JPS5949951B2 - oil-based ink composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an oil-based ink composition, more specifically, a low-odor and low-toxicity aliphatic hydrocarbon and/or alicyclic hydrocarbon, singly or as a mixture, and an alkyl soluble in this solvent. This invention relates to an oil-based ink containing a colorant consisting of a base of benzoic acid and a basic dye.

Conventionally, oil-based marking inks use aromatic hydrocarbons, particularly toluene, xylene, etc. as a solvent, and consist of oil-soluble dyes and film-forming resins.

This type of ink has been widely used because the written marks left after marking are excellent in water resistance and sunlight fastness, but the solvents used as solvents, such as toluene and xylene, have a strong odor and toxicity. There has been a demand for the use of alternative solvents and for oil-based marking inks containing such low odor and low toxicity solvents. Therefore, oil-based marking inks using aliphatic hydrocarbons and alicyclic hydrocarbons as solvents, which are said to have low odor and low toxicity, have been developed.
Here, it is most important to make a dye that dissolves in this solvent, and it is obtained by various methods described below, but these methods have the following drawbacks. (1)
To dissolve conventional oil-soluble dyes in aliphatic and alicyclic hydrocarbons, long-chain alkyl groups are introduced into the dyes to make them easily soluble. Alkylation of dyes is possible, but is generally synthesized from intermediates containing alkyl groups. In this case, the alkyl group is difficult to handle because it is an alkyl group or cycloalkyl group having particularly 4 or more carbon atoms, and the dye obtained is often semi-solid. The difficulty in synthesizing the intermediates and dyes directly contributes to the high cost of this type of dye. (
2) In order to solubilize general oil-soluble dyes, oil-based marking inks are prepared by dissolving the dyes in higher fatty acids, etc., in oleic acid, alkylphenols, especially nonylphenols, at 80 to 120°C, and then diluting with a solvent. However, because the ink contains higher fatty acids and alkylphenols, this type of ink has the disadvantage that it does not dry completely and is sticky.

(3) Oil-based marking inks that use dyes made by salting acidic dyes or basic dyes with cationic activators or anionic activators, because the writing traces are created by salting water-soluble dyes and activators. It is true that it is insoluble in water, but when water is present, it gradually becomes the original dye and activator, resulting in poor water resistance, and the viscosity of the activator remains in the dye, causing it to become sticky.

(4) A dye acid amide obtained by converting the carboxyl group and sulfone group of an acidic dye into chlorides and reacting them with amines soluble in aliphatic hydrocarbons and alicyclic hydrocarbons, such as oleylamine and laurylamine, is When converting a dye to chloride, thionyl chloride, phosphorus trichloride, or phosphorus pentachloride is used, and the resulting acid chloride is separated and reacted with an amine. Acid chloride has the disadvantage that it is difficult to handle, resulting in an expensive dye.

(5) Oil-based marking ink that uses alkylphenol/novolak resin as a film forming agent and solubilizer:
The dye is solubilized by a loose bond between the phenolic hydroxyl group and other dyes, but other solubilizers such as alkylphenols, especially nonylphenols, and higher fatty acids, especially oleic acid, must be used in combination. First, since the alkylphenol novolak resin is not used alone, the writing marks may be sticky, and since many components must be used, care must be taken to ensure their compatibility and solubility in solvents. The inventors of the present invention have finally completed the present invention as a result of intensive research aimed at solving the above-mentioned problems. That is, the present invention uses a colorant consisting of an oxycarboxylic acid acylated with a fatty acid having 4 or more carbon atoms and a basic dye base, and one or two aliphatic hydrocarbons and/or alicyclic hydrocarbons as a solvent. This is an oil-based ink composition characterized by using the above. An acylated oxyfatty acid with a fatty acid having 4 or more carbon atoms used in the present invention,
The fatty acids used in the acylating agent are as follows.

Butyric acid, valeric acid, capronic acid, purinic acid, lauric acid, myristic acid, palmitic acid, stearic acid 6
Saturated fatty acids such as behenic acid, unsaturated fatty acids such as crotonic acid, linoleic acid, and oleic acid, etc. The oxycarboxylic acids used include glyconeylactic acid, apple r (oxyglutano(i)) citric acid, isocitric acid, triglyceric acid, etc. Acylated oxycarboxylic acids can be easily obtained as semisolid substances by reacting oxycarboxylic acids and acylating agents in the presence of tertiary amines. It is easily soluble in aliphatic hydrocarbons and produces color by forming salts with basic dyes.The base of basic dyes that can be formed with salts can be easily obtained by neutralizing an aqueous solution of basic dyes with an alkali carbonate. As basic dyes, CI Basic Color 11, 2, 11,
CI Basic Orange 2, 14, 15, 21,
22, CI basic 1, 2, 9, 12
, 13, CI Basic Violet 1, 3, 7
, 10, 14, C Basic Bull 1, 3, 5
, 7, 9, 24, 25, 26, CI Basic Green 1, CI Basic Green 1, CI Basic Brown 1, CI
Basic Black 2, etc. The ratio of acylated oxycarboxylic acid to base is 3:1 to 1:3, and 2:
A ratio of 1 to 1:2 is desirable. In addition, low-odor, low-toxicity aliphatic hydrocarbons and alicyclic hydrocarbons that can replace aromatic hydrocarbons include normal hexane, isohexane, normal heptane, normal octane, isooctane, normal decane, and others with boiling points of 40°C or higher. Furthermore, as a mixture, petroleum benzene, gasoline, ligroin, grosine, petroleum spirits, petroleum naphtha, and cyclohexane, methylcyclohexane,
Such as ethylcyclohexane. In an actual oil-based ink composition, 5 to 20 weight percent of acylated oxyfatty acid is dissolved in the above solvent, and 1 to 20 weight percent of a basic dye base is added. If necessary, add alkylphenol novolac resin, coumaron indene resin, alkyd resin, and modified rosin resin. Examples of the oil-based marking ink of the present invention will be specifically explained below.

Example 1 A green oil-based marking ink was obtained by stirring the above components at room temperature.

Example 2 (Modified rosin, manufactured by Hatamakasei Co., Ltd.) 10% by weight ligroin (boiling point 75-120°C) 67'' A blue oil-based marking ink was obtained by stirring the above components at room temperature.

As explained above, the ink of the present invention uses an aliphatic hydrocarbon, aliphatic hydrocarbon, and an oxyfatty acid acylated with a fatty acid having 4 or more carbon atoms that is soluble therein as a base for a basic dye. When writing on the surface of plastic, glass, metal, or wood with an oil-based marking ink containing alkylphenol, especially nonylphenol, or fatty acid, especially oleic acid, as an oil-soluble dye solubilizer, It felt sticky for about a week, but when the ink of the present invention was used, no stickiness was observed after writing.

In addition, with oil-based marking inks that use salt-forming dyes consisting of acidic dyes, basic dyes, and activators, if the writing marks are immersed in water for one month, the dye will gradually dissolve into the water and become less concentrated. The ink of the present invention was free from splashing and had good water resistance. This invention. As explained above, since it is a low odor and low toxicity oil-based marking ink, it has the advantage that it can be used not only for general marking pens but also for stamp inks, recorder inks, etc.

Claims (1)

[Claims] 1. Using an oxycarboxylic acid acylated with a fatty acid having 4 or more carbon atoms, a coloring agent consisting of a basic dye base, and one or more aliphatic hydrocarbons and/or alicyclic hydrocarbons as a solvent. An oil-based ink composition characterized by: