JPH04100878A - Bonding method - Google Patents

Abstract

PURPOSE:To make it possible to temporarily fix adherends simply in a short time and to permanently bond them firmly by using a rapidly curable adhesive comprising a specified two-pack adhesive to be applied pack by pack and a durable adhesive comprising a two-pack adhesive. CONSTITUTION:A method of permanently bonding adherends with a durable adhesive while temporarily fixing them with a rapidly curalbe adhesive by using these adhesives together, wherein a catalytically curable acrylic two-pack adhesive to be applied pack by pack [a first composition containing a thermoplastic rubber, a (meth)acrylic ester, and an organic peroxide is used in combination with a second composition containing an accelerator for the decomposition of the organic peroxide]is used as the rapidly curable adhesive, and a two-pack adhesive (a first composition containing a modified silicone resin and a curing agent for epoxy resin and a second composition containing an epoxy resin and a curing agent for the modified silicone resin are mixed before use) is used as the durable adhesive. According to this method, in putting adherends together, they can be temporarily fixed in a short time without using other tools, and sufficient bonding performance can be revealed after curing the durable adhesive.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an adhesion method suitable for use in adhesion that requires temporary fixing, such as when adhering vertical surfaces or curved adherends. In particular, the present invention relates to an adhesive method using a combination of a fast-curing adhesive and a durable adhesive.

[Conventional technology]

JP-A-63-118387 discloses an adhesion method that uses a cyanoacrylate adhesive and a two-component epoxo resin in combination. That is, a method is disclosed in which the fast curing properties of a cyanoacrylate adhesive are used for temporary fixing, and the adhesive durability of a two-component mixed epochino resin is used for permanent adhesion.

The two-component adhesive used in this prior art is composed of a mixture containing an epoxy resin component and another compound containing an epoxy resin curing agent component. An anionic polymerization promoter is added to at least one of both formulations.

Furthermore, an adhesion method is also known in which a cyanoacrylate adhesive is used as a fast-curing adhesive and an adhesive mainly composed of a silicone-modified polymer is used as the main adhesive. In other words, temporary fixing is performed using the fast-curing properties of a cyanoacrylate adhesive, main adhesion is performed using an adhesive mainly composed of a silicone-modified polymer, and the elasticity of the adhesive that uses the silicone-modified polymer as a living body is used. A bonding method that can absorb vibrations, shocks, etc. is known.

By using the above-mentioned method of using a fast-curing adhesive and a durable adhesive in combination, the adherend can be temporarily fixed with the fast-curing adhesive. In other words, for example, when bonding an adherend surface that extends vertically or a curved adherend object, it is normally necessary to use another device to fix the adherend object immediately after bonding, but as described above, If a fast-curing adhesive is used, the adherend can be temporarily fixed, so the use of other tools can be omitted.

[Problem to be solved by the invention]

However, in all of the above prior descriptions, cyanoacrylate adhesives are used as fast-curing adhesives for temporary fixing. Although cyanoacrylate adhesives have a fast curing speed, they are easily degraded by water, heat, light, and the like. Therefore, when applied to adhesive parts that require long-term reliability and durability, the adhesive strength of the parts temporarily fixed by the cyanoacrylate adhesive gradually decreases,
Adhesion defects may occur. In other words, the problem is that the parts that are glued with a durable adhesive are firmly glued, but the parts that are glued with a cyanoacrylate adhesive for temporary fixing become adhesive defects, which impairs the reliability of the adhesion. was there.

Further, when the adherend is contaminated with oil, there is also the problem that a predetermined adhesive strength cannot be obtained unless the adherend is thoroughly cleaned.

Therefore, it is an object of the present invention to not only be able to temporarily fasten adherends in a short time without using any other equipment after bonding, but also to have sufficient adhesive performance after bonding, especially shear adhesive strength. Another object of the present invention is to provide an adhesion method that can exhibit peel adhesion strength, impact adhesion strength, long-term reliability and durability of adhesion.

