JPS63186723A - Civil engineering and construction material - Google Patents

Abstract

PURPOSE:To obtain the title material which can adhere strongly to concrete, is excellent in chemical resistance, abrasion resistance and durability, does not emit any foreign odor and is not limited in the place of application, by using a specified modified epoxy resin and an amine as principal components. CONSTITUTION:The title material mainly consisting of a modified epoxy resin (A) containing a bisphenol skeleton and a polysulfide skeleton and having epoxy groups on both ends (e.g., one obtained by reacting a polysulfide polymer with an excess of a bisphenol A epoxy resin) and an amine (B) (e.g., tri ethylenetetramine). This material can adhere strongly to concrete and excels in chemical resistance, abrasion resistance and durability, does not emit any foreign odor, is not limited in the place of application and can be suitably used as a grant for concrete, a coating agent for concrete floors, a surface protection lining for concrete, a tile adhesive, an adhesive for joining new and old concretes, a primer for painted floor materials, a seal coat pavement for road surfaces, etc.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to materials for civil engineering and construction.

More specifically, the present invention relates to a civil engineering and construction material that strongly adheres to concrete and has excellent chemical resistance.

[Conventional technology]

The main materials for civil engineering and construction are earth, rock, wood, cement, steel, etc., but various polymeric materials are used as auxiliary materials to compensate for the shortcomings of these materials and provide new properties.

Among them, epoxy resin has excellent adhesion, chemical resistance, durability, etc., and also has good wettability with concrete, so it can be used as an adhesive for repairing cracks in concrete, as a coating material for concrete floors, and as an adhesive for tiles. It is used as an adhesive for joining old and new concrete.

Among epoxy resins for civil engineering and construction, polyamidoamine-based epoxy resins for civil engineering and construction, which mainly contain polyamide or polyamine, have relatively weak adhesion to concrete.
■Shokodo) In the experimental example described on page 660,
In most of the test specimens, failure occurred between the concrete and the adhesive.

In addition, among epoxy resins for civil engineering and construction, polysulfide-based epoxy resins for civil engineering and construction, which contain polysulfide polymers in the curing agent, have extremely strong adhesion to concrete. @ Shokodo) As stated on page 660,
It was an epoxy resin for civil engineering and construction that did not lose its adhesive strength even after being exposed outdoors for 10 years, and had excellent chemical resistance and abrasion resistance.

[Problem that the invention seeks to solve]

Conventional polysulfide-based civil engineering and construction epoxy resins that contain polysulfide polymers in the curing agent have very strong adhesion to concrete, but polysulfide polymers with a unique mercaptan odor are mixed into the curing agent in an unreacted state. As a result, although the cured product is odorless after curing, the mercaptan odor emitted from the curing agent tends to limit the places where it can be applied when the main agent and curing agent are mixed and applied.

As a result of extensive research into epoxy resins for civil engineering and construction that have extremely strong adhesion to concrete, excellent chemical resistance and abrasion resistance, and have no mercaptan odor, the inventors discovered that they have a bisphenol skeleton. Modified epoxy resins that contain a polysulfide skeleton and both terminal groups are epoxy groups, and civil engineering and construction materials that have amines as their main components, are materials that strongly adhere to concrete and have no mercaptan odor. We have discovered this and arrived at the present invention.

[Means for solving problems]

The present invention has the following configuration.

(A) a modified epoxy resin containing a bisphenol skeleton and a polysulfide skeleton and having both terminal groups as epoxy groups; and (B) a civil engineering and construction material containing amines as a main component.

The modified epoxy resin of the present invention is an epoxy resin in which a polysulfide skeleton is 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, bisphenol AD
It has the same molecular structure as , halogenated bisphenol A1 bisphenol F1 halogenated bisphenol F, etc.

The polysulfide skeleton of the modified epoxy resin in the present invention is represented by the general formula % (where R and R' are alkyl groups having 1 to 4 carbon atoms, and the average of X is 1 to 3).

