JPS6031231B2 - 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 a soluble in this solvent. The present invention relates to an oil-based ink composition comprising an azo dye and a film-forming resin.

Oil-based marking inks, which have been used for marking the surfaces of glass, plastic, wood, paper, and other objects, generally contain an aromatic hydrocarbon such as toluene or xylene as a solvent and a dye that dissolves in this, that is, oil. It consists of a soluble dye and a film-forming agent, and was widely used because of its good water resistance and light resistance.

However, recently there has been a desire to develop oil-based marking inks that are less likely to cause pollution problems, ie, have less toxicity and odor. To resolve this issue,
It has been desired to develop an oil-based marking ink that uses alicyclic hydrocarbons instead of toluene and xylene, which are low-toxic and odorless aliphatic hydrocarbons, but the most important thing is to develop dyes that can be dissolved in such solvents. Such a dye is obtained by the method described below, and a low toxicity and low odor aliphatic hydrocarbon,
Although oil-based marking inks can be prepared by dissolving them in alicyclic hydrocarbons, these inks have the following drawbacks. That is, unlike conventional oil-soluble dyes, dyes soluble in m aliphatic hydrocarbons and alicyclic hydrocarbons can be produced by introducing a long-chain alkyl group into the dye molecule.

However, it is difficult to synthesize intermediates and dyes with this type of dye having the longest chain alkyl group when the number of alkyl groups is four or more, and the resulting dyes are often semi-solid. Synthesis *
This type of dye is expensive due to the difficulty and the fact that it is not a general purpose dye, and of course oil-based marking inks using this dye are expensive. ■ Furthermore, oil-based marking inks are made by dissolving general oil-soluble dyes that are soluble in aromatic hydrocarbons into aliphatic hydrocarbons and alicyclic hydrocarbons using solubilizers such as oleic acid and nonylphenol. When used for markings on transparent surfaces such as glass and plastics, the oleic acid and/or nonylphenol contained therein does not dry well and has the disadvantage that handwriting remains sticky forever.

{3} Oil-based marking inks that use salt-forming dyes consisting of acidic or basic dyes and cationic or anionic activators are known to cause handwriting to be immersed in water, whereupon the activator gradually dissolves, and then the dye also dissolves. Concentration decreases due to dissolution.

{4' The production of a dye by converting the carboxyl group and sulfon group of an acidic dye into chlorides and reacting them with amines soluble in aliphatic hydrocarbons and alicyclic hydrocarbons to form acid amides is as follows:
First, acidic dyes are reacted with thionyl chloride, phosphorus trichloride, and phosphorus pentachloride, and then with amines. is expensive, and if oil-based marking ink is used, it naturally has disadvantages such as high cost.

The present inventors have conducted various studies on means to overcome the drawbacks of the various ink compositions mentioned above (particularly poor water resistance and long handwriting drying time). By using this, the present invention was finally achieved.

That is, the present invention is based on the general formula (1) (where R, R2, R3, R4, and R5 are hydrogen, halogen, nitro group, sia/group, lower alkoxy group, or lower alkyl group).

R6 is hydrogen, a lower alkyl group, or x, Y, Z
At least one is an alkyl group having 11 or more carbon atoms, and the others are an alkyl group having 1 to 1 carbon atoms.
4, and M is chlorine or bromine.

). Next, the oil-based ink composition of the present invention will be explained in detail.

The dye, which is the main component of the present invention, is synthesized as follows. That is, a 2-hydroxyethyl-substituted disperse dye is halogenated to form a 2-halogen-substituted dye, and then reacted with a tertiary amine to form a quaternary ammonium salt. The reaction route for the oil-soluble dye derived from CI Disperse Violet 13 is as follows. '1' Halogenation reaction■ The quaternization reaction is very smooth.