[Means to solve the problem]

The bonding method of the present invention uses a fast-curing adhesive and a durable adhesive in combination. 2fi separately applied contact curing acrylic adhesive was used as the adhesive, and 2ff was used as the durable adhesive.
7. It is characterized by using a mixed adhesive.

In particular, the two-component adhesive is composed of a first composition containing a modified silicone resin and a uboxy resin curing agent, and a second composition containing an epoxy resin and a modified silicone resin curing agent. things are used.

([) Contact acrylic adhesive A In the present invention, as a fast-curing adhesive, a two-component separate application type contact-curing acrylic adhesive A, that is, referred to as a second generation acrylic thread binding agent, is used. A suitable adhesive is used.

Specifically, this adhesive A is thermoplastic rubber, (meth)
A first formulation (a,) comprising an acrylic acid ester and an organic peroxide as essential components and an organic i! ! ! It is used in combination with the second formulation (a2) containing an oxide decomposition accelerator as an essential component. That is, the first formulation (a,) is applied to the - side adhesion surface, and the second formulation (a2
) is a two-component separate application type adhesive that performs adhesion by applying and bonding the other adhering surface.

In this two-component separately applied contact-curing acrylic adhesive A, the (meth)acrylic acid ester partially graft-polymerizes to the thermoplastic rubber during adhesion, so the peel adhesive strength
A bonded portion having excellent shear bond strength and impact bond strength can be formed. Further, sufficient adhesive strength can be obtained even if the adhered surface is contaminated with oil.

That is, the bonding method of the present invention uses the above-mentioned two-component separately applied contact-curing acrylic adhesive A as a fast-curing adhesive for temporary fixing, thereby replacing the conventional cyanoacrylate adhesive. This method is characterized by overcoming problems in the method, namely, a decrease in adhesive strength at temporary fixing portions and the occurrence of adhesive defects.

Tsuchizawa! Possible! Rikkato The first composition (al) of the contact-curing acrylic adhesive A used in the bonding method of the present invention contains a thermoplastic rubber, and examples of such thermoplastic rubber include: Natural rubber, polychloroprene rubber, acrylonitrile-butadiene copolymer rubber, ethylene-propylene copolymer rubber, chlorosulfonated polyethylene, isobutylene-isoprene copolymer rubber, polyisoprene rubber, polyphtadiene rubber, or styrene-butadiene copolymer rubber, etc. Can be mentioned.

Examples of (meth)acrylic esters blended in the first formulation (a) include alkyl (meth)acrylates,
Hydroxyacrylic (meth)acrylate, glinosyl (
meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri( meth)acrylate, trimethylolethanetri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, polyester(meth)acrylate obtained by reaction of methacrylic acid, glycol, and polybasic acid, epoxy compound and (meth)acrylic Epoxy methacrylate obtained by reaction with acid, amide (meth)acrylate obtained by reacting polybasic acid with amino alcohol and then reacting with (meth)acrylic acid, hydroquine alkyl (meth)acrylate and polyisocyanate. Examples thereof include urethane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and diethylaminoethyl (meth)acrylate obtained by reacting with a compound.

In these descriptions, (meth)acrylic is used to include both methacrylic and acrylic. Moreover, the above (meth)acrylic esters may be used alone, or a mixture of two or more (meth)acrylic esters may be used.

Mountain) First formulation of organic peroxide contact curing acrylic adhesive A (al)
Examples of organic peroxides contained in Milperoxide, acetyl peroxide, lauroyl peroxide, 3,5.5-trimethanehexanol peroxide and the like can be mentioned. These organic peroxides may be used alone or in combination of two or more.

The above organic peroxide is blended to function as a catalyst during the polymerization of (meth)acrylic ester.

iv Oxide decomposition accelerator Second formulation of contact curing acrylic adhesive A (a2)
contains a decomposition accelerator for the organic peroxide described above, and examples of the decomposition accelerator for the organic peroxide include tetramethylthiourea, ethylaldehyde-aniline condensate,
Examples include dimethylaniline and dimethylparatoluidine.

