JP3043088B2 - Adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition containing an epoxy resin and a modified silicone compound having a functional group capable of reacting with an epoxy group and a reactive silicon group in one molecule.

[0002]

2. Description of the Related Art An adhesive having rubber elasticity after curing can absorb distortion caused by an external force, and is therefore suitable for attaching a structural material such as a tile.

As such an adhesive, for example, JP-A-61-268720 discloses a rubber-based organic polymer having at least one reactive silicon group in a molecule and a modified silicone compound with respect to an epoxy resin . Has been proposed. It is stated that by adopting such a composition, the brittleness of the epoxy resin cured product is improved, and a flexible cured product is thereby obtained.

An adhesive composition which gives a cured product having flexibility also has the above-mentioned modification with respect to an epoxy resin.
A compound containing a synthetic silicone compound is known (Katsuhiko Isayama, Adhesion, 32 (4), 149 (1988)). Such adhesive compositions include heavy calcium carbonate, colloidal calcium carbonate, hydrophobic finely divided silica and / or
It is known that sagging at the time of applying an adhesive can be prevented by blending various fillers such as an organic anti-sagging agent.

However, epoxy resin and modified silicone
In the conventional formulation example of the adhesive composition containing the compound, the sagging of the adhesive itself at the time of bonding is prevented, but when a structural material such as a tile is attached to the adherend extending in the vertical direction, However, the structural material immediately shifted downward, and was unsuitable as an adhesive for on-site construction.

However, if a larger amount of filler is contained in the adhesive composition, it is possible to prevent displacement of a relatively heavy structural material such as a tile at the time of bonding. However, when the content of the filler is increased, the viscosity of the adhesive becomes extremely high, and when the two-part adhesive is adjusted, it becomes very difficult to mix and apply the adhesive, and the workability is increased. There was difficulty in terms. Further, when the content of the filler is increased, there is a problem that the flexibility after curing is lowered, and the advantage of adding the modified silicone compound , which gives the cured product flexibility, is impaired.

[0007]

SUMMARY OF THE INVENTION The inventor of the present invention
It has been found that the above-mentioned problems can be solved by mixing a specific filler at a specific ratio with the epoxy resin and the modified silicone compound , and the invention has been completed and a patent application has been filed earlier (Japanese Patent Application No. Hei 10-26139). 2-217295).

[0008] The adhesive composition of the present invention is a modified silicone
Relative to emissions Compound 100 parts by weight of an epoxy resin 30-7
0 parts by weight, 50 to 90 parts by weight of colloidal calcium carbonate,
20 to 50 parts by weight of heavy calcium carbonate, 2 to 8 parts by weight of an organic anti-sagging agent, 5 to 15 parts by weight of hydrophobic finely divided silica, and 0.5 to 3 parts by weight of an organotin catalyst, It is excellent in flexibility and durability, and does not cause displacement when a tile or the like is adhered to an adherend extending in the vertical direction.

However, if the cured product is exposed to hot water for a long time after bonding, the cured product tends to deteriorate and become hard and brittle. Then, such a cured product has a problem that a structure such as a tile which is cracked and adhered by an impact or the like is easily peeled off.

[0010] In view of these points, the present invention provides an adhesive composition as described above, which maintains flexibility without aging even when exposed to hot water or the like. Aim.

[0011]

The adhesive composition of the present invention is an adhesive composition containing a modified silicone compound and an epoxy resin, and comprises the following three inventions.

[0012] The adhesive composition of the first invention has a structure in one molecule.
Amino groups, mercapto groups, epoxy groups that can react with epoxy groups
At least one functional group selected from a xy group and a carbonyl group;
And a silicon atom to which a hydrolyzable group or a hydroxyl group is bonded
Modified silicone compound having reactive silicon group
(Hereinafter, referred to as modified silicone compound), an epoxy resin, colloidal calcium carbonate, heavy calcium carbonate, organic
It is characterized by including a mechanical anti-sagging agent, hydrophobic finely divided silica, an organotin catalyst, and a blocked isocyanate urethane prepolymer.

The adhesive composition of the second invention is characterized in that the adhesive composition of the second invention contains a styrenated phenol. Further, the adhesive composition of the third invention is characterized in that an amino group capable of reacting with an epoxy group in one molecule.
Group, mercapto group, epoxy group, carbonyl group
One or more functional groups and a hydrolyzable or hydroxyl group
Having reactive silicon groups containing combined silicon atoms
Modified silicone compound (hereinafter referred to as modified silicone compound)
Hereinafter), epoxy resins, colloidal calcium carbonate, heavy calcium carbonate, organic-based anti-sagging agent, is characterized by comprising a hydrophobic fine silica powder, an organic tin catalyst and ketimine.

