black 1, Same 6, Same 10, Same 1
2,13 Liquid, Aizen Rhodamine B Base, Aizen Methyl Violet Base, Aizen Victoria Blue B Base (all made by Hodogaya Chemical Co., Ltd.), Oil Yellow CH, Oil Pink 330, Oil Blue 8
B, AL Yellow 1106D, 3101, AL Red 2308, Neo Super Yellow C-131, C-1
32, the same C-134, Neo Super Orange C-23
3, Neo Super Red C-431, Neo Super Blue C-555, Neo Super Brown C-732, C
-733 (manufactured by Chuo Gosei Kagaku Co., Ltd.), Oleosol Fast Yellow 2G, GCN, Oleosol Fast Orange GL, Oleosol Fast Red BL,
The same RL (all manufactured by Taoka Chemical Industry Co., Ltd.), Savinyl Yellow 2GLS, RLS, 2RLS, Savinyl Orange RLS, Savinyl Fire Red GLS, Savinyl Red 3BLS, Savinyl Pink 6BLS, Savinyl Blue RN , The same GLS, Sub Vinyl Green 2
GLS, Subvinyl Brown GLS (Sand, Switzerland), Magenta SP247%, Crystal Violet 10B250%, Malachite Green Crystal Conch, Brilliant Green Crystal H90
%, Spirit Soluble Red 64843 (Holiday, UK), Neptune Red Base 543,
Neptune Blue Base 634, Neptune Violet Base 604, Vasony Le Red 540, Bason Le Violet 600 (BASF, Germany)
And the like. The amount of the oil-soluble dye used is preferably 2 to 30% by weight based on the total amount of the oil-based ink.
The ink is preferably 2% by weight or more from the viewpoint of suitably maintaining the handwriting density. In addition, the ink is free from deposits, has good stability over time, and is used for writing instruments, recorders, and jet printers. 30 in terms of viscosity suitable for ejection
% By weight or less is preferred.

The aliphatic alcohol having 4 or less carbon atoms used in the oil-based ink of the present invention is used as a solvent.
Specifically, methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol,
Normal butyl alcohol, isobutyl alcohol and tertiary butyl alcohol are exemplified. These can be used alone or as a mixture of two or more, and it is preferable to add 10 to 90% by weight of the total amount of the oil-based ink.

The resin used in the oil-based ink of the present invention is used for improving the fixability of the ink film on the non-absorbing surface and adjusting the viscosity of the ink. For example, phenol resin, ketone resin, rosin resin, butyral resin, polyamide resin and the like can be mentioned. To give a specific example, Tamanol 100S and 510 are used as phenol resins.
(These are Arakawa Chemical Industries, Ltd.), Hitanol 150
1, 2501 (all manufactured by Hitachi Chemical Co., Ltd.), YP
-90, YP-90L, YS Polystar S145, #
2100, # 2115, # 2130, T80, T100, T115, T130, T145, Mighty Ace G125, and 150 (all manufactured by Yashara Chemical Co., Ltd.) as ketone resins K-ketone resin K- 90 (Arakawa Chemical Industry Co., Ltd.), Halon 80, 1
10H (manufactured by Honshu Chemical Co., Ltd.), synthetic resin AP, SK, 1201 (manufactured by Huls, Germany), and the like, as rosin resins, Hercoline D, Pentaline 255, and 261 (manufactured by Rika Hercules) (stock)
), Harrier Star NL, Neotor C, Gum Rosin X
(Harima Kasei Co., Ltd.), Gum Rosin WW (China), Ester Gum H (Arakawa Chemical Industry Co., Ltd.), etc. are used as butyral resins as Denka Butyral # 200.
0-L, # 3000-1, # 3000-2, # 3
000-4, # 3000-K (all manufactured by Denki Kagaku Kogyo Co., Ltd.), Eslec BL-1, BL-3, BL
-S and BX-10 (all manufactured by Sekisui Chemical Co., Ltd.) as AQ-nylon A-9 as polyamide resins.
0, A-70, A-50, P-70, K-8
0, K-14 (all manufactured by Toray Industries, Inc.), Newmide 825, 840 (manufactured by Casey Co., Ltd.), Tresin F
30, MF-30, EF-30T, M-20, TK5036 (all manufactured by Teikoku Chemical Industry Co., Ltd.), Versamide 744, 756, and 711 (all manufactured by Henkel Hakusui Co., Ltd.), Tomide # 90, # 92 (above, manufactured by Fuji Chemical Industry Co., Ltd.), Sunmide 611DK-1 and 6
15A (all manufactured by Sanwa Chemical Industry Co., Ltd.). These can be used alone or as a mixture of two or more, and the amount used is preferably 1 to 20% by weight based on the total amount of the oil-based ink.

