JPS6215595B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to colored 2-cyanoacrylate adhesive compositions.

2-Cyanoacrylate has traditionally been used to bond rubber, plastic, metal, etc., but there has been a demand for colored 2-cyanoacrylate adhesives to help identify the application of the adhesive. There is.

However, 2-cyanoacrylate is a monomer that undergoes anionic and radical polymerization, and has properties such as polymerization or decreased storage stability when other substances are added, so it is extremely difficult to color it with dyes. It was difficult.

The present inventors thought that the most preferable dye for coloring 2-cyanoacrylate was an oil-soluble dye, but when directly colored with such a dye, the viscosity increases due to polymerization over time during storage. Finally, I learned that the phenomenon of hardening occurs.

When the cause of this was investigated in detail, it was found that trace amounts of impurities such as bases adhering to the surface of the oil-soluble dye particles significantly inhibited the storage stability of the adhesive.

The present inventors investigated how to remove such adhering impurities from the surface of oil-soluble dye particles and obtain a stable colored 2-cyanoacrylate adhesive, and as a result, they found that cleaning with a specific acid is effective. Heading The invention has been completed.

That is, the present invention is a colored adhesive composition prepared by dissolving oil-soluble dye particles washed with a sulfonic acid or polyhalogenated carboxylic acid solution in a 2-cyanoacrylate adhesive.

Examples of the 2-cyanoacrylate used in the present invention include the following esters.

For example, alkyl esters such as methyl, ethyl, propyl, butyl, heptyl, octyl, and dodecyl; cyclohexyl esters; alkenyl and alkynyl esters such as allyl, crotyl, and propargyl; halogenated alkyl esters such as 2-chloroethyl and perfluoroalkyl; Examples include esters having an ether bond such as methoxyethyl, 2-ethoxyethyl, 3-methoxybutyl, and tetrahydrofurfuryl.

These 2-cyanoacrylates contain several to several hundred ppm of acids such as SO ₂ , HF, sultone, sulfonic acid, and phosphoric acid as stabilizers, and radical polymerization inhibitors such as hydroquinone, hydroquinone methyl ether, and catechol. Added in several hundred ppm. In some cases, a thickener such as polymethyl methacrylate or cellulose ester and a plasticizer such as dioctyl phthalate are also added to form an adhesive.

The oil-soluble dyes used for coloring the adhesive of the present invention include monoazo-based, diazo-based, anthraquinone-based, phthalocyanine-based, and triallylmethane-based dyes.

Specifically, for example, C.I. Solvent Yellow (C.I.
Solvent Yellow) 2, 6, 14, 15, 16, 19, 21,
33, 56, 61, 80, C.I. Solvent Orange (C.I.
Solvent Orange) 1, 2, 5, 6, 14, 37, C.I.
Solvent Red) 1, 3, 8, 23, 24, 121, C.I. Disperse Red 9 (C.
I. Disperse Red9), C.I. Solvent Violet (C.
I.Solvent Violet) 8, 13, 14, etc. (described in "Dye Handbook" published by Maruzen Co., Ltd., July 20, 1978, pp. 838-878).

These oil-soluble dyes have an azo group, an amino group, a quaternary ammonium group, or a hydroxyl group in the molecule, and are usually weak bases or neutral substances.
They are commercially available from dye manufacturers in the form of dyes or mineral salts of these dyes.

In the present invention, the specific acid for washing oil-soluble dyes is sulfonic acid or polyhalogenated carboxylic acid, and a dilute solution of such acid is used to wash the surface of the dye particles.

Specific examples of such sulfonic acids or polyhalogenated carboxylic acids include arylsulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, naphthylsulfonic acid, and hydroxyphenylsulfonic acid, methanesulfonic acid, and ethanesulfonic acid. , alkyl sulfonic acids such as trifluoromethanesulfonic acid, sulfonic acids such as chlorosulfonic acid, sulfamic acid, N-cyclohexylsulfamic acid, polyhalogenated acids such as trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, perfluorobutyric acid, etc. There are carboxylic acids.

These acids are used as dilute solutions (0.1-5% concentration) in water, trichloroethylene, benzene, toluene, methanol, ethanol, acetone, THF, methyl ethyl ketone, ethyl ether, etc.

For washing, a normal method for washing crystal particles is adopted, and a washing liquid is used in an amount of 1 to 10 times the amount of the oil-soluble dye (less than the equivalent weight of the dye amino group).

Such washing removes deposits on the surface of the dye particles, but the amino groups in the dye hardly react with the acid in the washing solution.

The washed and filtered dye is dried. In dyes purified in this way, the amino groups on the surface of the dye particles are only partially neutralized, while the amino groups in commercially available oil-soluble dyes remain unchanged. (Approximately 90% or more remains unchanged) The "normal salt of dye and acid" obtained by completely dissolving the dye in water or a solvent, adding more than an equivalent amount of acid to it, reacting, and concentrating it is cyanoacrylate. It is unsuitable as a coloring dye, and has the disadvantage that it significantly delays the setting time of the adhesive over time. Furthermore, there are disadvantages in that there are many purification operations such as dissolving, neutralizing, concentrating, filtering, and drying the dye, which is complicated and increases the number of erroneous operations.

In the present invention, the washed oil-soluble dye is 2-
It is added in an amount of 0.01 to 1%, preferably 0.05 to 0.5%, based on the cyanoacrylate, to obtain a cyanoacrylate adhesive in which a stably colored dye is dissolved.

The present invention will be specifically explained below with reference to Examples.

Example 1 Orient Oil Red #330 [Orient
Oil Red #330: Manufactured by Orient Chemical Co., Ltd.: C.I. Disperse Red 9 (C.I.
Disperse Red9)] was washed with 50 parts of 1% p-toluenesulfonic acid methanol solution for 5 minutes,
The purified dye obtained by over-drying is used as Aron Alpha #201.
(trade name, 2-cyanoacrylate adhesive manufactured by Toagosei Kagaku Kogyo Co., Ltd.) by adding 0.1% and dissolving it to obtain a red-colored cyanoacrylate adhesive. This colored product shows no change in viscosity (2 cp) and set time (5 seconds (natural rubber)) even if stored at 20℃ for half a year.
No delay was observed.

Example 2 Orient Oil Orange PS: Manufactured by Orient Chemical Co., Ltd.: C.I. Solvent Yellow 14 (C.I.
5 parts of Solvent Yellow 14) were mixed with 50 parts of 0.5% methanesulfonic acid ethanol solution, stirred in suspension (10 minutes), filtered and dried to purify.

Aron Alpha #202 (trade name, 2-cyanoacrylate adhesive manufactured by Toagosei Chemical Industry Co., Ltd.)
A 2-cyanoacrylate adhesive colored yellow was obtained by adding and dissolving 0.1%. This colored product is 20
Even after storage at ℃ for half a year, the viscosity was 100 cp and the set time was 10 seconds (natural rubber), which did not change from the initial state.

Example 3 Orient Oil Violet #730
[Orient Oil Violet #730: Manufactured by Orient Chemical Co., Ltd.: C.I. Solvent Violet 14
(C.I.Solvent Violet 14)] 5 parts were washed with 50 parts of 0.5% trifluoroacetic acid methanol solution, filtered and dried to obtain a purified dye. This was added and dissolved at 0.1% in Aron Alpha #101 (trade name, 2-cyanoacrylate adhesive manufactured by Toagosei Chemical Industry Co., Ltd.) to obtain a stable purple-colored 2-cyanoacrylate adhesive. . Even if this colored product is stored at 20℃ for half a year, the viscosity is 2 cp and the set time is 15 seconds (iron).
, and there was no change from the initial performance.

On the other hand, the viscosity of the product to which unrefined Orient Oil Violet #730 was added increased significantly within six months. In addition, it was found that those colored with dyes that were neutralized with trifluoroacetic acid and made into normal salts had a significantly slower set time after half a year, with a set time of 5 minutes or more (iron), which caused significant deterioration over time.

Example 4 Orient Oil Red RR: Orient Chemical Co., Ltd.: C.I. Solvent Red 24 (C.I.
5 parts of Solvent Red 24) were mixed with 50 parts of a 2% methanol solution of benzenesulfonic acid, stirred at room temperature, and left to stand to dry the dye particles to obtain a purified dye. Aron Alpha #201 with 0.1% of this added was a red colored product with excellent storage stability.

Claims (1)

[Scope of Claims] 1. A colored adhesive composition prepared by dissolving oil-soluble dye particles washed with a sulfonic acid solution or a polyhalogenated carboxylic acid solution in a 2-cyanoacrylate adhesive. 2 Oil-soluble dyes are C.I. Disperse Red 9 and C.I. Solvent Yellow 14.
Yellow14), C.I. Solvent Violet14 (C.I.Solvent Violet14) or C.I.Solvent Violet14)
I Solvent Red 24 (C・I・Solvent)
Red24), and the sulfonic acid solution or polyhalogenated carboxylic acid solution is benzenesulfonic acid, p-
The colored adhesive composition according to claim 1, which is an aqueous or alcoholic solution of an acid selected from toluenesulfonic acid, methanesulfonic acid, and trifluoroacetic acid. 3. The colored adhesive composition according to claim 1 or 2, wherein 0.01 to 1% of the oil-soluble dye is dissolved in the 2-cyanoacrylate.