JP2929113B2 - Curing accelerator composition for instant adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Object of the Invention "Industrial application field" The curing accelerator according to the present invention is for rapidly curing a cyanoacrylate-based instant adhesive, and is, for example, an electric industry, an automobile industry, and a machine. It is widely used in the assembly of parts made of metals, plastics, rubber, wood, ceramics, etc. in the fields of industry, precision industry, etc.
Also, at home, do-it-yourself, furniture repair, craft, handicraft,
It is widely used for repairing fishing gear.

“Conventional technology” Cyanoacrylate instant adhesives are widely used in many fields as described above, but lack gap filling properties, have difficulty in bonding porous materials, and have poor build-up adhesion. There are drawbacks such as possible.

As a solution to such a drawback, a method in which a curing accelerator is used in combination with these instant adhesives has heretofore been adopted (Japanese Patent Publication Nos. 43-5004 and 49-12094;
43476).

"Problems to be Solved by the Invention" However, when the instant adhesive is raised and adhered with these curing accelerators, when the cured adhesive is whitened and used for a product in which the adhesive portion is exposed on the surface, It was more likely that the product would have an undesirable appearance. When a solvent such as acetone is used in combination with a curing accelerator, the cured adhesive does not turn white, but the adherend is made of a material that can be attacked by a solvent such as an acrylic resin or an acrylic paint or the like. If the coating is applied so as to be eroded, the adherend is eroded by the curing accelerator, and similarly, there is a problem in appearance as a product.

The present inventors have continued to study to solve these problems and completed the present invention.

(B) Configuration of the Invention "Means for Solving the Problems" The present inventors have solved the problems of the curing accelerator by using a solvent composed of water and a water-soluble organic solvent in combination with a basic substance. The present invention has been completed by finding out what to do. That is, the present invention relates to a curing accelerator suitably used when applying a cyanoacrylate-based instant adhesive to gap filling, adhesion of a porous material, and build-up adhesion, and contains the following three components. The present invention relates to a curing accelerator composition for a cyanoacrylate-based instant adhesive.

A: triethylamine, diethylamine, butylamine, isopropylamine, tributylamine, N, N-dimethylaniline, N-ethyl-N-methylaniline, N,
At least one basicity selected from N-diethylaniline, N, N-dimethyltoidine, N-ethyl-N-methyltoluidine, N, N-diethyltoluidine, dimethylbenzylamine, ethanolamine, propanolamine, ethylenediamine Compound (hereinafter, referred to as “basic compound of the present invention”) B: water-soluble organic solvent C: water ○ basic compound of the present invention In the present invention, the base of the present invention Use an acidic compound. The content of the basic compound of the present invention in the curing accelerator is preferably 0.01 to 50% by weight, more preferably 0.1 to 20% by weight. As the ratio deviates from this range, the effect of promoting the polymerization becomes weaker, or the adhesive strength decreases.

As the basic compound of the present invention, triethylamine,
Diethylamine, butylamine, isopropylamine,
Tributylamine, N, N-dimethylaniline, N-ethyl-N-methylaniline, N, N-diethylaniline, N, N
-Dimethyltoidine, N-ethyl-N-methyltoluidine, N, N-diethyltoluidine, dimethylbenzylamine, ethanolamine, propanolamine, ethylenediamine, and the particularly preferred basic compound of the present invention is N, N-dimethyl. Aniline, N-ethyl-N-methylaniline, N, N-diethylaniline, N, N-dimethyltoluidine, N-ethyl-N-methyltoluidine, N, N-diethyltoluidine.

○ Water-soluble organic solvent The water-soluble organic solvent used in the present invention is a solvent that can be mixed alone with water to form a homogeneous system and is incompatible with water by itself, but is mixed with other solvents to obtain water. And a solvent capable of forming a homogeneous system. That is, the following are specific examples of the water-soluble organic solvent used in the present invention.

Methanol, ethanol, propyl alcohol, butyl alcohol, propylene glycol, butylene glycol, glycerin, diethylene glycol, acetone,
Methyl ethyl ketone, tetrahydrofuran, dioxane, methyl formate, ethyl formate, methyl acetate, glycol carbonate, acetate of ethylene glycol monomethyl ether, acetate of ethylene glycol monoethyl ether, glycol monomethyl ether, glycol monoethyl ether, glycol monobutyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonitrile, formamide, dimethylformamide, diethylformamide, acetamide, dimethylsulfoxide, methanol / toluene mixed solvent, methanol / fluorocarbon 113 mixed solvent, methanol / trichloroethylene mixed solvent, methanol / hexane mixed solvent, Meta Mixed solvent of methanol / cyclohexane, mixed solvent of methanol / cyclohexanone, mixed solvent of methanol / ethyl acetate, mixed solvent of methanol / propyl acetate, mixed solvent of methanol / butyl acetate, mixed solvent of ethanol / toluene, mixed solvent of ethanol / Fleon 113, ethanol / trichlor Ethylene mixed solvent, ethanol / hexane mixed solvent, ethanol / cyclohexane mixed solvent, ethanol / cyclohexanone mixed solvent, ethanol / ethyl acetate mixed solvent, ethanol / propyl acetate mixed solvent, ethanol / butyl acetate mixed solvent, ethanol / acetone mixed solvent, acetone / Fluorocarbon 113 mixed solvent, acetone / trichloroethylene mixed solvent, acetone / hexane mixed solvent, acetone / cyclohexane mixed solvent, acetone / cyclohexanone mixed solvent, Ton / ethyl acetate mixed solvent, acetone / propyl acetate mixed solvent, acetone / butyl acetate mixed solvent, ethanol / acetone / toluene mixed solvent, ethanol / acetone / Fleon 113 mixed solvent, ethanol / acetone / trichloroethylene mixed solvent, ethanol / acetone / Hexane mixed solvent, ethanol / acetone / cyclohexane mixed solvent, ethanol / acetone / cyclohexanone mixed solvent, ethanol / acetone / ethyl acetate mixed solvent, ethanol / acetone / propyl acetate mixed solvent, ethanol / acetone / butyl acetate mixed solvent, etc. .

