JP2000212495A - Oil-based red ink - Google Patents

Abstract

(57) [Problem] To provide an oil-based red ink having a high handwriting density and in which precipitation of a dye hardly occurs. SOLUTION: It comprises at least a red dye represented by Chemical formula 1, an aliphatic alcohol having 4 or less carbon atoms, a resin soluble in the aliphatic alcohol, and an alkylamine ethylene oxide derivative represented by Chemical formula 2. Characteristic oil-based red ink. Embedded image Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-based red ink used for writing instruments such as marking pens and brush pens, recorders, and jet printers.
More specifically, the present invention relates to an oil-based red ink having excellent handwriting density and stability over time.

[0002]

2. Description of the Related Art Conventionally, oil-based inks used for quick-drying marking pens and the like mainly contain 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, aromatic hydrocarbons such as toluene and xylene having a high dissolving power for oil-soluble dyes, 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.
It is required to use the following aliphatic alcohols, particularly ethyl alcohol, which is highly safe, as a solvent for oil-based inks.

However, oil-soluble dyes used as colorants in oil-based inks containing aromatic hydrocarbons, glycol ethers and the like as solvents have poor solubility in lower aliphatic alcohols and have a sufficient concentration for practical use. It is difficult to get. So far, as a method for solving this problem, there is a method in which a basic dye is reacted with an acid dye and / or a direct dye, an anionic surfactant or the like, which has relatively good solubility in lower aliphatic alcohols. It has been proposed to use oil-soluble dyes of the salt type. Therefore, when a red color tone is required in an oil-based ink using a lower aliphatic alcohol as a solvent, a salt-forming type red dye represented by Chemical Formula 1 is used as a main colorant.

[0004]

However, as an oil-based red ink for a marking pen, a large amount of a red dye represented by the formula (1) is added to increase the density of a handwriting and the sharpness of a color, or a complementary color thereof. In the case where a yellow dye is added, the initial solubility is good, but when stored for a long time, the association of the dye molecules increases, and the problem that the precipitate exceeding the solubility level in the solvent is formed and accumulated is formed. Have. The generation of precipitates can be caused by clogging of the capillary in the pen tip or the plastic extruded pen tip due to the clogging of the capillary, reduced ink concentration, and reduced productivity in the manufacturing process (for example, ink during ink filling). This causes problems such as clogging of a filling machine nozzle). It is an object of the present invention to provide an oil-based red ink having a high handwriting density and in which precipitation of a dye is hard to occur.

[0005]

The present invention provides a red dye represented by the formula (1), an aliphatic alcohol having 4 or less carbon atoms, a resin soluble in the aliphatic alcohol, and an alkylamine represented by the formula (2). An oil-based red ink comprising at least an ethylene oxide derivative.

The details will be described below. The red dye represented by Chemical formula 1 is used as a main colorant, and has good solubility in aliphatic alcohols having 4 or less carbon atoms among commercially available oil-soluble red dyes. This red dye can be easily produced by a conventionally known method. For example, an aqueous solution of a basic dye and an aqueous solution of an acid dye, a direct dye or an anionic surfactant are mixed and stirred at a temperature of room temperature to 100 ° C. Thereafter, the water-insoluble reaction product is filtered, washed with water and dried to obtain a red dye. A specific example will be described below.
C. I. Basiclet # 1 and C.I. I. As a salt-forming dye with Acid Yellow 23, Bali Fast Red 13
08 (manufactured by Orient Chemical Industry Co., Ltd.), AL Red 23
08 (Chuo Gosei Kagaku Co., Ltd.) and the like. I. Basiclet # 1 and C.I. I. As a salt-forming dye with Acid Yellow 42, Spirit Red 102 (manufactured by Orient Chemical Industries, Ltd.) and the like can be used. I. As a salt-forming dye of Basiclet # 1 and dodecyl (sulfophenoxy) -benzenesulfonic acid, Spiron Red C-GH (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like can be mentioned. These can be used alone or in combination. The amount of the red dye represented by Chemical Formula 1 is preferably 2 to 15% by weight based on the total amount of the oil-based red ink. It is preferably 2% by weight or more from the viewpoint of maintaining the handwriting density suitably.
The content is preferably 15% by weight or less from the viewpoint of maintaining good temporal stability and having a viscosity suitable for ink ejection when used for writing instruments, recorders, and jet printers.