The metamorphic system used in these inventions
The silicone compound is a silicon compound containing a functional group capable of reacting with an epoxy group and a reactive silicon group in one molecule as described above. And, as the functional group capable of reacting with the epoxy group, an amino group, a mercapto group, an epoxy group,
Carboxyl groups . Further, the reactive silicon group means a group which can be crosslinked by a silanol condensation reaction containing a silicon atom to which a hydrolyzable group or a hydroxyl group is bonded, and is disclosed in, for example, JP-A-61-268720. And a methyldimethoxysilyl group as described above.

The modified silicone compound as described above is commercially available, specifically, as Cyril 5B25 or Cyril 5B30 manufactured by Kaneka Corporation. The epoxy resins used in these inventions are for increasing the strength of the adhesive after curing, and include epichlorohydrin-bisphenol A epoxy resin, epichlorohydrin-bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, and urethane modified epoxy resin. Resins and the like can be mentioned, but are not limited to these epoxy resins, and generally used epoxy resins can be widely used. In particular, from the viewpoint of reactivity upon curing, it is preferable to use an epoxy resin having a plurality of epoxy groups in one molecule.

It goes without saying that a curing agent for curing the epoxy resin may be blended. As such a curing agent, for example, polyethylene tetramine,
Examples include tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine, 2,4,6-tris (dimethylaminomethyl) phenol. When the adhesive composition of the present invention is constituted as a two-part adhesive, the above-mentioned curing agent is contained in the other agent different from the one agent in which the epoxy resin is mixed.

In the present invention, the colloidal calcium carbonate is used as a thickener, and examples thereof include fatty acid-based, silicic acid-based, and sulfonic acid-based ones. It is preferred to use calcium. And the preferred amount is modified
The amount is 50 to 90 parts by weight based on 100 parts by weight of the silicone compound. When the amount is less than 50 parts by weight, the effect of improving thixotropic properties is not sufficient, and when the amount exceeds 90 parts by weight, the durability of the cured product tends to decrease.

Further, heavy calcium carbonate is also intended to be used as a thickener, there can be used those various particle size, its preferred amount is a modified silicone compound 100
20 to 50 parts by weight with respect to parts by weight, and if less than 20 parts by weight, the effect of enhancing the thixotropic property of the epoxy resin is small,
If the amount exceeds 50 parts by weight, the viscosity becomes too high and the workability deteriorates. In order to increase the durability of the cured product of the adhesive, it is preferable that the heavy calcium carbonate particles have not been subjected to a surface treatment.

Organic anti-sagging agents are compounded to increase thixotropic properties and prevent sagging (dripping) of adhesives, and include vegetable polymerization oils, hydrogenated castor oils, fatty acid amide waxes and the like. Among them, a hydrogenated castor oil type is particularly preferably used. If this anti-sagging agent is included in a large amount, the cured adhesive becomes brittle, so the modified silicone compound
It is preferably contained in the range of 2 to 8 parts by weight based on 100 parts by weight of the product .

The finely divided hydrophobic silica is blended to increase the strength of the cured product after bonding, and usually has a particle size of about 0.007 μm. Also,
As the hydrophobic finely divided silica, one whose surface is treated with a CH ₃ group, silicon oil, octylsilane, or the like is used.

If the amount of the hydrophobic silica is too large,
Since the cured product becomes too hard, it is preferred to be blended in the range of 5 to 15 parts by weight based on the modified silicone compound . The organotin catalyst is a catalyst for curing the modified silicone compound , and a butyltin laurate-based, butyltin phthalate-based catalyst or the like is used. The preferred compounding amount is 0.5 to 3 parts by weight with respect to 100 parts by weight of the modified silicone compound. When less than 0.5 part by weight, the effect of imparting thixotropic property is small, and when it exceeds 3 parts by weight, the effect of imparting thixotropic property is imparted. Tend to saturate and adversely affect the durability of the cured product after bonding.

The blocked isocyanate urethane prepolymer used in the first and second inventions is for imparting flexibility to the cured epoxy resin and improving hot water resistance. Then, the amount is strange
The amount is preferably about 4 to 40 parts by weight based on 100 parts by weight of the synthetic silicone compound . The reason is that if less than 4 parts by weight, the effect of imparting flexibility is small. This is because it has an adverse effect on the displacement prevention effect of the tile attached to the vertically extending adherend surface. Specifically, PRX manufactured by AC R
It is commercially available as -9187L or PRX-9188L.

In the two-part adhesive, the styrenated phenol used in the second invention is blended with the B agent (epoxy resin compound), and the viscosity of the B agent is adjusted by lowering the viscosity of the B agent. It is a non-reactive diluent that can be used to improve the workability when mixing with the agent A and improve the applicability of the mixture (adhesive). Further, it imparts flexibility to the cured product. It is desirable that the compounding amount be about 2 to 20 parts by weight based on 100 parts by weight of the modified silicone compound . Specifically, it is commercially available as D-512 manufactured by RC Corporation.

The ketimine used in the third invention is a compound represented by the following general formula (1) wherein the oxygen of the carbonyl group of the ketone is substituted with an imino group.

[0025]

Embedded image

In the formula, R ¹ , R ² , R ³ and R ⁴ are hydrogen, an alkyl group or phenyl group having 1 to 6 carbon atoms, and X is an alkylene group having 2 to 6 carbon atoms or an alkyl group having 6 to 12 carbon atoms. A non-adjacent arylene group is shown.

Specifically, it is commercially available as Yukyu Shell Epoxy Epicure H-3 or the like. Then, when the adhesive composition cures, ketimine is decomposed by water into ketones and primary amines, and this primary amine cures the uncured portion of the epoxy resin. If the amount is less than 1 part by weight per 100 parts by weight of the modified silicone compound , the amount is too small for the uncured portion of the epoxy resin, and sufficient effect is not obtained. Too large and not economical. Therefore, the amount of ketimine, denatured
The amount is preferably about 1 to 10 parts by weight based on 100 parts by weight of the corn compound .

In any of the inventions, the adhesive composition is usually prepared as a two-part adhesive mixed at the time of use. This agent A ( modified silicone compound compound)
And the preparation of agent B (epoxy resin formulation)
For example, the following composition is preferable.

Agent A Modified silicone compound 100 parts by weight Colloidal calcium carbonate 5 to 15 parts by weight Organic anti-sagging agent 2 to 8 parts by weight Hydrophobic finely divided silica 2 to 8 parts by weight Ketimine (third invention) 1 to 10 parts by weight Part B agent Epoxy resin 30 to 70 parts by weight Colloidal calcium carbonate 40 to 80 parts by weight Heavy calcium carbonate 20 to 50 parts by weight Hydrophobic finely divided silica 2 to 8 parts by weight Organotin catalyst 0.5 to 3 parts by weight Blocked isocyanate urethane pre Polymer (1st and 2nd inventions) 4 to 40 parts by weight Styrenated phenol (2nd invention) 2 to 20 parts by weight In the case of A agent and B agent blended in the above proportions, the structure of tiles and the like At the site where the materials are glued, the two agents can be mixed relatively easily. It is also possible to prepare such that the two agents only need to be mixed at a ratio of 1: 1 by volume. With such a mixing ratio, it is possible to easily measure the A agent and the B agent without weighing them on site. And can be used conveniently.

[0030]

Next, an embodiment of the present invention will be described. Example A of the first invention As Examples 1 to 5 and Comparative Examples 1 to 5, Agent A and Agent B were prepared at the ratios shown in Table 1.

The contents of each compounding agent in Table 1 are as follows. - Silyl 5B25, Silyl 5B30; modified silicone
Compound (Kanebuchi Chemical Industry Co., Ltd.) Epicoat 828; Bisphenol A-type glycidyl ether (Yukaka Epoxy Co., Ltd.) Tertiary amine (DMP-30); 2,4,6-tris (dimethylaminomethyl) phenol (Manufactured by Rohm and Haas) ・ Organic tin catalyst SB-65; dibutyltin dilaurate + dibutyltin oxide (manufactured by Sankyo Co., Ltd.) ・ Colloidal calcium carbonate; Whiten SB (manufactured by Shiraishi Industries) ・ Heavy calcium carbonate; cal Fine 200M (manufactured by Maruo Calcium Co., Ltd.)-Organic sagging inhibitor (Dispalon # 305); Castor oil-hardened oil (manufactured by Kusumoto Kasei Co., Ltd.)-Hydrophobic fine powder silica; Aerosil R-202 (manufactured by Nippon Aerosil Co., Ltd.)-Blocked isocyanate urethane pre Polymer; PR
X-9187L (manufactured by A.C.R. Co.) Further, Examples 1 to 5 and Comparative Examples 1 to 5 prepared as shown in Table 1
With respect to each of the two-part adhesives of No. 5, the A agent and the B agent were mixed at the ratio shown in Table 1 and used, and evaluated by the following method. The evaluation results are also shown in Table 1. (A) Two-liquid mixing property: A total of 400 g of the A agent and the B agent were placed on a plate, the two liquids were mixed with a spatula, and the mixing property was sensory evaluated. (B) Curing flexibility: A mixture of the A agent and the B agent is 70 mm ×
It was cast to a size of 40 mm × 2.5 mm in thickness, allowed to stand at room temperature for 2 days, cured and cured in a constant temperature bath at 50 ° C. for 2 days, and then the cured product was bent and its tearing state was evaluated organoleptically. . (C) Displacement of tiles: A mixture of Agent A and Agent B was applied to a vertically extending board, and the mixture was applied to the board at a rate of 1.2 kg / m ² using a 5 mm square dressing iron. , Then 60mm x 225mm x thickness 8mm, weight 2
Two 50 g tiles with back feet were stacked and bonded, and the slippage property in the initial state of bonding was visually evaluated. (D) flexibility after immersion in hot water;
It was cast to a size of 40 mm x 120 mm x 2.8 mm in thickness, left at room temperature for 2 days, cured in a 50 ° C constant temperature bath for 2 days, and then cured. It was immersed for a week, and the flexibility after the immersion and that without immersion were organoleptically evaluated. (E) elongation properties and tensile strength after immersion in hot water;
The cured product obtained in the same manner as in the case of the evaluation of flexibility was immersed in hot water under the same conditions.
The elongation (%) and the tensile strength (kg / cm ² ) were measured with a No. 3 dumbbell based on K-6301.

