JP2000345101A - Primer composition, and method for jointing concrete or mortar using the primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a primer composition enabling the dramatic extension of the allowance in time of jointing after coating in the jointing of concrete or mortar and capable of exhibiting excellent jointing performance even in the case where the groundwork is wet by compounding an amine hardener in an amount specific to an epoxy resin. SOLUTION: This primer composition is obtained by compounding (A) an epoxy resin (e.g. a bisphenol A-type epoxy resin), (B) a polyamine hardener, (C) a polysulfide polymer and (D) a tertiary amine compound, wherein the component B is 0.1-0.6 equivalent based on one equivalent of the component A. Further, it is preferable that the component B is one or more kinds selected from aliphatic polyamines, alicyclic polyamines, aromatic polyamines and modified compounds of these polyamines, and 1-60 pts.wt. and 0.1-3.0 pts.wt. of the component C and the component D, respectively are compounded based on 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an existing concrete or mortar base (hereinafter simply referred to as "base").
The present invention relates to an epoxy resin-based primer composition suitable for use in joining new concrete and mortar, and a method for joining concrete and mortar using the same.

[0002]

2. Description of the Related Art Generally, when a new concrete or mortar is to be used as a base material, the surface of the base material is roughened in order to increase an adhesion area and an anchoring effect. Although this method can be expected to have some effect in the short term, concrete and mortar do not have adhesiveness originally, and eventually lead to peeling. In order to prevent this peeling, acrylic
There is also a method of applying a primer composition such as an EVA-based or SBR-based composition and then continuing the application. However, the adhesion is not sufficient, and the cohesive force of these primer compositions themselves is smaller than that of concrete or mortar. Since it is low, there is also a problem in durability. To solve this problem, epoxy resin-based adhesives are widely used. This adhesive is a compound comprising a main agent containing an epoxy resin as a main component and an amine-based curing agent, and has excellent adhesiveness and, after curing, high cohesive strength and durability. Unfortunately, however, this type of adhesive has a time limit in the joining operation, and after applying an adhesive obtained by mixing a base material and a curing agent on a substrate, it is required to be at most 7 at room temperature.
If new concrete and mortar are not spliced within ８8 hours, the applied adhesive will harden and lose its effect. By the way, in general, when joining concrete and mortar, rebar is arranged on the joint of the foundation and a formwork is assembled, and then concrete and mortar are newly poured in. Is no longer practically possible. Therefore, the pre-applied adhesive has excellent joint performance (excellent adhesiveness, high cohesive strength and durability after hardening) before arranging the reinforcement, forming the formwork, and driving in the new concrete and mortar. The development of such a jointing agent has been desired.

[0003]

SUMMARY OF THE INVENTION According to the present invention, in the joining of concrete and mortar, the joining time after application is drastically extended, and even when the substrate is wet,
An object of the present invention is to provide a primer composition which exhibits excellent joint performance (excellent adhesiveness, high cohesive strength and durability after curing) at any time within the jointable time.

[0004]

Generally, in an epoxy resin-based adhesive, one equivalent of an amine-based curing agent is blended with respect to one equivalent of an epoxy resin. Therefore, epoxy resin 100
It is common to add an amine-based curing agent in an amount calculated by the following formula to parts by weight. The amount of the amine-based curing agent = amine equivalent / epoxy equivalent × 100 (parts by weight) However, the present inventors applied the primer composition to the epoxy resin by using the amine-based curing agent in an amount less than the equivalent. Immediately after that, of course, it was possible to splice even after three days, and found that it exhibited excellent splicing performance (excellent adhesiveness, high cohesion and durability after curing).
The prior invention was completed separately. Then, based on the prior invention, a polysulfide polymer and 3
By blending with a quaternary amine compound, it has been found that it exhibits excellent joint performance even on a wet substrate,
The present invention has been completed.

Specifically, the present invention provides (1) an epoxy resin, a polyamine-based curing agent, a polysulfide polymer, and a tertiary amine compound, wherein the polyamine-based curing agent is added in an amount of 0 to 1 equivalent of the epoxy resin. And (2) the polyamine-based curing agent is at least one selected from aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and modified products thereof. (1) The primer composition according to (1), wherein (3) 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 mixed with 100 parts by weight of the epoxy resin. ) Or (2), and (4) concrete or mould using the primer composition according to any of (1) to (3) above. It is a striking splicing method of the barrel.

Hereinafter, the present invention will be described in detail.
The primer composition of the present invention is prepared by adding a polyamine-based curing agent to 100 parts by weight of an epoxy resin having two or more epoxy groups in a molecule in an amount of 0.1 to 0.1 to 1 equivalent of the epoxy resin.
6 equivalents, preferably 0.2 to 0.4 equivalents (parts by weight) are blended, and the polysulfide polymer and the tertiary amine compound are contained, so that the jointable time is greatly extended. In addition, excellent splicing performance (excellent adhesiveness, high cohesive strength and durability after curing) can be exerted on a moist substrate any time within the splicable time. If the equivalent ratio of the polyamine-based curing agent to the epoxy resin is less than 0.1, the curing of the epoxy resin is insufficient and the cohesive force is not developed, so that the adhesiveness and durability are deteriorated, which is not preferable. On the other hand, if the ratio is more than 0.6, the time for joining is shortened, which is no different from the conventionally used epoxy resin adhesive. The polysulfide polymer is used in an amount of 1 to 60 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the epoxy resin.
30 parts by weight are blended. If the amount is more than 60 parts by weight, the cohesive strength after curing is reduced, and sufficient adhesiveness to a base (particularly, a wet base) and joint property cannot be obtained. The tertiary amine can be added as a curing accelerator. The amount of the tertiary amine is 0.1 to 5.0 parts by weight, preferably 0.1 to 3.0 parts by weight in order not to shorten the joint time. Appropriate amount.

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 of these resins. For example, polyglycidyl ether obtained by reacting a polyhydric alcohol such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol and epichlorohydrin: glycidyl obtained by reacting epichlorohydrin with a hydroxylcarboxylic acid such as P-hydroxybenzoic acid Ether ester: a polyglycidyl ester obtained by reacting a polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, furthermore, an epoxidized polyolefin, an alicyclic epoxy resin, urethane Examples include modified epoxy resins, but are not limited thereto.

Examples of the polyamine-based curing agent used in the present invention include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine and fatty acids. N-aminoethylpiperazine, laromin C-260 (BAS
F), mensendiamine, isophoronediamine, 1,
3-bisaminomethylcyclohexane, bis (4-amino-3-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, metaphenylenediamine as an aromatic amine, diaminodiphenylmethane, diaminodiphenylsulfone and the like can be used. . Also these epoxy adduct reactants,
Modified amines such as Mannich reactants, cyanoethylates, Michael reactants, ketimines and the like can also be used. However, even if the polyaminoamide-based curing agent is added in an excessively small amount, it has no effect on the jointability.

As a polysulfide polymer, thiochol LP-3 having a disulfide bond in the main chain and having an SH group at the end thereof and having an average molecular weight of about 1000 is used.
Alternatively, LP-33 (trade name, manufactured by Toray Thiokol) can be used. Examples of the tertiary amine include 2-dimethylaminoethanolamine, 2-diethylethanolamine, triethylamine, benzyldimethylamine,
4,6-tris (dimethylaminomethyl) phenol,
Compounds having a tertiary amino group in the molecule, such as benzyldiethylamine, can be used. The primer composition of the present invention is preferable because the adhesion to concrete and mortar and the durability are further improved by blending a coupling agent. As the coupling agent, for example, silane-based,
Titanate and aluminum are known, but silane coupling agents are particularly effective.

In the present invention, in order to improve the workability of the primer composition, an epoxy-based reactive diluent is used on the main agent side, and a non-reactive diluent, an organic solvent is used on both the main agent and the curing agent. Plasticizers can also be used. The epoxy-based reactive diluent is not particularly limited as long as it is a commercially available mono-, di-, or triepoxide. Non-reactive diluents include benzyl alcohol, nonylphenol, dinonylphenol, xylene resin, coumarone indene resin, isoparaffin mixture,
High boiling aromatic hydrocarbon compounds, white tar and the like can be used. As the plasticizer, various esters of phthalic acid type, phosphoric acid type and fatty acid type can be used. As the organic solvent, for example, 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-
And propanol and isopropanol. Further, the primer composition of the present invention, in order to prevent dripping when applied to the wall surface, ultrafine powder silica, calcium carbonate,
Surface-treated calcium carbonate, talc, mica, aluminum silicate and the like can be used alone or in combination. 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 1) Bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) 1
3 parts by weight of a modified aliphatic polyamine (Lacamide WH108S manufactured by Dainippon Ink and Chemicals, Incorporated) having an equivalent ratio of 0.1 to 00 parts by weight, and liquid polysulfide (Tiochol LP-3 manufactured by Toray Thiokol Co., Ltd.) 1
0 parts by weight, tertiary amine (Air Products Japan K.K.)
Ancamine K-54) (1 part by weight) was charged into each of polycontainers and stirred to obtain a primer 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 examined. The measurement results are shown in Table 1 together with the composition.

Example 2 Bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.)
100 parts by weight of modified aliphatic polyamine (Lacamide WH108S manufactured by Dainippon Ink and Chemicals, Inc.)
6 parts by weight equivalent to 0.2, 10 parts by weight of liquid polysulfide (Tiocoll LP-3 manufactured by Toray Thiokol Co., Ltd.) and 1 part by weight of tertiary amine (Ankamine K-54 manufactured by Air Products Japan K.K.) Parts and each was charged into a plastic container and stirred to obtain a primer 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 examined. The measurement results are shown in Table 1 together with the composition. (Example 3) A modified alicyclic polyamine (Ankamine 2074 manufactured by Air Products Japan KK) was used in an equivalent ratio of 100 parts by weight of a bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.). 15 parts by weight, equivalent to 3, 10 parts by weight of liquid polysulfide (Tiocoll LP-3 manufactured by Toray Thiokol Co., Ltd.), tertiary amine (Ankamine K- manufactured by Air Products Japan K.K.)
1), and 1 part by weight of each was charged into a polycontainer and stirred to obtain a primer 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.

(Example 4) Bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.)
For 100 parts by weight, 16 parts by weight of a modified aliphatic polyamine (Adeka Hardener EH220 manufactured by Asahi Denka Kogyo KK) having an equivalent ratio of 0.4, and 10 parts of liquid polysulfide (Tiochol LP-3 manufactured by Toray Thiokol Co., Ltd.) were added. 1 part by weight of a tertiary amine (Ankamine K-54 manufactured by Air Products Japan K.K.) was charged into a poly container and stirred to prepare a primer 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. (Example 5) A modified alicyclic polyamine (Ankamine 2074, manufactured by Air Products Japan K.K.) was used at an equivalent ratio of 100 parts by weight of bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.). 6 parts, 10 parts by weight of liquid polysulfide (Tiocoll LP-3 manufactured by Toray Thiokol Co., Ltd.) and tertiary amine (Ankamine K- manufactured by Air Products Japan K.K.)
1), and 1 part by weight of each was charged into a polycontainer and stirred to obtain a primer 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.

(Comparative Examples 1) to (Comparative Example 5) Various polyamine-based curing agents were added at an equivalent ratio of 0.05 to 100 parts by weight of a bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.). , 0.8,
1.0 equivalent (parts by weight), 10 parts of liquid polysulfide (Tiochol LP-3 manufactured by Toray Thiokol Co., Ltd.)
1 part by weight of a tertiary amine (Ankamine K-54 manufactured by Air Products Japan K.K.) was charged into a polycontainer and stirred to obtain a primer 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 examined. This (Comparative Example 1)-
(Comparative Example 5) is an example in which the blending amount of the polyamine-based curing agent is different from that of the present invention (Claim 1). The measurement results are shown in Table 2 together with the composition.

(Comparative Examples 6) to (Comparative Example 10) 100 parts by weight of a bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) is used. An amount corresponding to コ ー ル 0.4 (parts by weight), 10 to 80 parts by weight of liquid polysulfide (Tiochol LP-3 manufactured by Toray Thiokol Co., Ltd.)
1 to 10 parts by weight of a tertiary amine (Ankamine K-54 manufactured by Air Products Japan Co., Ltd.) was charged into each of the polycontainers and stirred to obtain a primer 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 compounding amount of the polysulfide polymer and / or the compounding amount of the tertiary amine is different from the present invention (Claim 3). Yes, (Comparative Example 9)
This is an example in which a polyaminoamide-based curing agent which does not have an effect on the splicing property even if the amount is too small is used. The measurement results are shown in Table 3 together with the composition.

[Evaluation Method] Joint Adhesion In order to evaluate the joint performance of the primer compositions of Examples and Comparative Examples, a concrete flat plate prepared according to JIS A 5304 “Concrete flat plate for pavement” has a dry surface. The primer composition was applied as it was. In the case of a wet surface, the concrete flat plate was immersed in water for 48 hours or more, the sufficiently wet concrete flat plate was taken out of the water, and the water on the surface was wiped lightly with a rag to immediately apply the primer composition. Immediately after application or after standing for 3 days on the primer composition, a cement mortar prepared according to JISR5201 “Physical test method for cement” was poured and cured at 20 ° C. for 28 days. After making a cut in the hardened cement mortar with dimensions of 40 x 40 mm until it reaches the underlying concrete, attach a steel attachment of the same dimensions and pull with a Kenken-type tensile tester to connect each primer composition. The bond strength was measured. Compressive strength The compressive strength of the primer composition after curing is determined according to JIS K72.
In accordance with 08 "Plastic Compression Test Method", the primer composition was poured into a mold so as to have a prescribed size, and after curing for 28 days, the measurement was carried out. -Compatibility The compatibility of the primer compositions was determined by placing each composition in a glass bottle and allowing it to stand for 7 days, and then observing the separation of components of each composition.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3] Destruction state ○: Destruction of foundation concrete or joint mortar △: Cohesive failure of primer or surface layer fracture of foundation concrete or joint mortar (no problem in practical use) ×: Destruction of interface of joint mortar

[0020]

As described above, the primer composition of the present invention comprises 100 parts by weight of an epoxy resin and 100 parts by weight of an amine-based curing agent in an equivalent ratio of 0.1 to 0.6 with respect to the epoxy resin, and a liquid polysulfide. 1 to 60 parts by weight of
By blending 0.1 to 5.0 parts by weight of the quaternary amine, excellent bondability can be exhibited even when the jointable time is remarkably long and the substrate is wet.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hidehiro Kitazawa 5-3-35 Nishibori, Urawa-shi, Saitama Prefecture Konishi Co., Ltd. (72) Inventor Hideharu Ito 5-3-35 Nishibori, Urawa-shi, Saitama Konishi shares F-term in the company Urawa Research Laboratory (reference) 2E172 DD04 4J038 DB001 DB061 JB03 JB05 KA03 PA07 PC04

Claims (4)

[Claims] 1. An epoxy resin, a polyamine-based curing agent, a polysulfide polymer, and a tertiary amine compound, wherein the polyamine-based curing agent is blended in an amount of 0.1 to 0.6 equivalent to 1 equivalent of the epoxy resin. A primer composition comprising: 2. The primer composition according to claim 1, wherein the polyamine-based curing agent is at least one selected from aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and modified products thereof. 3. The method according to claim 1, wherein 1 to 60 parts by weight of the polysulfide polymer and 0.1 to 3.0 parts by weight of the tertiary amine compound are added to 100 parts by weight of the epoxy resin. 3. The primer composition according to item 1. 4. Concrete, characterized by using the primer composition according to any one of claims 1 to 3.
Mortar connection method.