The ethylene oxide adduct of acetylene diol used in the oil-based ink of the present invention is used for improving the fixability of the handwriting and obtaining a vivid handwriting without color unevenness on the non-absorbing surface. As a specific example, Dynol 6
04 (manufactured by Air Products Japan Co., Ltd.). The amount used is 0.1% based on the total amount of the oil-based ink.
It is preferable to add about 3.0% by weight.

In addition to the above essential components, if necessary, a dye dissolving aid, a high-boiling solvent for preventing drying of the pen tip, a corrosion inhibitor for preventing metal corrosion, and imparting flexibility to the ink coating film. A plasticizer or the like for improving the adhesion can be appropriately selected and used. For example, the solvent as a dye dissolution aid is a high boiling alcohol solvent such as benzyl alcohol,
Glycol ether solvents such as ethylene glycol monophenyl ether, propylene glycol lower alkyl ether, and propylene glycol monomethyl ether acetate; and ester solvents such as ethyl acetate, butyl acetate, and ethyl lactate. Benzotriazole etc. are mentioned as a metal corrosion inhibitor. Examples of the plasticizer include phthalic acid ester, sebacic acid ester, phosphoric acid ester, adipic acid ester, maleic acid ester, stearic acid ester, and trimet acid ester.

Further, various surfactants can be used as a solubilizing agent for a dye, an anti-drying agent for a pen tip, an agent for improving applicability of ink, and an agent for improving ink ejection. Specifically, alkyl sulfates, N-acyl amino acids and salts thereof,
Anionic surfactants such as polyoxyethylene alkyl ether acetates and polyoxyethylene alkyl ether phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, sorbitan fatty acid esters, and decaglycerin fatty acid esters; Examples include silicone-based surfactants such as ether-modified silicone and alcohol-modified silicone.

The oil-based ink of the present invention can be obtained by stirring and mixing the above essential components using a conventionally known stirrer and uniformly dissolving them.

[0012]

In the present invention, the ethylene oxide adduct of acetylenic diol uniformly dissolves the resin or dye contained in the ink, and particularly improves the molecular orientation of the resin molecule with respect to the non-absorbing surface. Therefore, it is presumed that the fixing property to the non-absorbing surface is improved. In addition, since the oil which exists on the non-absorbing surface and causes color unevenness is surrounded and prevents the ink from repelling against the oil, a vivid color tone of handwriting without color unevenness can be obtained.

[0013]

The present invention will be described below in more detail with reference to examples. Example 1 NKS-1005 (fluorescent yellow dye, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 25.0 parts by weight Ethyl alcohol 57.0 parts by weight Benzyl alcohol 10.0 parts by weight Gum rosin WW (rosin resin, made in China) 5.6 Parts by weight Tamanol 510 (phenol resin, manufactured by Arakawa Chemical Industries, Ltd.) 2.0 parts by weight Dynol 604 (described above) 0.4 part by weight The above components were stirred for 4 hours with a stirrer to obtain an oily yellow ink.

Example 2 MPI-507.C (fluorescent pink dye, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 20.0 parts by weight Ethyl alcohol 28.0 parts by weight butyl acetate 46.0 parts by weight Tamanol 510 (described above) 5 1.0 part by weight Dynol 604 (described above) 1.0 part by weight The above components were stirred with a stirrer for 4 hours to obtain an oily pink ink.

Example 3 MPI-505 · C (fluorescent yellow dye, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 25.0 parts by weight Ethyl alcohol 23.0 parts by weight Propylene glycol monomethyl ether acetate 43.5 parts by weight YS Polystar S145 ( Phenol resin, manufactured by Yasuhara Chemical Co., Ltd. 8.0 parts by weight Dynol 604 (described above) 0.5 part by weight The above components were used in the same manner as in Example 1 to obtain an oily yellow ink.

Example 4 Aizen Spiron Red C-GH (oil-soluble dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 4.0 parts by weight Oil Blue 613 (oil-soluble dye, manufactured by Orient Chemical Industry Co., Ltd.) 1.0 Parts by weight Ethyl alcohol 75.8 parts by weight Benzyl alcohol 12.0 parts by weight Halon 110H (ketone resin, manufactured by Honshu Chemical Co., Ltd.) 7.0 parts by weight Dynol 604 (described above) 0.2 part by weight In the same manner as in Example 1, an oil-based purple ink was obtained.

Example 5 Oil Yellow CH (Oil-soluble dye, manufactured by Chuo Gosei Kagaku Co., Ltd.) 7.0 parts by weight Normal propyl alcohol 72.0 parts by weight Ethylene glycol monophenyl ether 12.0 parts by weight Synthetic resin SK (Ketone resin, manufactured by Huls, Germany) 8.0 parts by weight Dynol 604 (described above) 1.0 part by weight The above components were used in the same manner as in Example 1 to obtain an oily yellow ink.

Comparative Example 1 An oily pink ink was obtained in the same manner as in Example 1 except that Dynol 604 was used and ethanol was added in that amount.

Comparative Example 2 An oily yellow ink was obtained in the same manner as in Example 5 except that Dynol 604 was used and normal propyl alcohol was added in that amount.

The oil-based inks obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were applied to a writing instrument (pentel pen <green label> NN60 <flat core, bold type>, pentel) using a fiber nib and a batting. (Manufactured by Co., Ltd.), and a handwriting friction test and a handwriting color unevenness determination test were performed. Table 1 shows the results.

[0021]

[Table 1]

Handwriting friction test Clear sheet [thin mouth] (manufactured by Ricoh Educational Instruments Co., Ltd.)
Then, using a writing instrument filled with the above oil-based ink, the ink is uniformly applied once to the surface in a horizontal manner and dried for 10 minutes to obtain a test film. Next, a high-quality paper is placed on the test film, and a weight having a diameter of 50 mm at the bottom and a weight of 500 g is placed on the test film.
The hand-drawn state of the hand that has been moved a second time can be checked using an SM color computer (MODEL, SM-4, Suga Test Instruments Co., Ltd.)
Was used for the measurement. Judgment method: Based on the measurement results, the color difference ΔE of the handwriting before and after the test was calculated. It is evaluated that the smaller the value is, the less the handwriting peels due to friction.

Judgment test for unevenness in handwriting color A straight line of 20 cm was written at a constant speed of 10 cm / sec on a clear sheet (described above) using a writing instrument filled with the above oil-based ink, and dried for 10 minutes to obtain a test film. Ten points were arbitrarily selected from the handwriting and measured using an SM color computer (described above). Judgment method: Based on the measurement result, the density Y value of the handwriting is calculated, and the smaller the value ΔY obtained by subtracting the minimum value from the maximum value among the ten data, the smaller the color unevenness is evaluated.

[0024]

As described in detail above, the oil-based ink according to the present invention has the characteristics that it is excellent in the fixability of handwriting and that a vivid handwriting without color unevenness can be obtained.

Claims (1)

[Claims] 1. An oil-based ink containing at least an oil-soluble dye, an aliphatic alcohol having 4 or less carbon atoms, a resin, and an ethylene oxide adduct of acetylene diol.