JPS6146508B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a low odor and low toxicity ink, and more particularly to an oil-based ink that is not sticky and has excellent water resistance.

Conventionally, oil-based inks are composed of an aromatic hydrocarbon, sometimes toluene, xylene, and optionally a solvent such as butanol, an oil-soluble dye, a film-forming resin, and the like. This type of ink was widely used because it dries quickly and the handwriting after writing has excellent water resistance and sunlight resistance, but in recent years, problems have arisen due to the odor and toxicity of aromatic hydrocarbons such as toluene and xylene. Therefore, there has been a demand for low odor and low toxicity oil-based inks that use alternative solvents.

To solve this problem, attempts have been made to develop low-odor and low-toxicity oil-based inks using aliphatic hydrocarbons and alicyclic hydrocarbons as solvents, but the dyes used as colorants are Currently, it has not reached the implementation stage due to the following problems.

That is, in order to dissolve conventional oil-soluble dyes in aliphatic hydrocarbons and alicyclic hydrocarbons, long-chain alkyl groups are introduced into the dyes to make them easily soluble. Generally, dyes are alkylated by synthesizing them from an intermediate containing an alkyl group, but in this case, the alkyl group is difficult to handle because it is an alkyl group or a cycloalkyl group with a carbon number of 4 or more. Another problem is that it is difficult to synthesize intermediates and dyes.

A common method for solubilizing oil-soluble dyes is to dissolve the dye in a higher fatty acid, especially oleic acid, or an alkylphenol, especially nonylphenol, at 80 to 120°C, and then dilute it with a solvent to prepare an oil-based ink. Since the ink contains higher fatty acids and alkylphenols, the handwriting of this type of ink does not dry completely and is sticky.

Oil-based inks that use dyes made by salt-forming acidic or basic dyes with cationic activators or anionic activators will show that when the handwriting is immersed in water, the salt-forming dyes will become salt-formed from the water-soluble dye and the activator. Because it is a dye, it decomposes in the presence of water and gradually separates into the original dye and activator, resulting in poor water resistance.Depending on the type of activator, its viscosity may remain in the dye. Therefore, there is a problem that the handwriting appears sticky.

Ammonium salts consisting of acid dyes and long-chain alkyl amines have a weak salt-forming effect, so oil-based inks using these types of dyes are difficult to use because the acid dyes that make up the ammonium salts gradually dissolve into water. It has a problem of poor water resistance.

The present inventors have finally completed the present invention as a result of intensive research to solve the above-mentioned problems.

That is, the present invention provides an acid halide of an acid dye having the following general formula: (In the formula, R represents an alkyl group or an alkenyl group of 4 to 30.) This is an oil-based ink characterized by containing a coloring agent obtained by reacting with a monoglyceride represented by the following formula.

Monoglycerides are generally used in foods, cosmetics, medicines, paints, etc., and are easily available. Acid halogenides of acidic dyes can also be easily obtained by the action of thionyl chloride.
Furthermore, the colorant for the oil-based ink of the present invention can be easily synthesized using a conventional reaction apparatus.

For example, the colorant for the oil-based ink of the present invention can be easily obtained by heating monostearin and eosin acid chloride in a molar ratio of 1:1 in xylene as a solvent.

When the number of carbon atoms in the alkyl group or alkenyl group of the monoglyceride is 3 or less, hydrolysis of the acyl group,
Alkyl groups having 4 to 30 carbon atoms are undesirable due to decreased solubility in non-aqueous solvents, and if the number is 31 or more, it is difficult to obtain, and the concentration of the colorant becomes low due to the increased molecular weight. Alkenyl groups are preferred. Furthermore, the amount used is 1 in oil-based ink.
~20% by weight is desirable. Monoglycerides include monovalerin, monocaproin,
monocaprylin, monocaprin, monolaurin,
Monomyristin, monopalmitin, monomargarine, monostearin, monoolein, monolinolein, monolinolenin, etc. can be used.