[0007] Aliphatic alcohols having 4 or less carbon atoms are used as solvents. Specific examples include methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, and tertiary butyl alcohol. These can be used alone or as a mixture of two or more.
It is preferable to add 90% by weight.

[0008] Resins soluble in aliphatic alcohols having 4 or less carbon atoms are used for improving the fixability of the ink coating film on the non-absorbing surface and adjusting the viscosity of the ink. For example,
Phenol resins, ketone resins, rosin resins, butyral resins, polyamide resins, and the like. A specific example will be described below. Tamanol 1 as a phenolic resin
00S, 510 (above, manufactured by Arakawa Chemical Industry Co., Ltd.), Hitachil 1501, 2501 (above, manufactured by Hitachi Chemical Co., Ltd.), YS Polystar S145, YP-90L
(Above, manufactured by Yashara Chemical Co., Ltd.) and the like, as a ketone resin, ketone resin K-90 (Arakawa Chemical Industry Co., Ltd.)
Halon 80, 110H (Honshu Chemical Co., Ltd.)
Manufactured), synthetic resin AP, same SK, same 1201
(Supplied by Huls, Germany) and the like, as rosin resins, Hercoline D, Pentaline 255, and 261 (supplied by Rika Hercules KK), Harrier Star NL,
Neotol C, gum rosin X (Harima Chemical Co., Ltd.
Gum Rosin WW (produced in China), Ester Gum H (produced by Arakawa Chemical Industry Co., Ltd.), etc.
Denka Butyral # 2000-L, # 3000-1,
# 3000-2, # 3000-4, # 3000-
K (manufactured by Denki Kagaku Kogyo Co., Ltd.), S-REC BL-
1, BL-3, BL-S, BX-10 (all manufactured by Sekisui Chemical Co., Ltd.), etc.
AQ-Nylon A-90, A-70, A-50, P-70, K-80, K-14 (Toray Industries, Inc.)
Newmide 825, 840 (manufactured by Casey Co., Ltd.), Tresin F30, MF-30, EF
-30T, M-20, TK5036 (all manufactured by Teikoku Chemical Industry Co., Ltd.), Versamide 744, 756, and 7
11 (all manufactured by Henkel Hakusui Co., Ltd.), Tomide # 9
And # 92 (both manufactured by Fuji Kasei Kogyo Co., Ltd.) and Sunmide 611DK-1 and 615A (both manufactured by Sanwa Chemical Industry Co., Ltd.). These can be used alone or in combination. The amount of the resin soluble in the aliphatic alcohol having 4 or less carbon atoms is preferably 1.0 to 20.0% by weight based on the total amount of the oil-based red ink.
1.0% by weight or more is preferable in that the fixing power of the handwriting is suitably maintained, and 20.0% by weight or less in terms of achieving a viscosity suitable for ink discharge when used for writing implements, recorders, and jet printers. Is preferred.

The alkylamine ethylene oxide derivative represented by Chemical Formula 2 improves the solubility of the red dye represented by Chemical Formula 1 in aliphatic alcohols having 4 or less carbon atoms, and improves the aging stability of ink and the concentration of handwriting. Things. The alkylamine ethylene oxide derivative represented by Chemical formula 2 can be selected in accordance with the red dye in terms of the alkyl group composition in the chemical formula and the number of moles of ethylene oxide added. However, the total number of added moles of ethylene oxide in one structural unit needs to be in the range of 1 to 15, and if it exceeds 15, the effect of dissolving the dye is reduced. Specifically, Nissan Naimeen L-20
1, L-202, L-207, S-202, S-2
04, S-210, S-215 (the above are Nippon Oil & Fats Co., Ltd.)
Nikkol TAMNS-5, TAMNS-1
0, TAMNS-15, TAMNO-5, TAM
NO-10 and TAMNO-15 (manufactured by Nikko Chemicals Co., Ltd.). These can be used alone or in combination. The use amount of the alkylamine ethylene oxide derivative represented by Chemical formula 2 is preferably 0.5 to 10.0% by weight based on the total amount of the oil-based red ink. 0.5 in terms of keeping the effect of the stability over time of the ink suitable.
% Is preferable, and 10.0 wt% or less is preferable from the viewpoint of preventing deterioration of handwriting dryness and obtaining a suitable viscosity.

