JPH0613689B2 - Adhesive for concrete - Google Patents

Description

The present invention relates to an adhesive for concrete. More specifically, it relates to an adhesive for concrete that strongly adheres to concrete and has excellent chemical resistance.

[Conventional technology]

The main materials for civil engineering and construction are soil, rock, wood, cement, steel, etc., but various polymer materials are used as auxiliary materials that supplement the drawbacks of these materials and give new properties. Among them, epoxy resin has excellent adhesiveness, chemical resistance, durability, etc., and because it wets well with concrete, it is an adhesive for repairing crack injection in concrete, coating material for concrete floor, adhesion for tile. Agent,
It is used as an adhesive for connecting inner and new concrete.

Among civil engineering and construction epoxy resins, polyamideamine-based polyamidoamine-based civil engineering and construction epoxy resins have relatively weak adhesion to concrete, for example, Hiroshi Kakiuchi's "New Epoxy Resin" (issued,
In the experimental example described on page 660 of Shokoido Co., Ltd., most of the test pieces were broken between the concrete and the adhesive.

In addition, among the epoxy resins for civil engineering and construction, the polysulfide-based epoxy resin for civil engineering and construction, in which a polysulfide polymer is mixed in a curing agent, has a very strong adhesive force to concrete, and Hiroshi Kakiuchi's "New Epoxy Resin" (issued,
As stated on page 660 of Shokoido Co., Ltd.,
It was an epoxy resin for civil engineering and construction, which had excellent chemical resistance and abrasion resistance without lowering its adhesive strength even after exposure for 10 years outdoors.

[Problems to be solved by the invention]

The conventional polysulfide-based epoxy resin for civil engineering that has a polysulfide polymer compounded in the curing agent has very strong adhesion to concrete, but a polysulfide polymer with a unique mercaptan odor is compounded in the curing agent in the unreacted state. Therefore, although it becomes an odorless cured product after curing, when the main component and the curing agent are mixed and applied, the mercaptan odor generated from the curing agent tends to limit the installation site.

The present inventors have found that the adhesive strength to concrete is very strong, the chemical resistance is excellent in abrasion resistance, and further, the epoxy resin for concrete adhesion that does not have a mercaptan odor is repeatedly studied, and a bisphenol skeleton and a polysulfide skeleton are formed. It has been found that a modified epoxy resin that contains epoxy groups at both end groups and an adhesive for concrete containing amines as a main component strongly adheres to concrete and has no mercaptan odor. Has reached the present invention.

[Means for solving problems]

(A) A modified epoxy resin containing a bisphenol skeleton and a polysulfide skeleton, and having both end groups being epoxy groups, and (B) an amine as a main component, and the weight ratio of the polysulfide skeleton in the modified epoxy resin is 5 An adhesive for concrete, wherein the amount of the amines is 3 to 60 parts by weight with respect to 100 parts by weight of the modified epoxy resin,
An adhesive for concrete, which has a sufficient adhesive force even for wet concrete.

The modified epoxy resin of the present invention is an epoxy resin having a polysulfide skeleton introduced into an epoxy resin having a bisphenol skeleton.

The bisphenol skeleton of the modified epoxy resin in the present invention is, for example, bisphenol A or bisphenol A.
D, halogenated bisphenol A, bisphenol F,
It has the same molecular structure as halogenated bisphenol F.

The polysulfide skeleton of the modified epoxy resin in the present invention has the general formula —ROR′OR—Sx— (wherein R and R ′ are alkyl groups having 1 to 4 carbon atoms, and the average of x is 1 to 3). Shown.

Further, preferred polysulfide skeleton of the modified epoxy resin of the present invention is a _{-C 2 H 4 OCH 2 OH 2} H 4 -Sx- ( Note that the average of x is 1.5 to 2.5).

The modified epoxy resin in the present invention is produced, for example, by reacting an epoxy resin having a bisphenol skeleton with a substance having a polysulfide skeleton. The modified epoxy resin in the present invention is preferably produced by a method in which a substance having a polysulfide skeleton, for example, a polysulfide polymer and a bisphenol type epoxy resin are reacted in an excessive amount of the bisphenol type epoxy resin.

The modified epoxy resin in the present invention can be produced by a method using a solvent such as toluene or a method using a catalyst such as a tertiary amine, a solvent-free method, a reaction without a catalyst, or the like. The modified epoxy resin produced by the above method can also be used in the present invention.

In the modified epoxy resin according to the present invention, the weight ratio of the bisphenol skeleton to the polysulfide skeleton can be controlled by appropriately selecting the molecular weights of the substance having the polysulfide skeleton as the raw material and the bisphenol type epoxy resin. Further, the weight ratio of the bisphenol skeleton to the polysulfide skeleton can be controlled by selecting the reaction ratio of the substance having a polysulfide skeleton and the bisphenol type epoxy resin.

Regarding the weight ratio of the bisphenol skeleton and the polysulfide skeleton of the modified epoxy resin in the present invention, the effect aimed at by the present invention can be obtained by controlling the weight ratio of the polysulfide skeleton in the range of 5% to 75%. If the weight ratio of the polysulfide skeleton exceeds 75%, the cured product becomes soft and the strength decreases, which is not preferable.

Further, if the weight ratio of the polysulfide skeleton is less than 5%, the adhesiveness to concrete is lowered and curing shrinkage occurs, which is not preferable.

In the adhesive for concrete of the present invention, amines are compounded in addition to the modified epoxy resin.

Examples of amines blended in the present invention include triethylenetetramine, pentaethylenehexamine, isophoronediamine, cyclohexylamine, 1,2-diaminocyclohexane, and 1,3-bis (aminomethyl).
Cyclohexane, bis (4-amino-3-methylcyclohexyl) methane, m-xylenediamine, m-phenylenediamine, 4,4'-methylenedianiline, N-benzylethylenediamine, 1- (2-aminoethyl) piperazine, N , N-dimethylamino-n-propylamine, N, N, N'N'-tetramethylhexamethylenediamine, N-methylpiperidine, N, N'-dimethylpiperazine, dimethylaminomethylphenol, 2,4,
6-tris (dimethylaminomethyl) phenol, or a modified polyamine obtained by reacting an epoxy resin with excess polyamine, an oxide-modified epoxy resin adduct obtained by reacting a polyamine with an oxide compound, a cyanoethylated polyamine obtained by reacting a polyamine with acrylonitrile, Furthermore, polyamidoamine in which dimer acid and polyamine are condensed is exemplified.

The blending amount of the amines in the present invention varies depending on the kind of the amines, but it is usually preferable to blend 3 to 60 parts by weight with respect to 100 parts by weight of the modified epoxy resin.

In the concrete adhesive of the present invention, if necessary, silica sand, aluminum powder, carbon black, forastonite, clay, titanium oxide, iron oxide, silica, cyanine blue, coal tar, talc, calcium carbonate, bentonite, Fillers such as polyethylene powder, mica, lead chromate, nickel slag, and aluminum hydroxide, extenders, reinforcing materials, pigments, flame retardants and the like can be added.

〔Example〕

Next, the present invention will be described with reference to Synthesis Examples, Examples and Comparative Examples.

Synthesis Example 1 A 1-liter separable flask was charged with a polysulfide polymer ("Thiocol LP-" manufactured by Toray Thiocol Co., Ltd.).
3 ") 100 g and bisphenol A type epoxy resin (" Adeka Resin EP-4100 "manufactured by Asahi Denka Co., Ltd.) 2
00 g was added and the mixture was stirred at room temperature for 15 minutes.

Furthermore, 2,4,6-tris (dimethylaminomethyl)
0.05 g of phenol was added and stirred for 1 hour. After standing at room temperature for 24 hours, it was confirmed that all the polysulfide polymer had reacted with the bisphenol A type epoxy resin. At this time, the epoxy equivalent is 344 and the viscosity is 64.
It was 0 poise (25 ° C.), and the reaction product had no mercaptan odor.

Example 1 100 parts by weight of the epoxy resin of Synthesis Example 1 was mixed with 5 parts by weight of triethylenetetramine to bond concrete. The bonded concrete was cured at 20 ° C. for 7 days, and the flexural bond strength to the concrete was measured. The measuring method was in accordance with JIS A 6024 (1981) "Injected epoxy resin for building repair" (4.8) "Adhesive strength".
The results are summarized in Table 1. As shown in Table 1, the concrete to be adhered was broken and the adhesion was good.

Example 2 In Example 1, 17 parts by weight of bis (4-amino-3-methylcyclohexyl) methane was used instead of 5 parts by weight of triethylenetetramine to measure the adhesive strength to concrete. The results are summarized in Table 1. As shown in Table 1, the concrete to be adhered was broken and the adhesion was good.

Example 3 In Example 1, instead of 5 parts by weight of triethylenetetramine, a modified aliphatic polyamine (Asahi Denka Kogyo Co., Ltd.) was used.
The adhesive strength to concrete was measured using 23 parts by weight of "Adeka Hardener EH-230" manufactured by Adeka. The results are summarized in Table 1. As shown in Table 1, the concrete to be adhered was broken and the adhesion was good.

Example 4 In Example 1, a modified aromatic polyamine (Asahi Denka Kogyo Co., Ltd.) was used instead of 5 parts by weight of triethylenetetramine.
The adhesive strength to concrete was measured using 32 parts by weight of "Adeka Hardener EH-541" manufactured by Adeka. The results are summarized in Table 1. As shown in Table 1, the concrete to be adhered was broken and the adhesion was good.

Synthesis Example 2 A 1 liter separable flask was charged with a polysulfide polymer ("Thiocol LP-" manufactured by Toray Thiokol Co., Ltd.).
3 ") 93 g and bisphenol F-type epoxy resin (" Araldite XPY306 "manufactured by Nippon Ciba-Geigy Co., Ltd.)
165 g was added and the mixture was stirred at room temperature for 10 minutes. In addition, 2,
4,6-tris (dimethylaminomethyl) phenol
0.05 g was added and stirred for 2 hours. After being left at room temperature for 24 hours, the polysulfide polymer was completely bisphenol F.
It was confirmed that it was reacted with the epoxy resin. At this time, the epoxy equivalent is 310 and the viscosity is 140 poise (25
C.), and the reaction product had no mercaptan odor.

Example 5 100 parts by weight of the epoxy resin of Synthesis Example 2 was added with 2,4,6-
Tris (dimethylaminomethyl) phenol (7.5 parts by weight) was mixed and the flexural adhesion strength to concrete was measured in the same manner as in Example 1 (this is referred to as drying condition).
Furthermore, the same mixture was immersed in water at 20 ° C. for 1 day to bond concrete containing sufficient water. Room temperature and humidity (20 ℃ ± 1 ℃, humidity 90 ~ 100
%) And cured for 7 days to measure the flexural bond strength. (This is called wet condition). The measuring method is JIS A
6024 (1981) "Injection epoxy resin for building repair" (4.8) "Adhesive strength". The results are summarized in Table 2.

As shown in Table 2, the concrete to be adhered was broken, and the adhesion was good.

Example 6 100 parts by weight of the epoxy resin of Synthesis Example 1 was mixed with N, N,
N ', N'-tetramethylhexamethylenediamine 10
The parts by weight were mixed, and the bending adhesive strength to concrete was measured in the same manner as in Example 5. The results are summarized in Table 2. As shown in Table 2, the concrete to be adhered was broken, and the adhesion was good.

Example 7 12.3 parts by weight of 1- (2-aminoethyl) piperazine was mixed with 100 parts by weight of the epoxy resin of Synthesis Example 1, and the bending adhesive strength was measured in the same manner as in Example 5. The results are shown in Table 2.
Summarized in. As shown in Table 2, the concrete to be adhered was broken, and the adhesion was good.

Example 8 100 parts by weight of the epoxy resin of Synthesis Example 1 was mixed with 20 parts by weight of polyamidoamine ("Ancamide 501" manufactured by ACI Japan Limited), and bending adhesive strength was performed in the same manner as in Example 5. Was measured. The results are summarized in Table 2. As shown in Table 2, the concrete to be adhered was broken, and the adhesion was good.

Example 9 100 parts by weight of the epoxy resin of Synthesis Example 1 was mixed with 2,4,6-
7.5 parts by weight of tris (dimethylaminomethyl) phenol were mixed and the flexural adhesion strength to concrete was measured in the same manner as in Example 5. The results are summarized in Table 3. As shown in Table 3, the concrete, which was the adherend, was broken and the adhesion was good.

Furthermore, the same mixture was cured at 20 ° C. for 7 days, and the flexural strength and compression strength of the cured product were measured.

The results are summarized in Table 3. As shown in Table 3, the cured product was tough.

Example 10 To 100 parts by weight of the epoxy resin of Synthesis Example 1, 35 parts by weight of a bisphenol A type epoxy resin (“Sumiepoxy ELA115” manufactured by Sumitomo Chemical Co., Ltd.) was mixed and used as a main agent. As a curing agent, a mixture of 10 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol and 5 parts by weight of N-benzylethylenediamine was used. The main agent and the curing agent are mixed at a ratio of 135 parts by weight / 15 parts by weight,
In the same manner as in Example 9, the flexural adhesive strength to concrete and the flexural strength and compressive strength of the cured product were measured. The results are summarized in Table 3.

As shown in Table 3, the adhesiveness was good and the cured product was tough.

Comparative Example Bisphenol A type epoxy resin (Sumitomo Chemical Co., Ltd.)
"Sumiepoxy ELA115" manufactured by Sumitomo Chemical Co., Ltd. as a main agent, and 35 parts by weight of a polysulfide polymer ("Thiocol LP-3" manufactured by Toray Thiokol Co., Ltd.) as a curing agent.
4,6-Tris (dimethylaminomethyl) phenol 5
A mixture of 10 parts by weight of N-benzylethylenediamine and 10 parts by weight of N-benzylethylenediamine was used. 100 parts by weight of main agent and curing agent /
The mixture was mixed at a ratio of 50 parts by weight, and the bending adhesion strength to concrete and the bending strength and compression strength of the cured product were measured in the same manner as in Example 9. The results are summarized in Table 3. As shown in Table 3, the adhesiveness was good, and a tough cured product was obtained.
However, a mercaptan odor due to the polysulfide polymer was generated during mixing.

Example 11 The same formulation as in Example 10 was applied to a concrete surface and cured at 20 ° C. for 4 days.

A water pressure of ² kg / cm ² was applied for one year from the back surface of this concrete. One year later, the surface condition of the concrete was observed. Exudation of water from the concrete surface, or
It was confirmed that the concrete and the coating film did not peel off, and that the adhesive for concrete of the present invention had sufficient performance as a coating material for a concrete floor.

〔The invention's effect〕

(1) Since the adhesive for concrete of the present invention contains an epoxy resin having a polysulfide skeleton as a main component, it strongly adheres to concrete and has excellent chemical resistance, abrasion resistance, and durability.

(2) Since the concrete adhesive of the present invention does not contain a component having a mercaptan odor, the construction site is not limited by the odor.

(3) The adhesive for concrete of the present invention is an adhesive for repairing crack injection of concrete, a floor coating agent for concrete floor, a surface protection lining for concrete, an adhesive for tiles, an adhesive for splicing new and old concrete, a floor coating Suitable for material primer, road surface seal coat pavement, etc.

Claims (1)

[Claims] 1. A modified epoxy resin containing (A) a bisphenol skeleton and a polysulfide skeleton, and having both end groups being epoxy groups, and (B) an amine as a main component, wherein the polysulfide skeleton in the modified epoxy resin is contained. A weight ratio of 5 to 75%, and the compounding amount of the amines is 3 to 60 parts by weight with respect to 100 parts by weight of the modified epoxy resin.
An adhesive for concrete, which has a sufficient adhesive force even for wet concrete.