Acidic dyes include CI Acid Yellow 1, 3, 7, 11, 17, 19, 23, 25, and CI Acid Yellow.
29, 36, 38, 42, 44, 49, 59, 38
61, 70, 72, 76, 78, 79, 131,
135, 141, CI Acid Orange 1, 7,
8, 10, 19, 20, 24, 28, 41,
43, 51, 56, 63, 65, 67, CI Assisted Red 1, 6, 8, 9, 13, 14,
Same 18, Same 26, Same 27, Same 32, Same 35, Same 37, Same 42, Same
51, 52, 57, 80, 82, 83, 85,
87, 88, 89, 92, 94, 97, 106,
111, 114, 117, 118, 119, 129,
131, 134, 138, 145, 158, 249,
257, 265, 266, CI Acid Violet 7, 11, 15, 34, 41, 43, 48, CI
49, CI Assisted Blue 1, CI 9, 15, CI
22, 23, 25, 27, 29, 40, 41,
43, 45, 59, 62, 74, 78, 82,
83, 92, 93, 103, 112, 113, 117,
120, 126, 127, 129, 138, 140,
CI Assisted Green 3, 9, 16, 19,
Same 20, Same 25, Same 27, Same 28, Same 36, Same 40, Same 41, Same
44, CI Assisted Brown 2, CI 4, CI 13, CI
14, 20, 27, CI Assisted Black 1, 2, 7, 24, 26, 29, 31, 48,
50, 94, etc., are converted into acid halides using phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, thionyl chloride, etc. in the usual manner. The acid halide is then reacted with the monoglyceride to obtain a colorant that can be used in the present invention.

The amount of colorant used is preferably 0.5 to 20% by weight in the oil-based ink.

In addition to the above-mentioned colorants, the oil-based ink can use aliphatic hydrocarbons such as ligroin, mineral spirits, and solvent naphtha, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane as solvents. If necessary, alcohols and cellosolves can also be added. These solvents are 65 to 95% in oil-based inks.
It is preferred to use % by weight.

For fixing handwriting, rosin, rosin modified resin,
It is preferable to use at least one kind of phenolic resin, petroleum resin, etc. in an amount of 1 to 15% by weight in the oil-based ink composition.

The present invention will be specifically explained below with reference to Examples, in which "parts" represent "parts by weight".

Example 1 Colorant of the present invention (Acid chloride reaction product of monostearin and CI acid red 87) Ethylcyclohexane 80 parts Hytanol #133 10 parts (Alkylphenol novolac resin, manufactured by Hitachi Chemical Co., Ltd.) By mixing the above components and stirring at room temperature. A red oil-based ink was obtained.

Example 2 Colorant of the present invention (Monostearin and CI acid black 1
(acid chloride reaction product) Solvent naphtha 40 parts Diethylcyclohexane 30 parts Hitanol #133 10 parts (alkylphenol novolac resin, manufactured by Hitachi Chemical Co., Ltd.) Escorets 1071U 5 parts (petroleum resin, manufactured by Etsuso Co., Ltd.) Above components A blue oil-based ink was obtained by stirring and mixing at room temperature.

The inks of the present invention according to Examples 1 and 2 had good drying properties and no stickiness was observed even immediately after writing on non-permeable surfaces such as plastic, glass, and metal. In comparison, oil-based inks using alkylphenols or oleic acid as solubilizers
Stickiness was visible for about a week. In addition, oil-based inks using salt-forming dyes consisting of acidic or basic dyes and cationic activators or anionic activators, or ammonium salt dyes consisting of acidic dyes and long-chain alkylamines, will retain their handwriting in water for a month. When immersed for a while, the dye gradually dissolves into water and the concentration becomes diluted, but the ink of the present invention has very good water resistance.
Even after being immersed in water for a month, the concentration did not become diluted.

As explained above, the coloring agent that is the gist of the present invention can be easily obtained, and when made into oil-based ink, it has low odor, low toxicity, and is not sticky and has excellent water resistance. Therefore, it has the advantage that it can be used not only as a general marking ink but also as a stamp ink, a recorder ink, a jet printing ink, etc.

Claims (1)

[Claims] 1. The acid halide of the acid dye has the following general formula: (In the formula, R represents an alkyl group or an alkenyl group of 4 to 30.) An oil-based ink characterized by containing a colorant obtained by reacting a monoglyceride represented by: