JPH06128548A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide a new adhesive composition which can stick a structural material such as a tile to an upright surface without allowing the stuck material to displaced is excellent in workability, and can give a cured product excellent in flexibility and durability. CONSTITUTION:The composition contains an epoxy resin and a silicon compound having an epoxy-reactive functional group and a reactive silicon group in the molecule, and comprises 100 pts.wt. silicon compound, 30-70 pts.wt. epoxy resin, 50-90 pts.wt. colloidal calcium carbonate, 20-50 pts.wt. heavy calcium carbonate, 2-8 pts.wt. organic antisagging agent, 5-15 pts.wt. hydrophobic fine silica powder, 0.5-3 pts.wt. organotin catalyst, and 1-5 pts.wt. lightweight glass balloons.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an adhesive composition containing an epoxy resin and a silicon compound having a functional group capable of reacting with an epoxy group in the molecule and a reactive silicon group (hereinafter referred to as a modified silicon compound). In particular, regarding the flexibility and durability, when a tile or the like is adhered to the adherend that extends in the vertical direction, deviation does not easily occur and the weight is further reduced to improve the workability of the comb-like iron used during construction. Agent composition.

2. Description of the Related Art An adhesive having rubber elasticity after curing can absorb strain when an external force is applied, and is therefore suitable as an adhesive for attaching structural materials such as tiles. An example of an adhesive composition that gives such a soft cured product is disclosed in JP-A-61-268720.

In this prior art, the brittleness of an epoxy resin cured product is obtained by blending an epoxy resin with a rubber organic polymer containing at least one reactive silicon group in the molecule and the above-mentioned modified silicone compound. It is described that the softness of the cured product is obtained.

Further, JP-A-4-100881 discloses that an adhesive composition of this type is used as an adhesive used for adhering a tile or the like to an adherend surface extending in the vertical direction.

In the adhesive composition containing the epoxy resin and the modified silicon compound, heavy calcium carbonate, colloidal calcium carbonate, hydrophobic fine powder silica and / or
Alternatively, it is known that dripping at the time of applying an adhesive can be prevented by adding various fillers such as an organic dripping inhibitor.

However, in the conventional compounding example of the adhesive composition containing the epoxy resin and the modified silicone compound, although the adhesive itself is prevented from sagging, the tile or the like is adhered to the adhered surface extending in the vertical direction. When the structural material of (3) was pasted, the tiles and the like immediately slipped downward, which was unsuitable as an adhesive for site construction.

[0006] However, if a larger amount of the filler is contained in the adhesive composition, it is possible to prevent the displacement of relatively heavy structural materials such as tiles at the time of adhesion.

However, when the content of the filler is increased, the viscosity of the adhesive becomes very high, and when it is prepared as a two-component adhesive, it becomes very difficult to mix and apply the adhesive, and the work becomes difficult. It was difficult in terms of sex. Furthermore, when the content of the filler is increased, the flexibility after curing is reduced. That is, there is a problem in that the advantage of blending the modified silicon compound, that is, imparting flexibility to the cured product, is lost.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems, and an object of the present invention is to provide a structural material such as a tile on a vertical surface when the structural material is adhered to an adherend. It is an object of the present invention to provide a novel adhesive composition that gives a cured product that is less likely to cause slippage, has excellent workability, and has excellent flexibility and durability.

[0009]

Means for Solving the Problems The inventors of the present invention have made an intensive study by mixing various fillers and diluents in various proportions with respect to an epoxy resin and a modified silicon compound, and as a result, have identified a specific filler and the like. It was found that the above-mentioned problems can be achieved by mixing in the ratio of, and the present invention has been completed based on this finding.

That is, the adhesive composition of the present invention is characterized by having the following specific composition in the adhesive composition containing the epoxy resin and the modified silicon compound (a). In the present invention, (b) epoxy resin 30 is added to 100 parts by weight of the above-mentioned (a) modified silicone compound.
~ 70 parts by weight, (c) colloidal calcium carbonate 50-9
0 parts by weight, (d) 20 to 50 parts by weight of heavy calcium carbonate, (e) 2 to 8 parts by weight of organic anti-sagging agent, (f) 5 to 15 parts by weight of finely divided hydrophobic silica, (g) organic tin catalyst 0 .5-
3 parts by weight and (h) 1 to 5 parts by weight of lightweight glass hollow spheres are blended.

The present invention will be described in detail below. The modified silicon compound (a) used in the present invention is, as described above, a silicon compound containing a functional group capable of reacting with an epoxy group and a reactive silicon group in one molecule, and has the adhesive composition of the present invention. It is added in order to give flexibility to the cured product obtained from the product.

The functional group capable of reacting with the epoxy group includes
Examples thereof include an amino group, a mercapto group, an epoxy group and a carboxyl group.

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. As such a group, for example, a methyldimethoxysilyl group disclosed in JP-A-61-268720 is used.

As the modified silicon compound (a),
For example, the compound represented by the following structural formula may be mentioned.
It should be noted that this molecule contains one or more NH ₂ groups, and in order to show this, (to NH ₂ ) is described below in the structural formula.

[0015]

[Chemical 1]

Commercially available products of the above-mentioned modified silicon compound are, specifically, "Cyril 5B2" manufactured by Kanegafuchi Chemical Co., Ltd.
5 "or" Cyryl 5B30 "(molecular weight 5,000 to
10000) and the like.

The adhesive composition of the present invention contains an epoxy resin (b) in order to enhance the strength of the adhesive after curing. Epoxy resin (b) used in the present invention
Examples thereof include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, and urethane-modified epoxy resin, but are not limited to these epoxy resins and are generally used. The widely used epoxy resin can be used.

Among these epoxy resins (b), it is particularly preferable to use an epoxy resin having a plurality of epoxy groups in one molecule from the viewpoint of reactivity during curing.

As a curing agent for curing the epoxy resin (b), polyethylene tetramine, tetraethylene pentamine, diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine, 2,4,6-tris ( Dimethylaminoethyl) phenol and the like can be mentioned.

In the present invention, the above epoxy resin (b)
If the compounding amount of the above is small, the elongation of the cured product will be large, and if it is too large, the flexibility of the cured product will be lost.

In the case where the adhesive composition of the present invention is constituted as a two-component adhesive, the above-mentioned epoxy resin curing agent is contained in the other agent different from the one agent in which the epoxy resin is blended. To be done.

In the adhesive composition of the present invention, colloidal calcium carbonate (c) is blended as a thickener in the above-mentioned specific ratio. Colloidal calcium carbonate that can be used (c)
Examples thereof include fatty acid-based, silicic acid-based, sulfonic acid-based, and the like. In order to enhance thixotropy, it is preferable to use fatty acid-based colloidal calcium carbonate.

In the present invention, if the compounding amount of the colloidal calcium carbonate (c) is small, the thixotropic improvement effect is not sufficient, and if the compounding amount is large, the durability of the cured product decreases, so 100 parts by weight of the modified silicon compound (a) is used. 5 for department
It is limited to 0 to 90 parts by weight.

In the adhesive composition of the present invention, heavy calcium carbonate (d) is blended as a thickener, and the heavy calcium carbonate (d) having various particle diameters can be used. . Further, in order to enhance the durability of the cured adhesive, it is preferable to use heavy calcium carbonate that has not been surface-treated.

In the present invention, if the blending amount of the above-mentioned heavy calcium carbonate (d) is small, the thixotropic effect is small, and if the blending amount is too large, the viscosity becomes too high. Therefore, relative to 100 parts by weight of the modified silicon compound (a). 20-50
Limited to parts by weight.

In the adhesive composition of the present invention, an organic anti-sagging agent (e) is added in order to enhance thixotropy and prevent sagging of the adhesive. Examples of the organic anti-sagging agent (e) that can be used include vegetable polymerized oil-based, hydrogenated castor oil, fatty acid amide wax-based, and the like, but hydrogenated castor oil-based is preferable for enhancing thixotropy.

In the present invention, when the amount of the organic anti-sagging agent (e) is increased, the cured product becomes brittle, so the amount is limited to 2 to 8 parts by weight per 100 parts by weight of the modified silicon compound (a).

In the adhesive composition of the present invention, the hydrophobic finely divided silica (f) is blended in order to enhance the strength of the cured product, and normally a particle size of about 0.007 μm is used. . As the hydrophobic fine powder silica (f), those surface-treated with CH ₃ group, silicon oil, octylsilane or the like are used.

In the present invention, the hardened material becomes too hard when the amount of the above-mentioned hydrophobic finely divided silica (f) is increased, so that it is 5 per 100 parts by weight of the modified silicon compound (a).
Limited to ~ 15 parts by weight.

In the adhesive composition of the present invention, an organotin catalyst (g) is blended as a catalyst for curing the modified silicon compound (a). Examples of the organic tin catalyst (g) used include butyltin laurate type and butyltin phthalate type.

In the present invention, if the compounding amount of the organotin catalyst (g) is small, the thixotropic effect is small, and if it is too large, the thixotropic effect is saturated, and the durability of the cured adhesive is adversely affected. , Modified silicon compound (a) 1
It is limited to 0.5 to 3 parts by weight with respect to 00 parts by weight.

In the adhesive composition of the present invention, lightweight glass hollow spheres (h) are added in addition to the above-mentioned organic anti-sagging agent (e) in order to enhance thixotropy and prevent sagging of the adhesive. There is. As the lightweight glass hollow sphere (h) used,
Average particle density 0.12 to 0.49 g / cc, particle size 0.
Those having a low density and a high strength in the range of 01 to 0.3 mm and a compressive strength of 7 to 421 kg / cm ² are preferable in order to enhance thixotropic properties. As such a light glass hollow sphere (h), for example, Sumitomo "Scotch light glass bulb" manufactured by 3M Co., Ltd. may be mentioned.

In the present invention, when the compounding amount of the light-weight glass hollow spheres (h) is small, there is no effect of enhancing thixotropic properties, and when the compounding amount is too large, the cured product becomes brittle, so 100 parts by weight of the modified silicon compound (a) is used. It is limited to 1 to 5 parts by weight.

The adhesive containing the light weight glass hollow spheres (h) in the above-mentioned range by weight has the effect of reducing the resistance applied to the comb trowel when it is applied to a flat or vertical surface using the comb trowel. The workability is improved, and the cured product can be provided with flexibility.

[0035]

EXAMPLES Examples of the present invention will be described below. As Examples 1 to 5 and Comparative Examples 1 to 3, agents A and B were prepared in the proportions shown in Table 1 below. The contents of various compounding agents in Table 1 are as follows. -Modified silicon compound: "Cyril 5B2" manufactured by Kanegafuchi Chemical Co., Ltd.
5 "and" Cyryl 5B30 "-Epoxy resin: Yuka Shell Epoxy" Epicoat 828 "(component: bisphenol A type glycidyl ether) -Epoxy resin curing agent (tertiary amine): Rohm and Haas" DMP- " 30 "[component: 2,4,6-tris (dimethylaminomethyl) phenol] -organotin catalyst:" SB-65 "(component: dibutyltin dilaurate + dibutyltin oxide) manufactured by Sankyo Machine Co., Ltd.-colloidal sodium carbonate: Maruo Calcium "Calfine 200M" ・ Heavy sodium carbonate: Shiraishi Kogyo "Whiten S"
B "-Organic sagging preventive agent:" Disparlon # 30 "manufactured by Kusumoto Kasei Co., Ltd.
5 "(component: castor oil hydrogenated oil) -hydrophobic fine powder silica:" Aerosil R-202 "manufactured by Nippon Aerosil Co., Ltd.-Lightweight glass hollow sphere:" Scotch light glass bulb S-28 / 750 "manufactured by Sumitomo 3M Co., Ltd.

2) Evaluation of Adhesive The adhesive prepared by mixing the agents A and B in the ratio shown in Table 1 was evaluated by the following method, and the results are shown in Table 1. (1) Pot life: A total of 400 g of modified silicone compounding agent (A agent) and epoxy resin compounding agent (B agent) was placed on a plate, and the two liquids were mixed with a spatula and placed in an oven at 40 ° C. It was warmed up and sensory evaluated the dry time by touching with a finger. (2) Curing flexibility: 70 mm of a mixture of agents A and B
After being cast in a size of 40 mm x 2.5 mm and cured at room temperature for 2 days, it is cured in a constant temperature bath at 50 ° C for 2 days to cure, and then the cured product is bent and the teared state is functionalized. evaluated. (3) Tile misalignment: 1.5 kg / m of adhesive on a board extending in the vertical direction using a 5 mm square sharpening iron
^It is applied so that the ratio becomes ² , then 60 mm ×
Two 225 mm × 8 mm thick, 250 g weight porcelain wet tiles with soles were stacked and adhered to a board extending in the vertical direction, and the misalignment in the initial state of adhesion was visually evaluated. (4) Workability: A sensory evaluation of the workability of the worker when the worker combs it is performed.

[0037]

[Table 1]

As is clear from Table 1, the adhesives having the compounding ratios of Examples 1 to 5 all had a long pot life,
It also has excellent flexibility after curing, good workability,
Furthermore, it can be seen that the tiles are not displaced. On the other hand, it is understood that the adhesives having the composition ratios of Comparative Examples 1 to 3 cannot satisfy any of the pot life, the curing flexibility, the workability, and the tile misalignment.

[0039]

As described above, according to the present invention, since the pot life of the adhesive is extended, the economical efficiency is improved, and not only the flexibility after curing is excellent, but also When bonding structural materials such as tiles to the vertically extending surface,
It is possible to obtain an adhesive that is less likely to cause structural material displacement. Moreover, when configured as a two-component adhesive, it is possible to provide an adhesive for on-site construction which is excellent in workability and which can smoothly perform mixing, coating work and tool cleaning work.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display area C08K 7/28 NLD 7242-4J

Claims (1)

[Claims] 1. An adhesive composition comprising an epoxy resin and a silicon compound (a) having a functional group capable of reacting with an epoxy group and a reactive silicon group in one molecule, said (a) silicon compound For 100 parts by weight,
(B) Epoxy resin 30 to 70 parts by weight, (c) Colloidal calcium carbonate 50 to 90 parts by weight, (d) Heavy calcium carbonate 20 to 50 parts by weight, (e) Organic anti-sagging agent 2 to 8
Parts by weight, (f) 5 to 15 parts by weight of hydrophobic finely divided silica,
An adhesive composition comprising (g) 0.5 to 3 parts by weight of an organotin catalyst and (h) 1 to 5 parts by weight of lightweight glass hollow spheres.