JPS5836027B2 - 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 solvent and/or alicyclic hydrocarbon solvent alone or in a mixture; The present invention relates to an oil-based ink composition comprising a salt-forming compound of a dialkyl phenylgunidine and an acid dye that is soluble in this solvent, and a film-forming agent.

Oil-based marking inks that have traditionally been used for marking glass, plastic, wood, paper, and other objects generally use aromatic hydrocarbons such as toluene or xylene as solvents, and dyes that dissolve in these, i.e., oil-soluble dyes and film-forming agents. It was widely used because it has good water resistance and sunlight fastness.

However, recently there has been a desire to develop an oil-based marking ink that does not cause pollution problems, that is, is less toxic and has less odor.

To solve this problem, it has been desired to develop an oil-based marking ink that uses low toxicity and low odor aliphatic hydrocarbon solvents or alicyclic hydrocarbon solvents instead of toluene and xylene. The development of a dye soluble in such a solvent is of utmost importance, and the dye was obtained by the method described below.

This dye is processed using a low-toxicity and low-odor aliphatic hydrocarbon solvent.
Although oil-based marking inks can be prepared by dissolving them in alicyclic hydrocarbon solvents, these inks have the following drawbacks.

That is, (1) Dyes soluble in aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents can be produced by introducing long-chain alkyl groups into dye molecules, unlike conventional oil-soluble dyes. can.

Direct alkylation of dyes is possible, but generally intermediates with long chain alkyl groups are first synthesized and these dyes are combined.

In this case, since the alkyl group is particularly an alkyl group or a cycloalkyl group having 4 or more carbon atoms, it is difficult to synthesize intermediates and dyes, and the resulting dyes are often semi-solid.

Difficulties in synthesizing the intermediates and dyes and the fact that they are not general purpose dyes make this type of dye expensive.

Therefore, oil-based marking inks from this dye are expensive.

(2) Currently oil-soluble, which is soluble in aromatic hydrocarbon solvents. In order to solubilize a dye in an aliphatic hydrocarbon solvent or an alicyclic hydrocarbon solvent, it is dissolved in a higher fatty acid such as oleic acid or nonylphenol or an alkylphenol at 80 to 120°C, and then diluted with a solvent. Although an oil-based marking ink is obtained, this type 0 ink has the disadvantage that written marks are difficult to dry and remain sticky because they contain solubilizers such as oleic acid and nonylphenol.

(3) Inks prepared by making salts from acidic dyes or basic dyes and cationic activators or anionic activators and dissolving the salt-formed dyes use activators; When a handwritten mark is immersed in water, the activator gradually disappears, and then the dye also disappears, resulting in a decrease in density.

Furthermore, since the salt-forming dye with the activator is sticky and semi-solid, the handwritten marks also tend to be sticky.

(4) A type of dye in which the carboxyl group and sulfonic group of an acidic dye are each chlorinated and reacted with an amine soluble in an aliphatic hydrocarbon solvent or an alicyclic hydrocarbon solvent to form an acid amide is made by first dyeing the dye. To make acid chloride, it is reacted with thionyl chloride, phosphorus trichloride, and phosphorus pentachloride, but in industrial production, it is necessary to handle the chlorinating agent, extract the reactant, and separate the acid amide, which is the reactant with the amine. Dyes are expensive because it is difficult to

Unfortunately, oil-based marking inks from this type of dye can be costly.

(5) When using alkylphenol/novolak resin as part of the solubilizing agent, it alone has weak solubilization, so other solubilizing agents must be used together, and it is only possible to use ink that leaves sticky marks. This is something that cannot be obtained.

The inventors of the present invention have conducted various studies on ways to overcome the drawbacks of ink compositions as described above. As a result, the present inventors have found that these ink compositions can be overcome by using inexpensive acid dyes and salt-forming compounds of dialkyl phenyl guanidine. The problem was solved and the present invention was completed.

That is, the present invention comprises an oil-based ink comprising a colorant comprising a dialkyl phenyl guanidine acid dye represented by the following general formula (wherein n represents an integer from 4 to 20).

This dialkyl phenyl guanidine forms a salt with the acidic dye and solubilizes the dye as shown in the following formula (in the formula, n is an integer of 4 to 20, D is an acidic dye residue, and X is an anionic dissociative group).

) This salt can be dissolved by simultaneously adding dialkyl phenylanidine and an acid dye in an oil-based ink solvent, but the salt that can be precipitated by pouring an aqueous solution of an acid dye into an aqueous solution of dialkyl phenyl guanidine hydrochloride is filtered. An oil-based ink composition can be easily obtained by washing, drying, and dissolving in an oil-based ink solvent.

Next, the present invention will be explained in detail.

Examples of dialkyl phenyl guanidine that can be used in the present invention include dibutyl phenyl guanidine, diamyl phenyl guanidine, dihexyl phenyl guanidine, diheptyl phenyl guanidine, dioctyl phenyl guanidine, dinonylphenyl guanidine, didecyl phenyl guanidine, and didecyl phenyl guanidine. These include dodecyl phenyl guanidine, ditetradecyl phenyl guanidine, dihexadecyl phenyl guanidine, and dioctadecyl phenyl guanidine.

Examples of acidic dyes that can be salt-formed with dialkyl phenylguanidine include CI Acid Ero-1, CI Acid Ero-1, CI Acid Ero-3, CI Acid Ero-7,
11, 17, 19, 23, 25, 29, 36, 38, 42, 44, 49, 61, 7
0, 72, 76, 78, 79, 131, 1
35, 141, CI Ajit Orange 1, 7, 8, 10, 19, 20, 24, 28, 41
, 43, 51, 56, 63, 65, 67,
CI Assisted Red 1, 6, 8, 9, 13,
14, 18, 26, 27, 32, 35, 37, 42, 51, 80, 82, 85, 8
7, 88, 89, 92, 94, 97, 10
6, 111, 114, 117, 118, 11
9, 129, 131, 134, 138, 14
5, 149, 158, 249, 257, 26
5, 266, CI acid violet 7, 11
, 15, 34, 41, 43, 48, 49,
CI Acid Blue 1, 9, 15, 22, 2
3, 25, 27, 29, 40, 41, 43
, 45, 59, 62, 74, 78, 82,
83, 92, 93, 103, 112, 11
3, 117, 120, 126, 127, 12
9, 138, 140, CI Acid Green 3,
9, 16, 19, 20, 25, 27, 2
8, 36, 40, 41, 44, CI Assisted.
Brown 2, Brown 4, Brown 13, Brown 14, Brown 20, Brown 27,
CI Acid Black 1, 2, 7, 24, 2
There are 6, 29, 31, 48, 50, and 94.

Next, examples of aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents that can be used as low-odor, low-toxicity solvents to replace aromatic hydrocarbon solvents include normal hexane, isohexane, and normal hexane with a boiling point of 40°C or higher. Butane, normal octane, isooctane, normal decane, and mixtures thereof include petroleum benzine, gasoline ligroin, kerosene, petroleum spirit, petroleum naphtha, and cyclohexane, methylcyclohexane, dimethylcyclohexane, and the like.

Also, if necessary, an aromatic hydrocarbon solvent such as benzene,
Toluene, xylene, etc. may also be added.

In addition to the above-mentioned precepts, actual oil-based marking inks use resins as film-forming agents, such as alkylphenol novolac resins, coumaron-indene resins, modified rosin resins, and modified alkyd resins.

The oil-based marking ink contains 2 to 20% by weight of dialkyl phenylguanidine and 2 to 2% of acid dye.
It is desirable to contain 0% by weight, 5 to 30% by weight of resin, and 50 to 80% by weight of solvent.

If necessary, add an oil-soluble activator, rust preventive agent, and antistatic agent.

Examples of the present invention will be specifically described below with respect to oil-based marking inks, and the middle part of the example represents parts by weight.

Example 1 Didodecyl phenylguanidine 10 parts Eisen Acid Phloxine PB 5/l (CI Acid Red 92, manufactured by Hodogaya Chemical Co., Ltd.) Normal octane
75 part Hikunor 1133
10 (Octyl Phenovolac, manufactured by Hitachi Chemical) A salt is made from an aqueous solution of the hydrochloride of didodecylphenylguanidine among the above components and an aqueous solution of Eisen Acid Phloxine PB, separated and dried, and this is normalized. Mix and dissolve octane and hytanol 1133, or mix hytanol 1133, didodecylphenylguanidine, and crampon acid phloxine PB in normal octane at room temperature.
When the mixture was added and dissolved by stirring, a good red oil-based marking ink was obtained.

The same red oil-based marking ink was obtained by using 10 parts of ditetradecylphenylguanidine, dihexadecyl phenylguanidine, or dioctadecyl phenylguanidine in place of didodecylphenylguanidine.

Example 2 Dibutyl phenylguanidine 15 parts Patent Blue ■X 15ll (CI acid blue-1, manufactured by Sumitomo Chemical Co., Ltd.) Ligroin
60〃Kumaron resin (manufactured by Nippon Steel Chemical Co., Ltd.) 1
0 A blue oil-based marking ink was obtained by stirring a certain amount of the above at room temperature.

Example 3 Dioctylphenyl guanidine 20 parts Nigushin NB conc. 10 l/(CI Acid Black 2, manufactured by Sumitomo Chemical Co., Ltd.) Ethylcyclohexane
55 Harrier Star L
15/l (manufactured by Hatamakasei Co., Ltd., modified resin) A black oil-based marking ink was obtained by stirring the above ingredients at room temperature.

Suminol Milling instead of Nigrosin NB Conch
Black 8BX (manufactured by Sumitomo Chemical Co., Ltd.), Kayanol Milling Black VLG (manufactured by Nippon Kayaku Co., Ltd.), Diamond
Even when 10 parts of Fast Black BR Conc (manufactured by Mitsubishi Kasei Corporation) was used, a black oil-based marking ink was obtained.

As explained above, the oil-based ink of the present invention uses an acidic dye that is inexpensive and allows the hue to be selected arbitrarily, and a dye made by salt formation with dialkyl phenyl guanidine, and does not use a solubilizer, so it is easy to write. There is no trace (t-f = t), and since no salt-forming dye is used with the activator, the water resistance of the writing trace is good when immersed in water, and acid amide dye derived from acid dye and Since it is not an alkyl group-substituted dye, it does not require complicated steps for dye synthesis, and therefore has the advantage of providing an inexpensive dye.

In short, the handwritten marks made using the ink of the present invention dry quickly, and the density did not decrease even after being immersed in running water for one month.

Comparative examples that do not use the ink of the present invention do not have quick drying properties,
The stickiness lasted for 3 days, and the concentration clearly decreased after being immersed in running water for 1 month.

Claims (1)

[Scope of Claims] 1. An oil-based ink composition characterized by containing a colorant consisting of a dialkyl phenylguanidine represented by the following general formula and an acid dye. General formula (in the formula, n represents an integer from 4 to 20)