JPS6055550B2 - 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 in a mixture, and a soluble in this solvent. The present invention relates to an oil-based ink consisting of a long-chain dibasic acid and a disperse dye and/or a basic dye as a dye.

Conventional oil-based inks are composed of oil-soluble dyes and film-forming resins using aromatic hydrocarbons, 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 have excellent water resistance and sunlight fastness, but the solvents such as toluene and xylene have a strong odor and are problematic due to their toxicity. There has been a demand for low odor and low toxicity oil-based inks by using alternative solvents. Therefore, oil-based inks using aliphatic hydrocarbons and/or alicyclic hydrocarbons as solvents, which are said to have low odor and low toxicity, have been developed. However, none of them could be put to practical use due to the drawbacks described below. (1) Since conventional oil-soluble dyes do not dissolve in aliphatic hydrocarbons and alicyclic hydrocarbons, long-chain alkyl groups must be specifically introduced into the dyes.

In the alkylation of dyes, an alkylated intermediate is first synthesized, and then a dye is produced. However, because the synthesis of alkylated intermediates and the synthesis and separation of alkylated dyes are each very difficult, this type of dye is very expensive compared to its non-alkylated counterpart. . Therefore, this type of oil-based ink is also naturally expensive. (2)
Next, in order to solubilize without chemical reaction, disperse dyes and/or basic dyes are added to higher fatty acids, especially oleic acid, and alkylphenols, especially nonylphenols, at a concentration of 80 to 12%.
Oil-based ink is prepared by dissolving it at 0°C and diluting it with a solvent, but because the ink contains higher fatty acids and alkylphenols, the writing marks of this type of ink are made of non-permeable metals, It has the disadvantage that it does not completely dry on surfaces such as glass and plastic and remains sticky forever. (3) Oil-based inks that use acid dyes or basic dyes that have been salted with cationic activators or anionic activators, when the writing marks are immersed in water,
Since the advance dye consists of a water-soluble dye and an activator, it gradually dissolves into water, so it has poor water resistance.Depending on the type of activator used, it may be difficult to write on non-permeable paper. Due to its viscosity, handwriting tends to become sticky.

(4) A dye amide obtained by reacting an acidic dye in which the carboxyl group and sulfone group are each chlorinated with an amine soluble in aliphatic hydrocarbons and alicyclic hydrocarbons, such as oleylamine and laurylamine. Derivatives are difficult to use because of the unpleasant odor and inconvenience of handling the thionyl chloride, phosphorus trichloride, and phosphorus pentachloride used in the reaction, and the inconvenience of having to be careful when handling the acid chloride of the obtained dye. is expensive, and therefore this oil-based ink is also expensive.

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 uses 5 to 2 parts by weight of a dibasic acid having 12 to 20 carbon atoms as a coloring agent, 1 to 2 parts by weight of a base of a disperse dye and/or basic dye capable of forming a salt with the dibasic acid, An oil-based ink composition containing 50 to 9 parts of an aliphatic hydrocarbon and/or alicyclic hydrocarbon as a solvent, and optionally 5 to 2 parts of a soluble resin in the solvent. . The long-chain dibasic acid that is the gist of the present invention preferably has 12 to 20 carbon atoms.

If the number of carbon atoms is 11 or less, the solubility in aliphatic hydrocarbons and alicyclic hydrocarbons is not as good as that of those with 12 or more carbon atoms, and those with 21 or more carbon atoms cannot be advantageously produced industrially. This is because the amount required for salt production increases (due to the larger molecular weight). HOOC(CH2)10C00H decane-1,1 as a long chain dibasic acid with 12 to 20 carbon atoms
0 dicarboxylic acid HOOC (CH2) 14C00H tetradecane-1,14 dicarboxylic acid HOOC (CH2) 18
C00H octadecane-1,18 dicarboxylic acid 6-ethylhexadecane-1,16 dicarboxylic acid can be used.

