JPS6114192B2 - - 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 solvent alone or in combination, and an alkyl ketene dimer and an alkyl ketene soluble in the solvent. The present invention relates to an oil-based ink containing a colorant made by reacting a dimer with a dye having a reactive functional group. Conventionally, oil-based marking inks are composed of an oil-soluble dye and a film-forming resin using an aromatic hydrocarbon, particularly toluene, xylene, and if necessary, butanol as a solvent. This type of ink has been widely used because it dries quickly and the marks left after marking are highly resistant to water and sunlight, but solvents such as toluene and xylene have a strong odor and their toxicity is a problem. There has been a demand for low odor and low toxicity oil-based marking inks that use alternative 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. The most important requirement is to create a dye that dissolves in this odorless solvent, but when the dye obtained by the method described below is used in an oil-based marking ink to meet this demand, the following results are obtained. It has its drawbacks. That is, in order to dissolve conventional oil-soluble dyes in alicyclic hydrocarbons 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 with 4 or more carbon atoms, or a cycloalkyl group.
In particular, many dyes are semi-solid. The difficulty in synthesizing the intermediates and dyes directly contributes to the high cost of this type of dye. As a general means of solubilizing oil-soluble dyes, oil-based marking inks are prepared by dissolving the dyes in higher fatty acids, especially oleic acid, or alkylphenols, especially nonylphenols, at 80 to 120°C, and then diluting them with a solvent. Since the ink contains the higher fatty acids and alkylphenols used, this type of ink has the disadvantage that it does not dry completely and is sticky. Oil-based marking inks that use acid dyes or basic dyes to form salts with cationic activators or anionic activators will cause the salt-forming dyes to react with water-soluble dyes and activators when the writing marks are immersed in water. Since it is a salt-formed product, it decomposes in the presence of water and gradually separates into the original dye and the activator, resulting in poor water resistance.Depending on the type of activator, the viscosity of the dye may remain unchanged. , and therefore sticky marks can be seen on the handwritten marks. The amide derivative of the dye obtained by converting the carboxyl group and sulfone group of the acidic dye into chloride and reacting this with an amine soluble in aliphatic hydrocarbons or alicyclic hydrocarbons, such as oleylamine, laurylamine, etc., is first made into a dye. When converting into chloride, thionyl chloride, phosphorus trichloride, or phosphorus pentachloride is used as a chlorinating agent, and the resulting acid chloride is separated and reacted with an amine. Amide derivatives of dyes are generally produced in this way, but industrially they have the drawback of being expensive dyes because the chemicals used for acid chloridation and the handling of acid chloride dyes are troublesome. . The inventors of the present invention have finally completed the present invention as a result of intensive research in an attempt to solve the above-mentioned problems. That is, the present invention is an oil-based ink composition using a colorant made by reacting an alkyl ketene dimer represented by the following general formula with a dye having a functional group that reacts with the alkyl ketene dimer. general formula (In the formula, R represents an alkyl group having 4 or more carbon atoms.) The alkyl ketene dimer represented by the above general formula has strong reactivity and reacts with compounds having active hydrogen such as hydroxyl groups and amino groups in the following manner. This reaction is very easy to carry out, allowing an alkyl ketene dimer and a dye with active hydrogen to react in a hydrocarbon. It is relatively easy to manufacture, and can be made directly into ink by reacting in the solvent of oil-based ink. The colored product reacted with the alkyl ketene dimer is highly soluble in aliphatic hydrocarbons and/or alicyclic hydrocarbons, so there is no need to use a solubilizer, and oil-based inks using this dye are Handwriting marks will not be sticky. Therefore, the oil-based ink of the present invention is inexpensive because the coloring agent used