Moreover, a quaternary ammonium salt can also be obtained in good yield. It is easily soluble in aliphatic hydrocarbons and aliphatic hydrocarbons. Disperse dyes that can be used for halogenation and quaternization include CI Dispers Orange 5 and CI Dispers Orange 1.
, 2, 5, 7, 13, 16, 17, 19,
32, CI Disperse Violet 12, 13, 2
4, CI Jispers Brown 1, CI Jispers Black 4, etc. For this halogenation, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, sulfuryl chloride, thionyl chloride and phosphorus oxybromide, phosphorus tribromide, phosphorus pentabromide, sulfuryl bromide, and thionyl bromide are used. Halogenation can be easily carried out in a solvent that dissolves the disperse dye, and by subsequently adding a tertiary amine, the desired quaternary ammonium salt was obtained. Next, regarding the preparation of the oil-based marking ink of the present invention, the low odor and low toxicity solvents used are normal hexane, isohexane, normal heptane, normal octane, isooctane, and isohexane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, normal heptane, which has a boiling point of 40q○ or higher as an aliphatic hydrocarbon. Normal decane, petroleum penzyl, gasoline, ligroin, kerosene, petroleum spirit, petroleum naphtha, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexene, dimethylcyclohexane, and ethylcyclohexane are used as mixtures, and esterified products of the above-mentioned disperse dyes are used. 2 to 3% by weight, and 5 to 2% by weight of an alkylphenol novolac resin, modified rosin resin, or modified alkyd resin as a film forming agent.

Examples of tertiary amines that can be used include lauryldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, and oxyethylenedodecylamine. Furthermore, an oil-soluble activator, rust preventive, and antistatic agent are added as necessary. The oil-based marking ink of the present invention will be specifically explained below using Examples, in which "the middle part of the example" refers to parts by weight.

Example 1 Normal octane 74 parts Chroman resin (manufactured by Nippon Steel Chemical Co., Ltd.) 15 parts Emazole 41S (manufactured by Kao-Atlas Corporation, nonionic activator)
A purple oil-based marking ink was obtained by stirring one part of the above ingredients at room temperature.

Example 2 Harrystar-L (manufactured by Hatama Kasei Co., Ltd., modified rosin resin)
15 parts ethylcyclohexane 65 parts A red light oil-based marking ink was obtained by stirring the above ingredients at room temperature.

As mentioned above, the oil-based ink composition of the present invention halogenates a disperse dye having an N-substituted 2-hydroxyethyl group to form an N-substituted halogenoethyl group, and then at least one alkyl group having 11 or more carbon atoms. , Others are obtained by dissolving a quaternary ammonium salt obtained by reacting with a tertiary amine, which is a lower alkyl group having 1 to 4 carbon atoms, in an aliphatic hydrocarbon and/or alicyclic hydrocarbon, '1} Oil-based marking ink consisting of acid dye, basic dye, cationic activator, and salt-forming dye with anionic activator will wash away if the handwritten marks are left under running water for 24 hours, even if the combination of dye and activator is carefully considered. However, the oil-based marking ink of Example 1 of the present invention showed no decrease in concentration even when left in running water for 4 hours. The conventional oil-based marking ink required a touch dry time of 20 minutes or more at room temperature (30 qC) when written on the surface of a non-permeable material such as glass or plastic, but the touch dry time of the ink of the present invention was was less than 1 minute.

Furthermore, since aliphatic hydrocarbons and alicyclic hydrocarbons are used, it has low odor and low toxicity, making it extremely suitable not only for oil-based marking inks but also for other writing instrument inks, stamp inks, and recorder inks. suitable for

Claims (1)

[Claims] 1 General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. It is an alkyl group. R_6 is hydrogen, a lower alkyl group, or ▲ mathematical formula, chemical formula,
There are tables, etc.▼, and at least one of X, Y, and Z is an alkyl group with 11 or more carbon atoms, the others are lower alkyl groups with 1 to 4 carbon atoms, and M is chlorine or bromine. . 1. An oil-based ink composition characterized by dissolving the dye represented by ) in an aliphatic hydrocarbon or an alicyclic hydrocarbon together with a resin. 2. The oil-based ink composition according to claim 1, wherein the dye represented by the general formula (I) is ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 3. The oil-based ink composition according to claim 1, wherein the dye represented by the general formula (I) is ▲a mathematical formula, a chemical formula, a table, etc.▼.