In addition to the above essential components, if necessary, a complementary colorant for increasing the density of the handwriting and the sharpness of the color, a viscosity modifier for the ink, a corrosion inhibitor for preventing metal corrosion, and an ink coating. A plasticizer or the like that imparts flexibility to the film and enhances adhesion can be appropriately selected and used. For example,
Examples of the complementary colorant include an alcohol-soluble yellow dye. As a viscosity modifier of the ink, high-boiling alcohol solvents such as benzyl alcohol, ethylene glycol monophenyl ether, glycol ether solvents such as propylene glycol lower alkyl ether,
Ester solvents such as ethyl acetate and ethyl lactate are exemplified. Benzotriazole etc. are mentioned as a metal corrosion inhibitor. Plasticizers include phthalates, sebacates, phosphates, adipates,
Maleic acid ester, stearic acid ester, trimetic acid ester and the like can be mentioned.

Further, various surfactants can be used as an anti-drying agent for the pen tip, an agent for improving the applicability of the ink, and an agent for improving the ejection of the ink. Specifically, anionic surfactants such as alkyl sulfates, N-acyl amino acids and salts thereof, polyoxyethylene alkyl ether acetates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl ethers, sorbitan fatty acid esters , Nonionic surfactants such as decaglycerin fatty acid esters, fluorine surfactants such as perfluoroalkyl sulfonate and polyoxyethylene perfluoroether, and silicone surfactants such as polyether-modified silicone and alcohol-modified silicone Is mentioned.

The oil-based red 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.

[0013]

Normally, dye molecules are present in the solution in a state of several to several tens of units, but at a high concentration, they are more easily associated. Also, in aliphatic alcohols having 4 or less carbon atoms, which are solvents having a relatively high degree of ion dissociation, the salt-forming type oil-soluble dyes are stably present in the form of ion pairs in a dissolved state, It is thought that the change causes a change to an ion pair aggregate and a free ion.
Due to these effects, when a red dye represented by Chemical Formula 1 is used as a coloring agent for an oil-based red ink using a lower aliphatic alcohol as a solvent, if the amount of the dye used is increased to increase the concentration of handwriting, a long term It is considered that the amount of association of the dye ion pair increases with time, and a precipitate is formed beyond the solubility level in the solvent. The alkylamine ethylene oxide derivative represented by Chemical Formula 2 is a nonionic surfactant having a weak cationic property, and exists in a lower aliphatic alcohol in a good dissolved state or in the form of an activator micelle. . Therefore, when an alkylamine ethylene oxide derivative is used in an oil-based red ink using a red dye represented by Chemical formula 1, the complex is formed by bonding with the dye ion pair. The complex dissolves stably in the solution and prevents precipitation. Furthermore, the activator micelles wrap and redissolve the precipitates generated due to some influence. Therefore, it is presumed that precipitation of the dye can be prevented even when the ink is stored for a long period of time, and excellent handwriting density can be obtained when the ink is filled in a writing instrument.

[0014]

The present invention will be described below in more detail with reference to examples. Example 1 Varifast Red 1308 (Red dye represented by Chemical Formula 1, manufactured by Orient Chemical Industry Co., Ltd.) 8 parts by weight Spiron Yellow C-2GH (complementary colorant, Hodogaya Chemical Industry Co., Ltd.) 6 Parts by weight Ethyl alcohol 63 parts by weight Normal propyl alcohol 10 parts by weight Gum rosin WW (rosin resin, made in China) 10 parts by weight Nissan Nimeen L-201 (R ₃ is a dodecyl group, and m + n is 1; 3 parts by weight The above components were stirred with a stirrer for 4 hours to obtain an oily red ink.

Example 2 9 parts by weight of AL Red 2308 (a red dye represented by Chemical Formula 1, manufactured by Chuo Gosei Chemical Co., Ltd.) 5 parts by weight of oil yellow CH (colorant for complementary color, manufactured by Chuo Gosei Chemical Co., Ltd.) -65 parts by weight Halon 110H (ketone resin, manufactured by Honshu Chemical Co., Ltd.) 6 parts by weight Nissan Nimeen L-207 (alkylamine ethylene oxide derivative represented by Chemical Formula 2 wherein R ₃ is a dodecyl group and m + n is 7; 5 parts by weight of propylene glycol monomethyl ether (viscosity modifier) 10 parts by weight The above components were made in the same manner as in Example 1 to obtain an oily red ink.

Example 3 9 parts by weight of Spirit Red 102 (a red dye represented by Chemical Formula 1, manufactured by Orient Chemical Industry Co., Ltd.) 60 parts by weight of ethyl alcohol 15 parts by weight of isopropyl alcohol Tamanol 100S (phenol resin, Arakawa Chemical Co., Ltd.) Nikkol TAMNS-5 (alkylamine ethylene oxide derivative represented by Chemical Formula 2 wherein R ₃ is a stearyl group and m + n is 5, Nikko Chemicals Co., Ltd.) 4 parts by weight Benzyl alcohol (manufactured by Kogyo Co., Ltd.) Viscosity modifier) 5 parts by weight The above components were made in the same manner as in Example 1 to obtain an oily red ink.

Example 4 10 parts by weight of spiron red C-GH (red dye represented by Chemical formula 1, manufactured by Hodogaya Chemical Industry Co., Ltd.) 4 parts by weight of AL Yellow 3101 (colorant for complementary color, manufactured by Chuo Gosei Chemical Co., Ltd.) (manufactured by phenolic resin, Yasuhara Chemical Co.) Le 69 parts by weight of normal butyl alcohol 7 parts by weight YP-90L 8 parts by Nissan Nai Mean S-210 (R ₃ is octadecyl group, m + n is 10 STR2 - parts ethyl alcohol 2 parts by weight of the indicated alkylamine ethylene oxide derivative (manufactured by NOF CORPORATION) The above components were used in the same manner as in Example 1 to obtain an oily red ink.

Comparative Example 1 An oil-based red ink was obtained in the same manner as in Example 1, except that Nissan Nimeen L-201 was used and ethyl alcohol was added in that amount.

Comparative Example 2 Nissan Nimeen S-220 (an alkylamine ethylene oxide derivative in which the number of moles of ethylene oxide added is 20) was added to Nissan Nimeen S-220 in Example 1 except for Nissan Nimeen L-201, manufactured by NOF Corporation. ) Was obtained in the same manner as in Example 1 except for the addition of).

With respect to the oil-based red inks obtained in Examples 1 to 4 and Comparative Examples 1 and 2, an ink low-temperature aging test was performed. A writing instrument (Pentel Pen <Green Label> NN50 <Round Core>, Pentel Co., Ltd.) using a fiber core pen tip and batting was filled, and a handwriting density test was performed. Table 1 shows the results.

[0021]

[Table 1]

Ink low-temperature aging test The above oil-based red ink was sealed in a bottle with a lid, and kept at -20 ° C.
After being stored in a constant temperature chamber for one month, the ink was filtered with filter paper (manufactured by Advantech Toyo Co., Ltd.), and the state of the residue on the filter paper was confirmed.

Handwriting density test Clear sheet [thin mouth] (manufactured by Ricoh Educational Equipment Co., Ltd.)
Using a writing implement filled with the oil-based black ink,
The ink was uniformly applied once and dried horizontally, and the density was measured using an SM color computer (MODEL, SM-4, manufactured by Suga Test Instruments Co., Ltd.). The judgment method is evaluated using the luminous reflectance Y value, and the smaller the numerical value, the higher the density. (unit:%)

As described in detail above, the oil-based red ink according to the present invention does not precipitate even in a low-temperature aging test in which the dye is liable to precipitate. Can be

Claims (1)

[Claims] 1. A composition comprising at least a red dye represented by the chemical formula 1, an aliphatic alcohol having 4 or less carbon atoms, a resin soluble in the aliphatic alcohol, and an alkylamine ethylene oxide derivative represented by the chemical formula 2. Oil-based red ink characterized by the following. Embedded image Embedded image