■) Blending ratio of the first compound (al) In the first compound (a,), the above-mentioned thermoplastic rubber, (meth)acrylic acid ester, and peroxide are mixed in the following proportions. It is blended.

That is, 10 to 100 parts by weight of thermoplastic rubber and 0.1 to 5 parts by weight of organic peroxide are blended with respect to 100 parts by weight of (meth)acrylic ester.

vi) the second formulation (a2);
In a2), the organic peroxide decomposition accelerator described above is blended as a main component. It is sufficient if it is blended in excess with respect to the oxide.

■ 2Pa A Adhesive B The durable adhesive used in the adhesive method of the present invention is:
It is a two-component mixed adhesive B, specifically a first formulation (bl) containing a modified silicone resin and an epoxy resin curing agent.
) and a second formulation (b2) containing an epoxy resin and a modified silicone resin curing agent.

1) Modified silicone resin The modified silicone resin blended in the first formulation (b) has a main chain essentially of -R'-0-1 [wherein R1 has 1 to 4 carbon atoms] is 2
It is a polyether containing chemically bonded repeating units represented by [alkylene group] and having a functional silicon group at the end. - Examples include modified silicone polymers having a molecular weight of 2,000 to 16,000 and represented by the chemical formula below.

CH.

(CH30)-5i-CL-CL-CL-0-(CH-
CHz-0 taste-3-m -4CHzOh-C)Iz-CHz-CHz-5i-n
OcHs) -3-a However, R is an alkyl group such as a methyl group, m is an integer of O-2, and a is an integer of 1-3.

11 Epoxy The first formulation (bl) contains an epoxy resin curing agent along with the above-mentioned modified soric resin. As the epoxy resin curing agent, a wide variety of commonly used epoxy resin curing agents can be used, and there are no particular limitations. Examples of such epoxy resin curing agents include triethylenetetramine, diethylenetriamine, metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, isophoronediamine, 2.4.6-)lis(dimethylaminomethyl)phenol, and the like. Examples include compounds such as amines; tertiary amines; polyamide resins; imidazoles; and carboxylic anhydrides such as phthalic anhydride.

The second formulation (b2) of the 2-component adhesive B, which is a two-component mixture of 4 and 2-component adhesive B, contains an epoxy resin as a soil component. Examples of epoxy resins that can be used include bisphenol A, etc. Examples include a type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, and various alicyclic type epoxy resins. However, the epoxy resins that can be used are not limited to these, and a wide variety of epoxy resins known in -a can be used.

(2) Sifcon As a curing agent for curing the modified silicone resin contained in the above-mentioned formulation (bl), a tin carboxylate such as dibutyltin dilaurate or dibutyltin phthalate can be used.

A in vB When the first formulation (bl) and the second formulation (b,) are mixed, the modified silicone resin and the modified silicone resin curing agent react, and the epoxy resin hardens. The agent and epoxy resin react, and the adhesive gradually hardens. Therefore, the blending ratios of each compound (bt) and (bt) are as follows:
It may be selected as appropriate in the ratio necessary for curing the seed resin.

1""2 (filling discussion) The contact curing type acrylic adhesive A and the two-component mixed adhesive B described above may contain appropriate fillers and plasticizers.

Fillers that can be used include reinforcing fillers such as silica, precipitated silica, anhydrous silicic acid, hydrated silicic acid and carbon flanks: russoum carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide,
Fillers such as bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil and solas balloons; fibrous fillers such as asbestos, glass fibers and filaments.

Examples of plasticizers that can be added include phthalate esters such as dioctyl phthalate, dibutyl phthalate, or butylbenzyl phthalate; aliphatic dibasic acid esters such as dioctyl adipate, isodecyl succinate, and dibutyl sebacate. ; glycol esters such as diethylene glycol dibenzoate or pentaerythritol ester; aliphatic esters such as methyl niacetyl phosphorus; phosphoric acid esters such as tricresyl phosphate, trioctyl phosphate or octyldiphenyl phosphate; epoxy Epoquine plasticizers such as hydrogenated soybean oil or benzyl epoxystearate; and chlorinated paraffins may be mentioned, and these plasticizers can be optionally used alone or in the form of a mixture of two or more.

[Effect]

In the bonding method of the present invention, a two-liquid separation type contact curing acrylic adhesive A and 2m, and a mixed adhesive B are used in combination.

First, in the contact curing acrylic adhesive A, the first compound (al) and the second compound (a2) come into contact with each other immediately after adhesion, thereby starting polymerization of the (meth)acrylic ester, The adherend can be temporarily fixed in just a few minutes. Therefore, when adhering to a surface that extends vertically or when adhering a curved adherend against the warp, there is no need to use other equipment to hold down the parts to be adhered, or even if it is done, it only takes a short time. This makes it easy to carry out bonding work.

Furthermore, contact-curing acrylic adhesives have higher shear adhesive strength, peel adhesive strength, and
Since it has excellent impact adhesive strength and long-term reliability, no adhesive defects will occur even after a long period of time. Not only that, but also when used on an adhered part to which oil is attached, temporary fixing can be performed reliably.

Furthermore, in the bonding method of the present invention, following the temporary fixing using the contact-curing acrylic adhesive side, a two-component mixed adhesive B is applied.
The main adhesion is carried out using a method of applying adhesives, a cured adhesive with excellent durability is provided, and the adhesion is completed.

〔Effect of the invention〕

Therefore, according to the bonding method of the present invention, there is no need to use other tools when bonding adherends together, or even if they are used, they only need to be pressed for a very short time, so temporary fixing can be achieved in a short time. The durable adhesive can exhibit sufficient adhesive performance after curing. Therefore, a suitable adhesion method is provided when temporary fixing is required, such as when adhering to an adherend surface extending in the vertical direction or when adhering a warped adherend.

[Explanation of Examples]

As contact curing acrylic adhesive A, three types of sample numbers 1 to 3, consisting of the first formulation (a,) and second formulation (a2) shown in Table 1 below, were prepared. . In addition, all the numerical values in each composition are shown in parts by weight.

For comparison, methyl-
An α-cyanoacrylate adhesive was prepared as sample number A-4.

(Hereinafter, blank spaces) Table ■ In Table 1, NBR/N1pol DN401 Chlorosulfonated polyethylene...Vipanshi 20 (manufactured by DuPont) (manufactured by Nippon Zeon) Chlorobrene...Denka chloroprene A-100 ( i
! (manufactured by Kikagaku Co., Ltd.) Butyraldehyde aniline condensate: Tsukusera 8 (manufactured by Iriuchi Shinko Co., Ltd.) was used, respectively.

On the other hand, as the two-liquid mixed adhesive B, adhesives having four types of compositions B-1 to B-4 shown in Table 2 below were prepared.

Table 2 In Table 2, Cylyl 5B25...Modified silicone resin (manufactured by Kanebuchi Kagaku Kogyo Co., Ltd.) DMP-30...Tertiary amine tomide 280...Product name of polyamide made by Fuji Kasei Kogyo Co., Ltd. Epicote 828. Epicoat 815: Trade name of epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.

11 Back armpit contact curing acrylic adhesives A-1 to A-3 and methyl-α-cyanoacrylate adhesive A-4, and two-component mixed adhesives B-1 to B-4 as shown below. Adhesion was performed using the combinations shown in Table 3.

The adhesion was carried out by gluing a ceramic tile 2 measuring 45 x 45 x 6 m and weighing 30 g to a vertically extending slate plate 1, as shown in Figures 1 (a) and (b). .

That is, the first composition (a,) of adhesives A-1 to A-3 or the methyl-α-cyanoacrylate adhesive A-4 is placed in a circle with a diameter of 10 at the center of one main surface of the ceramic tile 2. , and apply 2 around the tangent circle (area with hatched dots).
A liquid mixed adhesive Bl was applied. On the other hand, adhesives A-1 to A- are placed in a circle with a diameter of 10 squares at the center of one main surface of the slate board 1.
A second formulation (a2) of No. 3 had been applied. Thereafter, the ceramic tile 2 was adhered to the slate plate 1, and the time until the ceramic tile 2 stopped shifting or falling even when the hand was removed was measured. The results are also shown in Table 3.

Furthermore, after adhesion, it was left at 20° C. for 7 days, and the shear strength of the bonded portion was measured. The results are also shown in Table 3.

Table 3 *) There were some uncured parts.

Originally, A-1 is easily affected by the polymerization inhibition effect of 02, but
When B-1 is used, it is difficult to receive this effect because it is cut off from the outside air. Therefore, in the example surrounded by B-1, no uncured state occurs.

The above-mentioned contact curing acrylic adhesive A-1 and methyl-α-cyanoacrylate adhesive A-4, and 2M mixed adhesive B-1-B-4 are shown in Table 4 below. Adhesion experiment 2 was conducted using the combinations shown in . As shown in Figure 2, the adhesive was attached to mild steel plates 3 and 4 with a width of 25 m and a thickness of 1.6 m.
was prepared, and a 25 m long area at one end of the other mild steel plate 3 was used as the bonding area. Applying the first formulation of adhesive A-1 (al) or methyl-α-cyanoacrylate adhesive A-4 in a 10 aa++ diameter circle in the center of the adhesive area;
Two-component mixed adhesives B-1 to B-4 were applied to the surrounding adhesive area (area marked with dotted hunting). In addition, on the other mild steel plate 4 side, adhesive A
A second formulation (a2) of -1 was applied.

These mild steel plates 3 and 4 were bonded together as shown by the arrows in the figure, and the shear strength was measured after being left at a temperature of 23°C for 7 days. The results are shown in Table 4.

In addition, in this adhesion experiment 2, experiments were conducted both in the case where the mild steel plate 3.4 was degreased with acetone in advance, and in the case where it was bonded after being degreased with acetone and coated with rust preventive oil. As the rust preventive oil, Oil Coat 7 (manufactured by Idemitsu Petrochemical Co., Ltd.) was used.

Further, the shear strength was also measured 7 days after immersion in hot water at 80° C. after adhesion. The results are also shown in Table 4.

(The following is a blank space) Table 4 (Units are kg/a!) As is clear from Table 4, the combination of comparative examples, that is, the bonding method using a cyanoacrylate adhesive as a fast-curing adhesive, It can be seen that the shear strength is significantly reduced when rust preventive oil is attached, and the shear strength is also significantly reduced when immersed in hot water.

On the other hand, in the combination of Examples, the shear strength is not so great even if the rust preventive oil is attached to the surface of the mild steel plate 3.4 or even if it is immersed in hot water for 7 days. It can be seen that there is no decline.

[Brief explanation of the drawing]

1A and 1B are perspective views for explaining the bonding method in Adhesion Experiment 1, and FIG. 2 is a perspective view for explaining the bonding method in Adhesion Experiment 2, respectively. In the figure, l is a slate board, 2 is a ceramic tile, 3.4
indicates a mild steel plate. Figure 1 (d) Patent applicant: Tansui Chemical Industry Co., Ltd. (Koshi Co., Ltd.)

Claims (2)

[Claims] (1) In a method in which a quick-curing adhesive and a durable adhesive are used in combination, the fast-curing adhesive is used for temporary fixing and the durable adhesive is used for main bonding. An adhesion method characterized in that a separately applied contact curing acrylic adhesive is used and a two-component mixed adhesive is used as the durable adhesive. (2) The two-component adhesive is composed of a first compound containing a modified silicone resin and an epoxy resin curing agent, and a second compound containing an epoxy resin and a modified silicone resin curing agent. The adhesion method according to claim 1, characterized in that: