JPH11349912A - One-component type elastic adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an one-component type elastic adhesive excellent in balance of curing speed and storing stability having excellent adhesive manifestation to wet surface by compounding Portland cement as a filler to an one-component type epoxy resin based adhesive obtained by compounding a modified silicone resin to an epoxy resin. SOLUTION: This adhesive comprises (A) 100 pts.wt. of the epoxy resin, (B) 10 to 500 pts. of the modified silicone resin and (C) 10 to 200 pts. of the Portland cement. Preferably compounded with 50 to 200 pts. of the component B and 20 to 100 pts. of the component C. The preferable molecular weight of the component A is 300 to 1000. Poly(methyldimethoysilily ether) is cited as the component B. On the point of bestowing thixotropy, a surface processed calcium carbonate is preferably compounded as the filler other than the component C. Dehydrating agent, curing agent for the epoxy resin, curing catalyst for the modified silicone resin and a silane compound is preferably compounded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-component elastic adhesive having a good balance between curing speed and storage stability, and having excellent adhesiveness even on a wet surface.

[0002]

2. Description of the Related Art One-part epoxy resin adhesives, which have been used as adhesives for concrete and mortar surfaces at construction sites and the like, do not have sufficient adhesiveness. The adhesion to the surface was not satisfactory. Therefore, a one-component elastic adhesive excellent in adhesiveness to a wet surface is desired from the viewpoint of shortening the construction period. In addition, a one-pack type epoxy resin-based adhesive in which a modified silicone resin is mixed with an epoxy resin is known, but its wet surface adhesiveness is poor, so that the construction is restricted.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a one-component elastic adhesive which has a good balance between curing speed and storage stability, and has excellent adhesiveness even on a wet surface. I do.

[0004]

Means for Solving the Problems The inventor of the present invention uses Portland cement as a part of a filler for a one-pack type epoxy resin-based adhesive in which a modified silicone resin is blended with an epoxy resin, so that adhesion to a wet surface is greatly improved. It was found that the present invention was improved, and the present invention was completed. That is, the present invention provides a one-component elastic adhesive containing at least 100 parts by weight of an epoxy resin, 10 to 500 parts by weight of a modified silicone resin and 10 to 200 parts by weight of Portland cement. The content of the modified silicone resin is 50 to
Preferably, the content is 200 parts by weight, and the content of the Portland cement is 20 to 100 parts by weight.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The epoxy resin used in the present invention is:
Any epoxy resin having a molecular weight of 300 to 2,000 having two or more epoxy groups may be used. Examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, modified epoxy resin obtained by hydrogenating these, glycidyl ester. Type epoxy resin, novolak type epoxy resin, urethane modified epoxy resin having a urethane bond, nitrogen-containing epoxy resin epoxidized metaxylenediamine or hydantoin, polybutadiene, or rubber-modified epoxy resin containing NBR, and the like. It is not limited to these. Further, the molecular weight is preferably 300 to 2000,
300-1000 is more preferred. If the molecular weight of the epoxy resin is less than 300, hardness is hardly developed, and
Above, the viscosity increases. If the number of epoxy groups is less than 2, the hardness is hardly developed.

The modified silicone resin used in the present invention has the following formula (1)

Embedded image (Wherein, R ¹ is a monovalent hydrocarbon group having 1 to 12 carbon atoms;
² is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 to 2. ) Is a polyether polymer having a hydrolyzable silicon functional group at the terminal. More specifically, poly (methyldimethoxysilyl ether) and the like are exemplified.
One of these polyether polymers may be used alone, or two or more thereof may be used in combination. The modified silicone resin is cured by moisture in the air in the presence of the modified silicone resin catalyst.

The amount of the modified silicone resin used is 10 to 500 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the epoxy resin. If the amount exceeds 500 parts by weight, the adhesiveness deteriorates, and if it is less than 10 parts by weight, the flexibility of the cured epoxy resin deteriorates. In the present invention, the incorporation of the modified silicone resin is important for imparting flexibility to the cured epoxy resin.

[0008] In the present invention, Portland cement is blended as at least a part of the filler. By replacing a part of calcium carbonate, which has been conventionally used as a filler, with Portland cement, the adhesiveness when the wet surface is used as the construction surface is improved, and the adhesiveness after curing is also good. The amount of Portland cement is 10 to 200 parts by weight, preferably 20 to 100 parts by weight, per 100 parts by weight of the epoxy resin. If the amount is less than 10 parts by weight, the wet adhesion deteriorates, and if it exceeds 200 parts by weight, the thixotropy may decrease, and the storage stability deteriorates.

As a filler other than Portland cement, the present invention optionally includes surface-treated calcium carbonate,
Heavy calcium carbonate may be blended. Heavy calcium carbonate may be completely replaced with Portland cement, but surface-treated calcium carbonate is preferably blended from the viewpoint of thixotropy imparting, especially when the vertical surface is used as the construction surface, the surface-treated calcium carbonate is blended. More preferred.

In addition, the adhesive of the present invention preferably contains a dehydrating agent, an epoxy resin curing agent, a modified silicone resin curing catalyst, and further contains a silane compound. The silane compound used in the present invention is an aminoalkylalkoxysilane, an epoxyalkylalkoxysilane, a mercaptoalkylalkoxysilane, or an alkoxysilane derivative that is a copolymer thereof.
Specific examples include aminopropyltrimethoxysilane, a reaction product of aminopropyltrimethoxysilane and vinyltrimethoxysilane, and commercially available products can be used.

The curing agent for the epoxy resin used in the present invention is not particularly limited as long as it is a one-pack curing agent, but ketimine represented by the following formula (2) is preferable.

Embedded image (Wherein, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a functional group having a molecular weight of 300 or less including carbon, hydrogen and oxygen, X ¹ and X ² is an alkylene group having 2 to 6 carbon atoms or 6 to 1 carbon atoms.
2 is a non-adjacent arylene group, and m is an integer of 0 or more. Ketimine is stably present in the absence of moisture, but functions as a curing agent for epoxy resins because it becomes a primary amine due to moisture. This enhances the storage stability of the one-component elastic adhesive of the present invention and improves the curability during use. As such ketimines, 1,
2-ethylenebis (isopentylideneimine), 1,2
Hexylenebis (isopentylideneimine), 1,2
Propylene bis (isopentylideneimine), p, p
-Biphenylenebis (isopentylideneimine), 1,
2-ethylenebis (isopropylideneimine), 1,3
-Propylene bis (isopropylidene imine), p-phenylene bis (isopropylidene imine), (diethylene triamine methyl isobutyl ketone polycondensate) phenyl glycidyl ether adduct and the like. The amount of ketimine used is 1 to 6 with respect to 100 parts by weight of the epoxy resin.
0 parts by weight, preferably 10 to 30 parts by weight. If the amount is less than 1 part by weight, the curing rate becomes slow, which is not preferable. On the other hand, if the amount exceeds 60 parts by weight, the epoxy resin is easily cured at the time of storage, and storage stability is unfavorably reduced.

The modified silicone resin curing catalyst used in the present invention is a catalyst for curing the above modified silicone resin, and more specifically, a tin compound such as dibutyltin oxide or a carboxylic acid such as lead octylate. Metal salts, amine salts such as dibutylamine-2-ethylhexoate and the like are used. The amount of the modified silicone resin curing catalyst used is 0.1 to 100 parts by weight of the modified silicone resin.
Preferably, the amount is from 10 to 10 parts by weight.

The present invention may further contain, if necessary, an antioxidant such as titanium oxide, a pigment such as carbon, and other additives such as a surfactant, a viscosity modifier, a solvent, and a plasticizer. These are appropriately added according to the use of the adhesive of the present invention.

The one-component elastic adhesive of the present invention comprises additives such as the epoxy resin, modified silicone resin, Portland cement, calcium carbonate, epoxy resin curing agent, modified silicone resin curing catalyst, silane compound and dehydrating agent. , Manufactured by mixing according to a conventional method, and stored in a sealed container. The one-component elastic adhesive thus produced can be applied to a wet construction surface such as mortar or concrete to exhibit good adhesiveness, but other properties are not impaired. It goes without saying that the adhesive of the present invention can also be used on a dry surface.

[0015]

EXAMPLES Production of one-component elastic adhesives (Examples 1 to 4
And Comparative Example 1) epoxy resin (YD-128, manufactured by Toto Kasei Co., Ltd.)
Poly (methyldimethoxysilylethyl ether) (MSP-S203, manufactured by Kaneka Corporation) as a modified silicone resin, surface-treated calcium carbonate (Calfine 20)
0, Maruo Calcium), Portland Cement (Portland Cement, Nippon Cement), Heavy Calcium Carbonate (Snowlight SSS, Shiraishi Calcium)
At room temperature using a high-viscosity mixing stirrer (20 To
rr or less), and the epoxy resin curing agent (Epicure H)
-3, manufactured by Yuka Shell Co., Ltd.) and dioctyl phthalate solution of dibutyltin oxide (No. 918, manufactured by Sankyo Synthetic Co., Ltd.) as a modified silicone resin curing catalyst were added in the same manner, followed by stirring under reduced pressure. An example one-component elastic adhesive was prepared. The compositions of the adhesives of Examples and Comparative Examples are shown in Table 1 below.

Evaluation The following items were evaluated for the adhesives of the above Examples and Comparative Examples. The viscosity, thixotropy and tack-free time were measured immediately after production and after standing at 60 ° C. for 3 days. Viscosity: JIS K6833 using a single cylinder rotational viscometer
Was measured at 1 rpm. Viscosity: JIS K6833 using a single cylinder rotational viscometer
Was measured at 10 rpm. Thixotropy: The value of viscosity / viscosity was taken as the thixo index. Tack free time: The above composition was left in an atmosphere of 20 ° C. and 60% RH, and the time required for the surface of the composition to cure was measured.

Further, the adhesives of Examples and Comparative Examples were applied to the wet mortar and the tiles as adherends, allowed to stand at 20 ° C. for 28 days, and then subjected to a Kenken-type tensile test. The strength (N / mm ² ) and the destruction state were evaluated. The destruction state was visually classified as follows. cf: cohesive fracture (mortar fracture) Tcf: thin layer fracture (adhesive layer fracture) Af: interface fracture ((mo) interface between mortar and adhesive,
(T) Interface between tile and adhesive) The evaluation results are shown in Table 1 below.

[0018]

[Table 1]

[0019]

According to the present invention, it is possible to provide a one-component elastic adhesive having improved storage stability and improved curing speed with improved adhesion to a wet surface without changing other physical properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C04B 24:28)

Claims (2)

[Claims] A one-component elastic adhesive containing at least 100 parts by weight of an epoxy resin, 10 to 500 parts by weight of a modified silicone resin and 10 to 200 parts by weight of Portland cement. 2. The content of the modified silicone resin is 50 to 50.
2. The one-component elastic adhesive according to claim 1, wherein the amount is 200 parts by weight, and the content of the Portland cement is 20 to 100 parts by weight.