JPS5836028B2 - Yusei Ink Seibutsu - 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 are composed of oil-soluble dyes and film-form resins.

This type of ink has been widely used because the written marks left after marking are excellent in water resistance and sunlight resistance, but the solvents used, such as toluene and xylene, have a strong odor and their toxicity is a problem. There has been a demand for the use of alternative solvents and for oil-based marking inks containing 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) 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.

Alkylation of dyes is possible, but is generally avoided 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 combining the intermediate and the dye is directly linked to the high cost of this type of dye.

(2) In order to solubilize general oil-soluble dyes, the dyes are dissolved in higher fatty acids, especially oleic acid, alkylphenols, especially nonylphenols, at 80 to 120°C, and then
Oil-based marking ink is prepared by diluting it with a solvent, but because the ink contains higher fatty acids and alkylphenols, the disadvantage of this type of ink is that it does not dry completely and is sticky. has.

(3) For oil-based marking inks that use dyes in which acidic dyes or basic dyes are salt-formed with cationic activators or anionic activators, the writing marks are formed by salt-forming the water-soluble dye and the activator. It is true that it is insoluble in water, but when water is present, it gradually becomes the original dye and activator, so water resistance is poor, and the viscosity of the activator remains in the dye, making it sticky. It will be done.

(4) The acid dye's carboxyl group and sulfonate group are converted into chlorides, and reacted with amines soluble in aliphatic hydrocarbons and alicyclic hydrocarbons, such as oleylamine and lariulamine. When making chloride, use thionyl chloride, phosphorus trichloride, and phosphorus pentachloride,
It can be obtained by separating the obtained acid chloride and reacting it with an amine, but from an industrial perspective, it has the disadvantage that it becomes an expensive dye because the acid chloride obtained by the reaction is difficult to handle. are doing.

(5) Oil-based marking ink that uses alkylphenol/novolac resin as a film forming agent and solubilizer:
This method solubilizes dyes through loose bonds between phenolic hydroxyl groups and other dyes, but other solubilizers such as alkylphenols, especially nonylphenols, higher fatty acids, especially oleic acid, etc. must be used in combination, and alkylphenols and other solubilizers must be used together. Since novolak resin is not used alone, the writing marks are 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 conducted intensive research to solve the above-mentioned problems, and have finally completed the present invention.

That is, the present invention uses a colorant consisting of an alkylbenzoic acid and a basic dye base represented by the following general formula (1), and one or more aliphatic hydrocarbons and/or alicyclic hydrocarbons as a solvent. This is an oil-based ink used.

By using the general formula alkylbenzoic acid, conventional basic dyes can be used as is, making it possible to obtain inexpensive oil-soluble dyes.Compared to alkylphenols and oleic acids, alkylbenzoic acids are semi-solid. This has successfully solved the problems of conventional oil-based inks, such as the fact that the ink is not sticky.

Examples of the alkylbenzoic acids used in the present invention include amylbenzoic acid, hexylbenzoic acid, heptylbenzoic acid, octylbenzoic acid, nonylbenzoic acid, decylbenzoic acid, dodecylbenzoic acid, tetradecylbenzoic acid, hexadecylbenzoic acid, and octadecylbenzoic acid. be.

The general synthesis method is described in Ogawa Ohka, Vol. 59, 135 (1956).
and by the method described in Kimura and Kashiwaya Yukagaku 24, 121 (1975).

Alkylbenzoic acids can be used even if they are not pure.

This alkylbenzoic acid is easily soluble in aliphatic hydrocarbons,
Because it contains a carboxyl group in its molecule, it easily forms salts with basic dye bases and develops color.

The basic dye base that can be used is obtained by neutralizing an aqueous solution of the basic dye with an alkali carbonate.

Basic dyes include CI Basic Yellow 1, 2, 11, CI Basic Orange 2, 14, 15, 21, 22, CI Basic Red 1, 2, 9,
Same 12, Same 13, CI Basic Violet 1, Same 3
, 7, 101 14, CI Basic Blue 1, 3, 5, 7, 9, 24, 25, 26, CI
These include Basic Green 1, CI Basic 4, CI Basic Brown 1, and CI Basic Black 2.

In addition, examples of low-odor, low-toxicity aliphatic hydrocarbons and alicyclic hydrocarbons that can replace aromatic hydrocarbons include normal hexane, isohexane, normal hebutane, normal octane, isooctane, and normal decane with boiling points of 40°C or higher. , further mixtures include petroleum benzene, gasoline, ligroin, grosine, petroleum spirit, petroleum naphtha, and cyclohexane, methylcyclohexane, ethylcyclohexane, etc.

The actual oil-based ink composition is prepared by dissolving 5 to 50% by weight of alkyl benzoic acid in the above solvent, and adding 1 to 50% by weight of a basic dye base.
Add 20% by weight.

If necessary, alkylphenol novolac resin, coumaron indene resin, alkyd resin, etc. may be added.

Hereinafter, examples of the oil-based marking ink of the present invention will be specifically explained.

Example 1 Dodecylbenzoic acid 10 parts Eisenmalachite Green Base 10 parts (base of CI Basic Green 4, manufactured by Hodogaya Chemical Co., Ltd.) Hytanol 1133 10 parts (octylphenol resin, manufactured by Hitachi Chemical Co., Ltd.) Normal octane 70 parts The above resins and dyes Stir the base in the solvent at room temperature to dissolve it.
A green oil-based marking ink was obtained.

Example 2 Octylbenzoic acid 5 parts Eisen Victoria Blue BO base 5 parts (base of CI Basic Blue 7, manufactured by Hodogaya Chemical Co., Ltd.) Hariestar L 10 parts (manufactured by Hatamakasei Co., Ltd., modified Kuchijin resin) Rig-in ( Boiling point 75-120'C') 8
0 parts The above resin and dye base were stirred and dissolved in a solvent at room temperature to obtain a blue oil-based marking ink.

As explained above, since the ink of the present invention consists of a coloring agent of an aliphatic hydrocarbon, an alkyl benzoic acid having a carboxyl group in the molecule soluble in the aliphatic hydrocarbon, and a basic dye base, alkyl phenol is used, especially alkyl phenol. When an oil-based marking ink containing nonylphenol or a fatty acid, particularly oleic acid, as a solubilizer for oil-soluble dyes was written on the surface of plastic, glass, metal, or wood, it remained sticky for about a week, but when the ink of the present invention was used, In this case, no stickiness was observed after writing.

In addition, with oil-based marking inks that use salt-formed dyes of acidic dyes, basic dyes, and activators, if the writing marks are immersed in water for a month, the dye will gradually dissolve into the water and the concentration will become thinner. The ink of the present invention did not smear and had good water resistance.

Claims (1)

[Scope of Claims] 1. A coloring agent consisting of an alkylbenzoic acid base represented by the following general formula (1) and a basic dye, and one or two aliphatic hydrocarbons and/or alicyclic hydrocarbons as a solvent. An oil-based ink composition characterized by using the above. General formula (in the formula, n represents an integer from 5 to 18)