can be easily produced, and the solubilizing agent is required because it dissolves in aliphatic hydrocarbons and/or alicyclic hydrocarbons, which have low odor and low toxicity. It has the advantage of not leaving sticky marks and being water resistant. The alkyl ketene dimer used in the present invention is an alkyl having 4 or more carbon atoms, such as butyl, amyl, hexyl, hebutyl, octyl, nonyl, decyl, dodecyl, tetradodecyl, hexadecyl, octadecyl, and the like. Dyes containing active hydrogen, such as hydroxyl or amino groups, that easily react with this alkyl ketene dimer are generally based on basic dyes, such as CI Basic Cred 1, CI Basic Violet 1, CI Basic Violet 1, CI Basic Blue 5, and CI Basic Blue 5. , 7, 26, CI Basic Brown 1,
The bases of CI Basic Black 2 and the mordant dyes are CI Mordant Yellow 1, CI Mordant Yellow 5, CI Mordant Orange 4, CI Mordant Red 3,
CI Mordant Blue 1, 13, CI Mordant Brown 1, 14, CI Mordant Black 7, 9, 51, CI Disperse Yellow 1, 7, CI Disperse Orange 3, CI Mordant Black 5, CI dispersion thread 5, same 7, same 15, same
17, 58, CI Disperse Violet 1, 8, CI Disperse Blue 1, 7, 26, CI
Disperse Black 1, 2, oil-soluble dyes: CI Solvent Orange 1, 14, CI Solvent Red 3, CI Solvent Valeolet 8,
CI Solvent Blue 11, CI Solvent Blue 12, CI Solvent Green 3, CI Solvent Brown 3, CI Solvent Brown 5, CI Solvent Black 7, etc. Low odor and low toxicity aliphatic hydrocarbons to replace aromatic hydrocarbons, and alicyclic hydrocarbons with boiling points of 40°C or higher include normal hexane, isohexane, normal heptane, normal octane, isooctane, normal decane, and mixtures. Examples include petroleum benzene, petroleum spirits, petroleum naphtha, and cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane. Alkylphenol novolak resin, coumaron indene resin, alkyd resin, modified rosin resin, etc. are added as necessary. A desirable oil-based ink composition uses 1 to 20 parts by weight of a colorant obtained by reacting an alkyl ketene dimer with a dye having a functional group having active hydrogen in a solvent, and 5 to 20 parts by weight of a resin. Furthermore, the dye reacted with the alkyl ketene dimer that forms the gist of the present invention may be synthesized once and dissolved in an oil-based ink solvent, or the alkyl ketene dimer and the dye having active hydrogen in the oil-based ink solvent may be reacted to form an ink as it is. It is also possible. The present invention will be described in detail below using examples. "Example Middle" indicates parts by weight. [Example] Normal octane 70 parts Hexadecylketene dimer 10〃 (manufactured by Nippon Oil & Fats Co., Ltd., trade name Newpel #1000) Sumikalon Blue BR 10〃 (manufactured by Sumitomo Chemical Co., Ltd., CI Disperse Blue 26) Hytanol # 1133 10 (manufactured by Hitachi Chemical Co., Ltd., octylphenol novolak resin) 10 parts of hexadecyl ketene dimer are dissolved in 70 parts of normal octane at room temperature. Next, adjust the liquid temperature to 40-50
℃, gradually add 10 parts of Sumikalon Blue BR powder, and stir at the same temperature for 2 hours to complete the reaction. Filter the contents and add hytanol #1133 to the filtrate.
A reddish blue oil-based ink is obtained by dissolving 10 parts. In order to compare with this example, an oil-based marking ink was also prepared as Comparative Example 1 using the same amounts of nonylphenol and oleic acid instead of the hexadecyl ketene dimer used in this example. Also, as comparative example 2, Victoria Blue F4R
An oil-based ink was prepared using a colorant obtained by salting (CI Solvent Blue 2, manufactured by BASF) with a phosphate surfactant. Tests were conducted by filling each ink into a felt pen and writing on a polyethylene film. The results are shown in the table.

【table】

[Table] As described above, the present invention is an oil-based ink with low odor and toxicity, and because of its good drying and water resistance, it is generally used not only as a marking ink but also as an ink for stamps, ink for recorders, etc. There are advantages to using it.

Claims (1)

[Claims] 1. A coloring agent made by reacting an alkyl ketene dimer represented by the following general formula with a dye having a functional group that reacts with the alkyl ketene dimer; an aliphatic hydrocarbon and/or alicyclic hydrocarbon as a solvent; An oil-based ink composition characterized by using one or more hydrocarbons. general formula (In the formula, R represents an alkyl group having 4 or more carbon atoms)