JP2003301158A - Adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve such problems that, when exterior materials such as a tile and the like are bonded onto a concrete bed, the execution has been carried out by using a cement mortar formulated with a polymer emulsion, whereas involving the problems that the bonding layer is deteriorated with an alkali continuously soaking out from the concrete bed and also lacks in deformation- following properties due to its rigidity, thus generating cracks thereto, resulting actual examples of lifting, peeling and removal of the exterior materials. <P>SOLUTION: A two-liquid type adhesive composition consisting of an epoxy resin-based liquid A and a modified silicone resin-based liquid B, in which both the resins are composited matrix-like is developed in this invention. The adhesive composition is excellent in adhesiveness and deformation-following properties, and since it is also composited with soda-lime borosilicate glass microballoons having alkali resistance, the problems of lifting, peeling and removal of the exterior materials are solved therewith. <P>COPYRIGHT: (C)2004,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition for bonding an exterior material such as a tile or a stone to a substrate, and more particularly, to a liquid A based on an epoxy resin. And a two-liquid type adhesive composition comprising a liquid B based on a modified silicone polymer. 2. Description of the Related Art Conventionally, a fixing material made of polymer cement mixed with a polymer dispersion has been used for fixing an exterior material such as a tile or a stone material to a substrate. Although these adhesives have bondability and adhesiveness, they have basic properties, but they are hard and do not have deformation follow-up properties.
Due to the difference in dimensional change between the base material and the exterior material, peeling and cracking are likely to occur at the bonded portion, causing so-called floating and peeling of the exterior material. If the exterior material comes off, it may lead to personal injury and cannot be left as it is.
In addition, if the floating part is left for a long period of time, water will permeate from the floating part and cause water leakage, and in winter, the permeated water freezes and expands in volume. This, in turn, was a factor, further damaging the groundwork. [0003] On the other hand, when an exterior material such as a tile is adhered to a concrete base, a phenomenon has been observed in which alkali of the concrete oozes into the adhesive layer and deteriorates the adhesive layer. Alkali in concrete leaches into the adhesive layer due to rainwater infiltration, etc., and reaches the interface of the resin component, filler, and other aggregates of the adhesive layer. Causes micro cracks. For this reason, the floating, peeling,
It had caused the spalling. [0004] In the case where floating or peeling occurs, if it is left unattended, it may cause peeling, which may result in personal injury as described above. Therefore, prompt repair is required. For repairing floating and peeled parts, inject epoxy resin into these parts and re-fix the exterior material to the base, or peel off the peeled part and rejoin the exterior material with the adhesive or cement mortar to the peeled part Repair work was performed. However, in the case of epoxy resin, since the adhesive layer is hard and lacks conformability to deformation, it is inevitable that floating and peeling occur, and maintenance is required at an appropriate time. [0005] The present invention is excellent in the following problems, that is, excellent in following up the movement of the base and the exterior material,
An adhesive composition that does not cause cracking, peeling, or the like at the joint between the base and the exterior material, and that does not cause deterioration due to alkali caused by the concrete base and that can facilitate maintenance. It is. SUMMARY OF THE INVENTION The present invention has been made as a result of intensive studies in view of such circumstances, and is based on a liquid A based on an epoxy resin and a modified silicone polymer. The present invention relates to an adhesive composition comprising a liquid B, which solves problems such as floating, peeling, and peeling of an exterior material, and deterioration of an adhesive layer due to alkali which cannot be avoided in a concrete base. It was done. Solution A of the present invention comprises an epoxy resin, a curing catalyst for a modified silicone polymer, a hollow body, and a filler which is appropriately blended. Solution B is a modified silicone polymer having a reactive silicon group, and a dehydrating agent for the modified silicone polymer. , An epoxy resin curing agent and an adhesion improver. Further, if necessary, a physical property modifier for improving the tensile properties, a plasticizer, an anti-sagging agent, a reinforcing agent, an antioxidant, an antioxidant, an ultraviolet absorber and the like are appropriately added. [0008] Epoxy resins used in the liquid A include:
Examples include flame-retardant epoxy resins such as epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, glycidyl ether of tetrabromobisphenol, novolak type epoxy resin, and hydrogenated bisphenol A type epoxy resin. The suitable amount of the epoxy resin to be added is 100 to 70 parts by weight based on 100 parts by weight of the modified silicone polymer, and a preferable compounding can be appropriately selected. As the curing catalyst for the modified silicone polymer, tin compounds such as dibutyltin dilaurate, dioctyltin malate, dibutyltin phthalate, tin octylate, amine salts such as dibutylamine-2-ethylhexoate, other acidic catalysts and the like. Basic catalysts and the like,
These may be used alone or in combination of two or more. Examples of the hollow body to be mixed with the liquid A or the liquid B include shirasu balun, perlite, fly ash balun, alumina balun, zirconia balun, glass bubble, and the like. The use of a micro hollow body is preferred. The soda-lime borosilicate glass has a soda content (Na2
O) is obtained by replacing a part of O) with boron (B2O3), and has improved chemical durability, and has a particle diameter of 10 to 1
Those having a size of 00 μm, preferably 40 to 80 μm are suitable for use. The true specific gravities of S22, K25, K37, and K46, which are the product numbers of Scotchlite “Glass Bubbles”, which is a 3M soda-lime borosilicate glass used in Examples of the present invention, are 0.220 and 0.250, respectively. , 0.
370 and 0.460, and the specific gravity of each is 0.13.
5, 0.155, 0.230, and 0.285 are used, but a variety having a large true specific gravity and a large bulk specific gravity has a strong hollow body wall film, and thus has better performance. Examples of the filler include powders such as calcium carbonate, kaolin, silica, titanium oxide, zinc oxide, and carbon black. Modified silicone polymers blended in Solution B include JP-B-45-36319 and JP-B-46-121.
54, JP-A-50-156599, JP-A-55-8312
3, Nos. 55-135135, etc., and are not particularly limited, and generally have a main chain of polyoxyalkylene or polyolefin and a crosslinkable hydrolyzable silyl group at a terminal. Are included. Examples of the polyoxyalkylene include polyoxyethylene, polyoxypropylene, polyoxybutylene, and the like. Examples of the polyolefin include polyisobutylene. Further, examples of the crosslinkable hydrolyzable silyl group include a methoxysilyl group and an ethoxysilyl group. In addition, as a molecular weight,
It is preferably 4000 to 30,000, and the molecular weight distribution is preferably 1.6 or less. The reactive silicon group is a group which can be crosslinked by a silanol condensation reaction containing a silicon atom to which a hydrolyzable or hydroxyl group is bonded, and is typically represented by the following formula. (Where X is a hydroxyl group or a hydrolyzable group, R
Is a monovalent hydrocarbon group or a triorganosiloxy group having 1 to 20 carbon atoms, a is 0, 1, 2 or 3, b is 0, 1 or 2, and 1 ≦ (sum of a and b), m Is 0 or an integer of 1 to 18). When X is a hydrolyzable group, the reactive silicon group undergoes a hydrolysis reaction and a silanol condensation reaction with water in the presence or absence of a silanol condensation catalyst to crosslink. When X is a hydroxyl group, the reactive silicon group is crosslinked by performing a silanol condensation reaction in the presence or absence of a silanol condensation catalyst. Specific examples of the hydrolyzable group include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Among these, the hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3. Examples of the dehydrating agent for the modified silicone polymer include silane compounds such as silane coupling agents such as vinyltrimethoxysilane, glycidoxypropyltrimethoxysilane and aminopropyltolumethoxysilane, and ethyl orthoformate. Can be These dehydrating agents are used in an amount of 1 to 100 parts by weight of the modified silicone polymer.
It is desirable to mix at a ratio of 10 to 10 parts by weight. As a curing agent for the epoxy resin, a commonly used curing agent for an epoxy resin is used. For example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, aminoethylpiperazine, xylylenediamine, Phenylenediamine,
Examples thereof include amines such as diaminodiphenylmethane and diaminodiphenylsulfone, tertiary amines, polyamide resins, imidazoles, dicyandiamides, and polyamide resins. These curing agents are epoxy resin component 1
It is blended at a desired level in the range of 0.1 to 100 parts by weight based on 00 parts by weight. Hereinafter, the present invention will be described with reference to Examples and Comparative Examples. Examples 1 to 5, Comparative Example 1 Epoxy resin (Adeka Resin BPAE4, Asahi Denka Co., Ltd.)
100), tin-based catalyst (Nitto Kasei Corporation, Neostan U-2)
20), calcium carbonate (Maruo Calcium Co., Ltd. Calfine 200M), water, soda-lime borosilicate glass (Sumitomo 3M Co., Ltd. S22, K25, K37, K46),
A liquid, modified silicone polymer (Kaneka Cyril Co., Ltd., Kaneka Cyril Co., Ltd.) containing an aluminosilicate hollow body (Nippon Philite Co., Ltd., Philite FG, particle size 5 to 300 μm) and polypropylene glycol having a molecular weight of 3000 as a dilution viscosity modifier as shown in the table EST250),
Calcium carbonate (Maruo Calcium Co., Ltd. Calfine 2)
00M), a vinyl silane as a dehydrating agent (Dowconing Toray Co., Ltd. SZ6300), an aminosilane as an adhesion improver (SH602, Dow Corning Toray Co., Ltd.)
0), using solution B containing tertiary amine tris (dimethylaminomethyl) phenol as a curing agent for the epoxy resin as shown in the table, and blending solution A and solution B as shown in Table 1. The adhesive compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were prepared. Formulations are given in parts by weight. [Table 1] Using the adhesives prepared in Examples and Comparative Examples, a mortar and a ceramic tile were adhered as described below and subjected to an adhesion test. * Preparation of adhesion test piece After applying each adhesive to the surface of the mortar prepared by the method specified in JISR5201, using a comb iron, JIS
A ceramic tile specified in A5209 is crimped. The adhesive that has run out of the adhesive surface is immediately removed. Next, a pulling jig is bonded to the surface of the ceramic tile with an epoxy resin adhesive. * Test method The bonded test piece was left for 336 hours under the conditions of 23 ± 2 ° C. and 50 ± 5% RH, then immersed in a saturated aqueous solution of calcium hydroxide at 60 ± 2 ° C. for 168 hours, and then the test piece was run under running water. After immersion in water at 23 ° C for 24 hours, wipe off with a cloth and immediately conduct a tensile test. The results of the adhesion test are shown in Table 2, and the adhesive strength of the adhesive of the example was excellent. [Table 2] The adhesive composition according to the present invention comprises a liquid A containing a curing agent for an epoxy resin and a modified silicone resin, a modified silicone resin, a dehydrating agent for the modified silicone resin and an epoxy resin curing agent. And B solution, which has semi-permanent preservability in the state of each solution.
In addition, the mixture of the two components is formed by combining the hard epoxy resin and the modified silicone resin with elasticity in a matrix, so that an adhesive layer with excellent deformation followability can be formed and floats from the base of the exterior material, Problems such as peeling and peeling were eliminated. In addition, the two-component mixed and reaction-cured product forms an adhesive layer in which soda-lime-borosilicate glass with excellent chemical durability is formed. There is a problem that the adhesive layer is deteriorated due to leaching, but such a problem can be eliminated and the exterior material can be applied to the concrete foundation with a sense of security.

Claims (1)

Claims 1. A liquid containing an epoxy resin, a modified silicone polymer curing catalyst, a modified silicone polymer, a dehydrating agent for the modified silicone polymer, and a B liquid containing an epoxy resin curing agent. Liquid A or B
An adhesive composition comprising a liquid and a hollow body made of soda-lime borosilicate glass.