Dyes that form salts with this dibasic acid include disperse dyes having primary, secondary, and tertiary amines capable of forming salts in their molecules;
Basic dye bases can be used. As a disperse dye, C.I. I. Dispers Yellow O, Same 42, C Sat Dispers Orange 1, Same 3, Same 11, C. I. Dispersed red 11, same 15sC soil dispersed violet 1
, 4, 8, C. I. Dispers Blue 1, same 3,
C.I. Basic Yellow 2, C.I. Basic Orange 2, C.I. Basic Orange 2, C.I. Basic Orange 2, C.I. Basic Orange 2, C.I. Basic Orange 2, C.I. Basic Orange 2, C.I. 9, C.I. Basic Violet 1,
Same 3, Same 10, Same 14, C. I. basic blue 1,
Same 3, Same 5, Same 7, Same 9, Same 2 tun, Same 2 Mi C. I. Basic Green 1, Basic Green 4, C. I. Basic brown 1
,C. I. Basic Black 2 etc. can be used.

The amount of the dibasic acid to be used corresponds to the amount of the salt-forming dye used, and is preferably 5 to 2 parts by weight.

It is desirable to use 1 to 2 parts by weight of the dye; if it is less than 1 part by weight, the ink will be too thin as an oil-based ink, and if it is more than 2 parts by weight, it will have a high viscosity and cannot be used practically. Aliphatic hydrocarbons and alicyclic hydrocarbons are used as low-odor and low-toxicity solvents with boiling points of 4.
1) C or higher normal hexane, isohexane, normal heptane, normal octane, normal decane, and mixtures such as petroleum benzine, petroleum spirit, petroleum naphtha, cyclohexane, ethylcyclohexane, etc.

The amount used is preferably 50 to 9 parts. If necessary, 5 to 20 parts by weight, preferably 10 to 15 parts by weight of an alkylphenol novolak resin, coumaron indene resin, alkyd resin, or modified rosin resin are used as the film-forming resin. Examples will be described in detail below, and the middle part of the example represents parts by weight. Example 1 Normal octane 70ml11
-ethyl 7-hexadecene 1.18 dicarboxylic acid
10 (U2O
-B: Manufactured by Okamura Oil Co., Ltd.)C. I. Base of Basic Violet 10 5 (Rhodamine B base manufactured by Hodogaya Chemical Co., Ltd.) Alkylphenol novolak resin
15 (Hitanol #1133: manufactured by Hitachi Chemical Co., Ltd.) A bluish red oil-based ink was obtained by stirring the above components at room temperature.

Example 2 Petroleum ligroin (boiling point 75-12rc) 75 parts Decane-1.10 dicarboxylic acid 10 (
Sl2 top: Okamura Oil Co., Ltd.) C. I. Disperse Blue 15〃 (Miketon Fast Bull Extra Ni manufactured by Mitsui Toatsu Chemical Co., Ltd.) Modified Rosin 10〃 (Harrier Star L: manufactured by Hatama Kasei Co., Ltd.) By stirring the above ingredients at room temperature, you can create a reddish color. A blue oil-based ink was obtained.

As explained above, using dyes that can form salts with aliphatic hydrocarbons and/or alicyclic hydrocarbons, or long-chain dibasic acids that are soluble in mixed oils such as petroleum naphtha, etc. With the ink of the present invention, no stickiness was observed even after writing on non-permeable surfaces such as plastic, glass, metal, and wood.

On the other hand, oil-based inks using alkylphenol, especially nonylphenol, or fatty acids, especially oleic acid, as solubilizers for oil-soluble dyes remained sticky for about a week when written on the surface of these non-permeable substrates. Also, with oil-based inks that use salt-forming dyes consisting of acidic dyes and/or 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 diluted, but this The ink of the invention did not smudge and had good water resistance. As explained above, since the present invention is an oil-based ink with low odor and low toxicity, it has the advantage that it can be used not only as a general marking ink but also as a stamp ink and a recorder ink.

Claims (1)

[Claims] 1 5 to 20 parts by weight of a dibasic acid having 12 to 20 carbon atoms, 1 to 20 parts by weight of a base of disperse dye and/or basic dye that can form salts with the dibasic acid, aliphatic hydrocarbon and/or alicyclic An oil-based ink composition comprising 50 to 90 parts by weight of one or more hydrocarbons.