[0032]

[Table 1]

As Examples 2 to 10 of the second invention, Agents A and B were prepared at the ratios shown in Table 2, respectively.

The contents of each compounding agent other than those used in Examples 1 to 5 are as follows. Styrenated phenol; D-512 (manufactured by AC R) In addition, with respect to each of the two-part adhesives of Examples 6 to 10 prepared as shown in Table 2, A agent and B agent were used in the proportions shown in Table 2. The mixture was used and evaluated by the same method as described above. The evaluation results are also shown in Table 2.

For comparison, Comparative Examples 1 to 5 are shown again in Table 2.

[0036]

[Table 2]

As Third Invention Examples 11 to 15, Agents A and B were prepared at the ratios shown in Table 3, respectively.

The contents of each compounding agent other than those used in Examples 1 to 5 are as follows. Ketimine: Epicure H3 (manufactured by Yuka Shell Epoxy Co.) In addition, with respect to each of the two-pack adhesives of Examples 11 to 15 prepared as shown in Table 3, the agents A and B were mixed and used in the ratio shown in Table 3. Then, evaluation was performed in the same manner as described above. The evaluation results are shown in Table 3.

For comparison, Comparative Examples 1 to 5 are shown again in Table 3.

[0040]

[Table 3]

As is clear from Tables 1 to 3, Example 1
It can be seen that all of the adhesive compositions Nos. To 15 have good two-component mixing properties, excellent flexibility after curing, and almost no tile displacement. Moreover, even after immersion in hot water, the elongation was good and the flexibility was maintained.
On the other hand, the adhesive compositions of Comparative Examples 1 to 5 containing no blocked isocyanate urethane prepolymer, styrenated phenol or ketimine have a small elongation rate and a high hardness after immersion in hot water. And lost flexibility.

[0042]

As described above, all of the adhesive compositions of the first to third inventions have an appropriate thixotropic property and are excellent not only in flexibility after curing but also in tiles. Used to glue structural materials such as
The displacement of the structural material is unlikely to occur. In addition, even after the influence of hot water, the flexibility after curing is not lost,
Good adhesion is maintained over a long period.

Continuation of the front page (56) References JP-A-63-43986 (JP, A) JP-A-49-133432 (JP, A) JP-A-3-263478 (JP, A) JP-A-2-308877 (JP) JP-A-60-221419 (JP, A) JP-A-58-219218 (JP, A) JP-A-60-115819 (JP, A) JP-A-60-1006827 (JP, A) 3-192183 (JP, A) JP-A-4-168187 (JP, A) JP-A-55-75471 (JP, A) JP-A-1-272623 (JP, A) JP-A-4-1220 (JP, A) A) JP-A-60-228583 (JP, A) JP-A-4-100787 (JP, A) JP-A-50-28598 (JP, A) JP-A-52-134645 (JP, A) -5983 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 1/00-201/10 CA (STN) REGISTRY (STN) Patent file (PATOLIS)

Claims (3)

(57) [Claims] 1. A can react with the epoxy groups in a molecule Ami
Groups, mercapto groups, epoxy groups, and carbonyl groups
One or more functional groups and hydrolyzable groups or hydroxyl groups
Modified silicone compound having a reactive silicon group containing a bound silicon atom , epoxy resin, colloidal calcium carbonate, heavy calcium carbonate, organic anti-sagging agent, hydrophobic finely divided silica, organotin catalyst, and blocked isocyanate urethane An adhesive composition comprising a prepolymer. 2. The adhesive composition according to claim 1, comprising a styrenated phenol. 3. An amino group capable of reacting with an epoxy group in one molecule.
Groups, mercapto groups, epoxy groups, and carbonyl groups
One or more functional groups and hydrolyzable groups or hydroxyl groups
Including modified silicone compound having reactive silicon group containing bonded silicon atom , epoxy resin, colloidal calcium carbonate, heavy calcium carbonate, organic anti-sagging agent, hydrophobic finely divided silica, organotin catalyst and ketimine An adhesive composition comprising: