JP4475698B2 - Primer composition and method for joining concrete and mortar using the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an epoxy resin primer composition suitable for use in transferring new concrete and mortar to existing concrete and mortar base (hereinafter simply referred to as “base”), and concrete and mortar using the same. It relates to the method of joining.
[0002]
[Prior art]
In general, when new concrete or mortar is handed over to the base, the surface of the base is roughened for the purpose of increasing the bonding area and anchoring effect.
This method can be expected to have some effect in the short term, but eventually concrete or mortar does not have adhesiveness, and eventually peels.
In order to prevent this peeling, there is a method in which the primer composition such as acrylic, EVA or SBR is applied to the base in advance and then succeeded, but the adhesion is not sufficient, and the aggregation of the primer composition itself is not possible. Since the force is smaller than that of concrete and mortar and the alkali resistance is low, there is a problem in durability.
Epoxy resin adhesives are widely used to solve this problem.
This adhesive is a compound composed of a main component mainly composed of an epoxy resin and an amine curing agent, and is excellent in adhesiveness and has high cohesive strength and durability after curing. Unfortunately, however, this type of adhesive has time constraints on the joining operation, and after applying an adhesive containing a mixture of the main agent and curing agent to the substrate, it can take up to 7-8 hours at room temperature. If new concrete and mortar are not handed over, the applied adhesive will harden and lose its effectiveness.
By the way, generally, when concrete and mortar are handed over, the concrete and mortar are driven in after placing the reinforcement and assembling the formwork, and once such work is done, the adhesive is grounded. It is virtually impossible to apply to.
Therefore, before placing the bars, assembling the formwork and placing new concrete and mortar, the pre-applied adhesive possesses excellent splicing performance (excellent adhesion, high cohesion and durability after curing). Development of such a joining agent has been desired.
[0003]
[Problems to be solved by the invention]
In the present invention, in the joining of concrete and mortar, the jointable time after coating is dramatically extended, and even with a wet base, excellent jointing performance at any time within the jointable time ( The present invention provides a primer composition that exhibits excellent adhesiveness and high cohesion and durability after curing.
[0004]
[Means for Solving the Problems]
In general, in an epoxy resin adhesive, 1 equivalent of an amine curing agent is added to 1 equivalent of epoxy resin.
Therefore, it is usual to mix | blend the quantity of amine type hardening | curing agents calculated by following Formula with respect to 100 weight part of epoxy resins.
Amount of amine-based curing agent = amine equivalent ÷ epoxy equivalent × 100 (parts by weight)
However, the present inventors use an amine-based curing agent in an amount less than an equivalent amount with respect to the epoxy resin, so that the primer composition can be transferred after 3 days, as a matter of course immediately after coating, and has excellent punching. It was discovered that the joint performance (excellent adhesiveness, high cohesion and durability after curing) was exhibited, and a prior invention was completed separately.
And based on the above-mentioned prior invention, it has been found that by further blending a polysulfide polymer and a tertiary amine compound, it exhibits excellent splicing performance even on a wet base, and the present invention is completed. I came to let you.
[0005]
Specifically, the present invention
1. An epoxy resin, a polyamine-based curing agent, a polysulfide polymer, and a tertiary amine compound are contained, and 0.2 to 0.4 equivalent of the polyamine-based curing agent is blended with respect to 1 equivalent of the epoxy resin, and the epoxy resin 100 Primer composition used for jointing concrete or mortar, characterized by blending 1 to 60 parts by weight of polysulfide polymer and 0.1 to 3.0 parts by weight of a tertiary amine compound with respect to parts by weight ,
2. 1. The polyamine-based curing agent is at least one selected from aliphatic polyamines, alicyclic polyamines, aromatic polyamines or modified products thereof. The primer composition according to
3 . 1. Or 2. A method for joining concrete or mortar, characterized in that the primer composition described in 1) is used.
[0006]
The present invention is described in detail below.
In the primer composition of the present invention, a polyamine curing agent is added in an amount of 0.1 to 0.6 equivalents, preferably 0 to 100 parts by weight of an epoxy resin having two or more epoxy groups in the molecule. The amount (parts by weight) corresponding to 2 to 0.4 equivalents is blended and the polysulfide polymer and the tertiary amine compound are contained, so that the jointable time can be greatly extended and wet. Even with respect to the ground surface, excellent joining performance (excellent adhesiveness, high cohesive strength and durability after curing) can be exhibited at any time within the jointable time.
If the equivalent ratio of the polyamine curing agent to the epoxy resin is less than 0.1, the epoxy resin is not sufficiently cured and does not exhibit a cohesive force. On the other hand, if the amount ratio is larger than 0.6, the jointable time is shortened, which is no different from the conventionally used epoxy resin adhesives.
The polysulfide polymer is blended in an amount of 1 to 60 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the epoxy resin. When it is 60 parts by weight or more, the cohesive force after curing is lowered, and sufficient adhesion to a base (particularly a wet base) and jointability cannot be obtained.
The tertiary amine can be added as a curing accelerator, and the amount added is 0.1 to 5.0 parts by weight, preferably 0.1 to 3.0 parts by weight in order not to shorten the joining time. Appropriate amount.
[0007]
The epoxy resin used in the present invention may be any liquid or solid resin having an average of two or more epoxy groups per molecule, and may be a mixture thereof.
For example, polyglycidyl ether obtained by reacting a polyhydric alcohol such as bisphenol A, bisphenol F, bisphenol AD, catechol and resorcinol with epichlorohydrin: glycidyl obtained by reacting a hydroxyl carboxylic acid such as P-hydroxybenzoic acid with epichlorohydrin Ether ester: Polyglycidyl ester, phenol novolac epoxy resin, cresol novolac epoxy resin obtained by reacting polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin, epoxidized polyolefin, alicyclic epoxy resin, urethane Examples include, but are not limited to, modified epoxy resins.
[0008]
Examples of the polyamine curing agent used in the present invention include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, and alicyclic amine. N-aminoethylpiperazine, laromine C-260 (BASF), mensendiamine, isophoronediamine, 1,3bisaminomethylcyclohexane, bis (4-amino3-methylcyclohexyl) methane, diaminocyclohexylmethane, 3, 9-bis (3-aminopropyl) 2,4,8,10 tetraoxaspiro (5,5) undecane, m-xylylenediamine as an aliphatic amine containing an aromatic ring, metapheny as an aromatic amine Njiamin, diaminodiphenylmethane, diaminodiphenyl sulfone and the like can be used. In addition, modified amines such as these epoxy adduct reactants, Mannich reactants, cyanoethylates, Michael reactants, ketiminates and the like can also be used. However, the polyaminoamide type curing agent is ineffective in splicing properties even if blended in an excessive amount.
[0009]
As the polysulfide polymer, thiocol LP-3 or LP-33 (trade name, manufactured by Toraythiol Co., Ltd.) having a disulfide bond in the main chain and having an average molecular weight of about 1000 and having a terminal SH group is used. it can.
Tertiary amines include 2-dimethylaminoethanolamine, 2-diethylethanolamine, triethylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldiethylamine, etc. Can be used.
The primer composition of the present invention is preferable because the adhesion and durability to concrete and mortar are further improved by adding a coupling agent.
As the coupling agent, for example, silane, titanate, and aluminum are known, and silane coupling agents are particularly effective.
[0010]
In the present invention, for the purpose of improving the workability of the primer composition, an epoxy reactive diluent is used on the main agent side, and a non-reactive diluent, an organic solvent, and a plasticizer are used for both the main agent and the curing agent. Can be used.
The epoxy reactive diluent is not particularly limited as long as it is a commercially available mono, di, or triepoxide. As the non-reactive diluent, benzyl alcohol, nonylphenol, dinonylphenol, xylene resin, coumarone indene resin, isoparaffin mixture, high boiling aromatic hydrocarbon compound, white tar and the like can be used. As the plasticizer, various esters of phthalic acid, phosphoric acid and fatty acid can be used. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cellosolve, methyl cellosolve, n-propanol, isopropanol and the like. It is done.
Furthermore, the primer composition of the present invention uses ultrafine powder silica, calcium carbonate, surface-treated calcium carbonate, talc, mica, aluminum silicate, etc. alone or in combination to prevent sagging when applied to the wall surface. be able to.
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
[0011]
【Example】
( Reference Example 1 )
Equivalent ratio of modified aliphatic polyamine (Rakkamide WH108S manufactured by Dainippon Ink & Chemicals, Inc.) is equivalent to 0.1 with respect to 100 parts by weight of bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) 3 Part by weight, 10 parts by weight of liquid polysulfide (Toyothiol Co., Ltd., thiocol LP-3), 1 part by weight of tertiary amine (Air Products Japan Co., Ltd. Ancamine K-54), each charged in a plastic container and stirred. The primer composition was obtained. This composition was applied to dry and wet concrete, and the adhesive strength and compressive strength were measured according to the evaluation method described later, and the compatibility of the composition was examined. The measurement results are shown in Table 1 together with the composition.
[0012]
(Example 1 )
6 equivalent weight ratio of modified aliphatic polyamine (Da Nippon Ink Chemical Co., Ltd. racamide WH108S) to 100 parts by weight of bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) 6 Part by weight, 10 parts by weight of liquid polysulfide (Toyothiol Co., Ltd., thiocol LP-3), 1 part by weight of tertiary amine (Air Products Japan Co., Ltd. Ancamine K-54), each charged in a plastic container and stirred. The primer composition was obtained. This composition was applied to dry and wet concrete, and the adhesive strength and compressive strength were measured according to the evaluation method described later, and the compatibility of the composition was examined. The measurement results are shown in Table 1 together with the composition.
(Example 2 )
15 parts by weight of an equivalent ratio of 0.3 equivalent of a modified alicyclic polyamine (Ancamine 2074 manufactured by Air Products Japan Co., Ltd.) to 100 parts by weight of bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) , 10 parts by weight of liquid polysulfide (Thiocol LP-3 manufactured by Toray Rethiocol Co., Ltd.) and 1 part by weight of tertiary amine (Ancamin K-54 manufactured by Air Products Japan Co., Ltd.) were each charged in a polycontainer and stirred. It was set as the composition. The composition was applied to dry and wet concrete, and the joint strength and compressive strength were measured according to the evaluation method described later, and the compatibility of the composition was observed. The measurement results are shown in Table 1 together with the composition.
[0013]
(Example 3 )
16 parts by weight of the equivalent ratio of a modified aliphatic polyamine (Adeka Hardener EH220, manufactured by Asahi Denka Kogyo Co., Ltd.) to 100 parts by weight of bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) , 10 parts by weight of liquid polysulfide (Thiocol LP-3 manufactured by Toray Rethiocol Co., Ltd.) and 1 part by weight of tertiary amine (Ancamin K-54 manufactured by Air Products Japan Co., Ltd.) were each charged in a polycontainer and stirred. It was set as the composition. The composition was applied to dry and wet concrete, and the joint strength and compressive strength were measured according to the evaluation method described later, and the compatibility of the composition was observed. The measurement results are shown in Table 1 together with the composition.
( Reference Example 2 )
30 parts by weight of an equivalent ratio of 0.6 equivalent of a modified alicyclic polyamine (Ancamine 2074 manufactured by Air Products Japan Co., Ltd.) to 100 parts by weight of bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) , 10 parts by weight of liquid polysulfide (Thiocol LP-3 manufactured by Toray Rethiocol Co., Ltd.) and 1 part by weight of tertiary amine (Ancamin K-54 manufactured by Air Products Japan Co., Ltd.) were each charged in a polycontainer and stirred. It was set as the composition. The composition was applied to dry and wet concrete, and the joint strength and compressive strength were measured according to the evaluation method described later, and the compatibility of the composition was observed. The measurement results are shown in Table 1 together with the composition.
[0014]
(Comparative Example 1) to (Comparative Example 5)
Equivalent ratio of various polyamine type curing agents to 0.05, 0.8 and 1.0 (parts by weight) with respect to 100 parts by weight of bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) , 10 parts by weight of liquid polysulfide (Toyothiol Co., Ltd., thiocol LP-3), 1 part by weight of tertiary amine (Air Products Japan Co., Ltd. Ancamine K-54), each charged in a plastic container and stirred. A primer composition was obtained. This composition was applied to dry and wet concrete, and the adhesive strength and compressive strength were measured according to the evaluation method described later, and the compatibility of the composition was examined. These (Comparative Example 1) to (Comparative Example 5) are examples in which the blending amount of the polyamine curing agent is different from that of the present invention (Claim 1). The measurement results are shown in Table 2 together with the composition.
[0015]
(Comparative Example 6) to (Comparative Example 10)
For 100 parts by weight of bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.), various polyamine-based curing agents in an equivalent ratio of 0.2 to 0.4 (parts by weight), liquid polysulfide ( 10 to 80 parts by weight of thiocol LP-3 manufactured by Toray Rethiokol Co., Ltd. and 1 to 10 parts by weight of tertiary amine (Ancamin K-54 manufactured by Air Products Japan Co., Ltd.), respectively, are charged into a plastic container and stirred. It was set as the composition. The composition was applied to dry and wet concrete, and the joint strength and compressive strength were measured according to the evaluation method described later, and the compatibility of the composition was observed. These (Comparative Example 6) to (Comparative Example 8) and (Comparative Example 10) are examples in which the blending amount of the polysulfide polymer and / or the blending amount of the tertiary amine is different from the present invention (Claim 3). Yes, (Comparative Example 9) is an example using a polyaminoamide-based curing agent that has no effect on splicing properties even if incorporated in an excessive amount. The measurement results are shown in Table 3 together with the composition.
[0016]
〔Evaluation methods〕
In order to evaluate the joining performance of the primer compositions of Examples and Comparative Examples, the primer composition was applied as it was to a concrete plate prepared according to JIS A5304 "Concrete concrete plate for paving". . In the case of the wet surface, the concrete flat plate was immersed in water for 48 hours or more, and the sufficiently wet concrete flat plate was taken out of the water, and the surface was lightly wiped with a waste cloth and immediately applied with the primer composition. Immediately after application or after standing for 3 days on the primer composition, cement mortar prepared according to JIS R5201 “Cement physical test method” was applied and cured at 20 ° C. for 28 days. After cutting the hardened cement mortar with a size of 40 x 40 mm until reaching the underlying concrete, glue the steel attachment of the same size and pull it with a Kenken-type tensile tester, and transfer each primer composition The bond strength was measured.
-Compressive strength The compression strength after curing of the primer composition was measured after casting the primer composition in a mold so as to have a specified size according to JISK 7208 "Plastic compression test method" and curing for 28 days. .
-Compatibility The compatibility of the primer composition was determined by putting each composition in a glass bottle and leaving it for 7 days, and then observing whether or not the components of each composition were separated.
[0017]
[Table 1]
[0018]
[Table 2]
[0019]
[Table 3]
Destruction state ○: Destruction of ground concrete or jointed mortar Δ: Cohesive failure of primer, or surface layer destruction of ground concrete or jointed mortar (no problem in practical use)
X: Fracture of the interface of the joining mortar [0020]
【The invention's effect】
As described above, the primer composition of the present invention is composed of 100 parts by weight of epoxy resin, 1 part by weight of liquid polysulfide, and 1 part by weight of amine-based curing agent in an equivalent ratio of 0.1 to 0.6 with respect to epoxy resin. By mixing 0.1 part and 5.0 parts by weight of tertiary amine, excellent adhesiveness is exhibited even when the jointable time is remarkably long and the base is wet.

Claims (3)

An epoxy resin, a polyamine-based curing agent, a polysulfide polymer, and a tertiary amine compound are contained, and 0.2 to 0.4 equivalent of the polyamine-based curing agent is blended with respect to 1 equivalent of the epoxy resin, and the epoxy resin 100 1 to 60 parts by weight of a polysulfide polymer and 0.1 to 3.0 parts by weight of a tertiary amine compound are blended with respect to parts by weight . A primer composition used for casting concrete or mortar.   2. The primer composition according to claim 1, wherein the polyamine curing agent is at least one selected from an aliphatic polyamine, an alicyclic polyamine, an aromatic polyamine, or a modified product thereof. A method for joining concrete or mortar, wherein the primer composition according to claim 1 or 2 is used.