Among these water-soluble organic solvents, those preferred for the present invention include methanol, ethanol, propyl alcohol, butyl alcohol, a mixed solvent of methanol / toluene, a mixed solvent of methanol / fluorocarbon 113, a mixed solvent of methanol / trichloroethylene, and a mixed solvent of methanol / hexane. Solvent, methanol / cyclohexane mixed solvent, methanol / cyclohexanone mixed solvent, methanol / ethyl acetate mixed solvent, methanol / propyl acetate mixed solvent, methanol / butyl acetate mixed solvent, ethanol / toluene mixed solvent, ethanol / fluorocarbon 113 mixed solvent, ethanol / Trichlorethylene mixed solvent, ethanol / hexane mixed solvent, ethanol / cyclohexane mixed solvent, ethanol / cyclohexanone mixed solvent, ethanol / ethyl acetate mixed solvent, ethanol Le / propyl acetate mixed solvent,
Ethanol / butyl acetate mixed solvent, ethanol / acetone mixed solvent, ethanol / acetone / toluene mixed solvent, ethanol / acetone / CFC 113 mixed solvent, ethanol / acetone / trichloroethylene mixed solvent, ethanol / acetone / hexane mixed solvent, ethanol / acetone / Cyclohexane mixed solvent, ethanol / acetone / cyclohexanone mixed solvent, ethanol / acetone / ethyl acetate mixed solvent, ethanol / acetone / propyl acetate mixed solvent, and ethanol / acetone / butyl acetate mixed solvent.

Further, among these solvents, a solvent having a boiling point of 30 to 160 ° C. is preferable from the viewpoint of ease of use such as quick drying property of the curing accelerator.

Particularly preferred are alcohols such as methanol, ethanol, propyl alcohol and butyl alcohol.

○ Water The content of water in the present invention depends on the use environment such as temperature and humidity when used in combination with the instant adhesive, the type of basic compound of the present invention, the amount added, and the type of water-soluble organic solvent. However, in consideration of workability such as quick drying of the applied curing accelerator which does not whiten the cured product of the instant adhesive, the content is 5% by weight or more, and more preferably 15% by weight or more and 80% by weight. % Or less.

○ Deodorant Some basic compounds, solvents, etc. of the present invention contained in the present invention have a strong odor and may not be preferable for use.Therefore, in order to reduce this odor or to deodorize, It is preferred to add a deodorant to the inventive curing accelerator.

As the deodorant to be used in combination, those which not only reduce or deodorize the amine odor, but also do not impair the properties of the cyanoacrylate-based instant adhesive, and further contribute to improving the adhesive curing speed and strength of the adhesive are desirable.

In the present invention, a substance that deodorizes, reduces, or neutralizes a bad smell is referred to as a deodorant. As the deodorant that is preferably used in the present invention, various natural products collected from plants (for example, as commercial products, Airwick "Lion oils and fats." Or its separated extract as the active ingredient,
Alternatively, there are compounds that mask malodors (for example, vanillin, benzyl acetate, phenethyl alcohol, etc.) and synthetic compounds that react with other malodor components (for example, maleic acid, fumaric acid, lauryl methacrylate, surfactants, etc.). ).

○ Cyanoacrylate-based instant adhesive The curing accelerator of the present invention is used as a curing accelerator for a cyanoacrylate instant adhesive, and the following is the main component of the instant adhesive, 2-cyanoacrylate. It is shown by a general formula.

R in the above formula is an alkyl, alkenyl, cyclohexyl, aryl, or alkoxyalkyl group, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, allyl, cyclohexyl Benzyl, methoxyethyl, ethoxyethyl, methoxypropyl and the like.

Many cyanoacrylate instant adhesives are commercially available, but the curing accelerator according to the present invention can be used as a curing accelerator when using those commercially available adhesives. It is.

○ Usage method The curing accelerator of the present invention can be used widely for industrial purposes and home use in combination with a cyanoacrylate instant adhesive, for example, when bonding wood, paper, and leather, a curing accelerator is used on one side. By applying an instantaneous adhesive to the other side and attaching them together, instantaneous setting is possible. In addition, an adhesive body having a large gap is first coated with a curing accelerator and then coated with an adhesive, whereby an adhesive having fast bonding and strong adhesive strength can be obtained.

In addition, in the case of performing a raised bonding for the purpose of reinforcing the bonding portion, a method of applying a curing accelerator to the adhesive applied thereon and curing the adhesive is preferable.

"Action" By combining a water-soluble organic solvent and water, the present inventors cured from the adhesive having the curing accelerator previously proposed in JP-A-59-66471 and JP-A-62-43476. When the accelerator is applied, the disadvantage that the cured product of the adhesive becomes white is eliminated, and the disadvantage that the curing accelerator attacks the adherend such as acrylic resin and acrylic paint due to the use of the organic solvent is also eliminated. I could get rid of it.

In addition, the reduction in the amount of the organic solvent in the curing accelerator reduces the toxicity and flammability to workers when working in a small room, which is preferable in terms of safety.

Such an effect has been found for the first time by the present inventors.

By these effects found by the present inventors, the present invention solves the problems of the previously proposed curing accelerator and provides a more excellent curing accelerator.

"Examples" Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples.

Example 1 N, N-diethylaniline (2 g), ethanol (63 g), and water (35 g) were mixed and used as a curing accelerator. An instant adhesive “Aron Alpha # 201 (manufactured by Toagosei Chemical Industry Co., Ltd.)” is applied on a brown bakelite plate, and a final curing accelerator is applied thereon. The cured instant adhesive was almost transparent and did not impair the appearance of the bakelite plate. Similarly, an instant adhesive "Aron Alpha GEL-10" is applied on a black ABS resin plate.
(Manufactured by Toagosei Chemical Industry Co., Ltd.) "
Apply the main curing accelerator. The cured instant adhesive was almost transparent, and did not impair the appearance of the ABS resin plate. The acrylic resin plate was immersed in the main curing accelerator for one week, but there was no change in the resin plate.

Examples 2 to 12 A curing accelerator having the composition shown in Table 1 was prepared, and the same test as in Example 1 was conducted. The results are summarized in Table 1.

Comparative Example 1 N, N-diethylaniline (2 g) and ethanol (98 g) were mixed and prepared as a curing accelerator. An instant adhesive “Aron Alpha # 201 (manufactured by Toagosei Chemical Industry Co., Ltd.)” is applied on a brown bakelite plate, and a final curing accelerator is applied thereon. The instant adhesive hardened to white and was not desirable in appearance of the board.

Similarly, an instant adhesive "Aron Alpha GEL-10 (manufactured by Toagosei Chemical Industry Co., Ltd.)" is applied on a black ABS resin plate, and a final curing accelerator is applied thereon. The instant adhesive hardened to white and was not desirable in appearance of the board. The acrylic resin plate was immersed in the main curing accelerator for one week, but there was no change in the resin plate.

Comparative Examples 2 to 4 Curing accelerators having the compositions shown in Table 2 were prepared, and the same tests as in Comparative Example 1 were performed. The results are summarized in Table 2.

Comparative Example 5 N, N-diethylaniline (2 g) and acetone (98 g) were mixed and prepared as a curing accelerator. An instant adhesive “Aron Alpha # 201 (manufactured by Toagosei Chemical Industry Co., Ltd.)” is applied on a brown bakelite plate, and a final curing accelerator is applied thereon. The cured instant adhesive was almost transparent and did not impair the appearance of the bakelite plate. Similarly, black AB
An instant adhesive "Aron Alpha GEL-10 (manufactured by Toagosei Chemical Industry Co., Ltd.)" is applied to the S resin plate, and a final curing accelerator is applied thereon. The cured instant adhesive was almost transparent, and did not impair the appearance of the ABS resin plate. When the acrylic resin plate was immersed in the main curing accelerator for one week, the resin plate was almost completely dissolved.

Comparative Examples 6 to 8 A curing accelerator having the composition shown in Table 2 was prepared, and the same test as in Comparative Example 5 was performed. The results are summarized in Table 2.

(C) Effects of the Invention By using the curing accelerator of the present invention, filling of gaps with a cyanoacrylate instant adhesive, bonding of a porous material, and adhesive bonding can be performed easily and speedily, and the appearance of the adherend can be improved. You can do it without loss. This will speed up the assembly of parts made of metals, plastics, rubber, wood, ceramics, and other materials in the electrical, automotive, mechanical, and precision industries. It can be used more conveniently in repairs, crafts, handicrafts, fishing, etc., and its contribution is very large.

Claims (1)

(57) [Claims] A curing accelerator composition for a cyanoacrylate instant adhesive, comprising the following three components: A: triethylamine, diethylamine, butylamine,
Isopropylamine, tributylamine, N, N-dimethylaniline, N-ethyl-N-methylaniline, N, N-
At least one basic compound B selected from diethylaniline, N, N-dimethyltoidine, N-ethyl-N-methyltoluidine, N, N-diethyltoluidine, dimethylbenzylamine, ethanolamine, propanolamine, ethylenediamine : Water-soluble organic solvent C: Water