Furthermore, a preferable polysulfide skeleton of the modified epoxy resin of the present invention is Cz Ha OCH20Cz Ha S X- (however, 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, such as a polysulfide polymer, and a bisphenol-type epoxy resin are reacted in a state in which the bisphenol-type epoxy resin is in excess.

The modified epoxy resin of the present invention can be produced by a method using a solvent such as toluene, a method using a catalyst such as tertiary amines, or a method of reacting without a solvent or catalyst. A modified epoxy resin produced by the method described above can also be used in the present invention.

In the modified epoxy resin of 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 raw material having a polysulfide skeleton and the bisphenol type epoxy resin. Furthermore, by selecting the reaction ratio of the substance having a polysulfide skeleton and the bisphenol type epoxy resin, the weight ratio of the bisphenol skeleton to the polysulfide skeleton can be controlled.

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

Furthermore, if the weight ratio of the polysulfide skeleton is less than 5%, adhesion to concrete decreases and curing shrinkage occurs, which is not preferable.

In the civil engineering and construction materials of the present invention, amines are blended in addition to the modified epoxy resin.

Examples of the amines to be blended in the present invention include triethylenetetramine, pentaethylenehexazine, isophoronediamine, cyclohexylamine, 1,2-diaminocyclohexane, and 1,3-bis(aminomethyl).
Cyclohexane, bis(4-amino-3-methylcyclohexyl)methane, m-xylene diamine, m-phenylene diamine, 4,4'-methylene dianiline, N-
Benzylethylenediamine, 1-(2-aminoethyl)
piperazine, N,N to 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 an excess of 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, Further examples include polyamide amine, which is a condensation of dimer acid and polyamine.

The amount of amines in the present invention varies depending on the type of amines, but it is usually preferably 3 to 60 parts by weight per 100 parts by weight of the modified epoxy resin.

In the civil engineering and construction material of the present invention, silica sand, aluminum powder, carbon black, phorastonite, clay, titanium oxide, iron oxide, silica, cyanine blue, coal tar, talc, calcium carbonate, bentonite, Fillers such as polyethylene powder, mica, lead chromate, 2.7K slag, aluminum hydroxide, fillers, reinforcing materials, pigments, flame retardants, etc. can be added.

〔Example〕

Next, the present invention will be explained by giving synthesis examples, examples, and comparative examples.

Synthesis Example 1 Put the polysulfide polymer into a 1-liter separable flask and prepare Thiokol LP-3 (made by Thiokol).
100 g and 200 g of bisphenol A type epoxy resin ("Adeka Resin EP-4100" manufactured by Asahi Denka Kogyo ■) were added and stirred at room temperature for 15 minutes.

Furthermore, 2,4,6-tris(dimethylaminemethyl)
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 epoxy resin. At this time, the epoxy equivalent was 344 and the viscosity was 6.
40 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 bending adhesive strength to the concrete was measured. The measurement method is JIs A 6024 (1981) r Injection epoxy resin J (4,8) r Adhesive strength for building repair.
I followed. The results are summarized in Table 1. As shown in Table 1, the adherend concrete was destroyed and the adhesiveness 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, and the adhesive strength to concrete was measured. The results are summarized in Table 1. As shown in Table 1, the adherend concrete was destroyed and the adhesiveness was good.

Example 3 In Example 1, instead of 5 parts by weight of triethylenetetramine, 23 parts by weight of modified aliphatic polyamine (Adeka Hardner EH-230 manufactured by Asahi Denka Kogyo ■) was used to measure the adhesive strength to concrete. did. The results are in Table 1
summarized in. As shown in Table 1, the adherend concrete was destroyed and the adhesiveness was good.

Example 4 In Example 1, instead of 5 parts by weight of triethylenetetramine, 32 parts by weight of modified aromatic polyamine ("ADEKA HARDNER EH-541" manufactured by Asahi Denka Kogyo ■) was used to measure the adhesive strength to concrete. did. The results are in Table 1
summarized in. As shown in Table 1, the adherend concrete was destroyed and the adhesiveness was good.

Table 1 Synthesis Example 2 Put the polysulfide polymer into a 1 liter separable flask ("Thiokol LP-3" made by Thiokol)
93g and 165g of bisphenol F type epoxy resin (“Araldite XPY306” manufactured by Ciba Geigy Japan)
and stirred at room temperature for 10 minutes. Furthermore, 2,4.6-)
0.05g of Lis(dimethylaminomethyl)phenol
and stirred for 2 hours. After standing for 24 hours at room temperature, it was confirmed that all of the polysulfide polymer had reacted with the bisphenol F type epoxy resin. The epoxy equivalent at this time was 310, the viscosity was 140 poise (25°C), and the reaction product had no mercaptan odor.

Example 5 To 100 parts by weight of the epoxy resin of Synthesis Example 2, 2°4.6-
7.5 parts by weight of tris(dimethylaminomethyl)phenol was mixed and the bending adhesive strength to concrete was measured in the same manner as in Example 1 (this is referred to as dry condition).

Furthermore, the same mixture was immersed in water at 20° C. for one day to adhere the concrete that had been sufficiently soaked with water. Place the bonded concrete at room temperature and humidity (20℃±1℃, humidity 90-100℃)
%) conditions for 7 days, and the bending adhesive strength was measured. (This is called a wet condition). The measurement method is JIS
A 6024 (1981) r Injection epoxy resin for building repair J (4, 8) "Adhesive strength". The results are summarized in Table 2.

As shown in Table 2, the adherend concrete was destroyed and the adhesiveness was good.

Example 6 N was added to 100 parts by weight of the epoxy resin of Synthesis Example 1.

10 parts by weight of N,N',N'-tetramethylhexamethylenediamine were mixed, and the bending adhesive strength to concrete was measured in the same manner as in Example 5. The results are in Table 2
summarized in. As shown in Table 2, the adherend concrete was destroyed and the adhesiveness 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 in Table 2
summarized in. As shown in Table 2, the adherend concrete was destroyed and the adhesiveness was good.

Example 8 100 parts by weight of the epoxy resin of Synthesis Example 1 was mixed with 20 parts by weight of polyamide amine (ACI Japan Ltd. "Ancamite 501"), and the bending adhesive strength was measured in the same manner as in Example 5. was measured. The results are summarized in Table 2. As shown in Table 2, the adherend concrete was destroyed and the adhesiveness was good.

Table 2 Example 9 To 100 parts by weight of the epoxy resin of Synthesis Example 1, 2°4.6-
) 7.5 parts by weight of lith(dimethylaminomethyl)phenol was mixed, and the bending adhesive 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 adherend, concrete, was destroyed in all cases, and the adhesion was good.

Furthermore, the same mixture was cured at 20° C. for 7 days, and the bending strength and compressive 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 10 100 parts by weight of the epoxy resin of Synthesis Example 1 was mixed with 35 parts by weight of a bisphenol A epoxy resin ("Sumi Epoxy ELAI 15" manufactured by Sumitomo Chemical Co., Ltd.), and this was used as a main resin. As a curing agent, a mixture of 1 part of 2.4.6-tris(dimethylaminomethyl)phenol (lffi part) and 5 parts by weight of N-benzylethylenediamine was used.

The base agent and the hardening agent were mixed at a ratio of 135 parts by weight/15 parts by weight, and the bending adhesive strength to concrete and the bending strength and compressive 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 the cured product was strong.

Comparative example Bisphenol A type epoxy resin (manufactured by Sumitomo Chemical)
The main ingredient is Sumiepoxy ELA115"), and as a curing agent, 35 parts by weight of polysulfide polymer ("Thiokol LP-3" manufactured by Toshi Thiokol ■), 5 parts by weight of 2,4.6-tris(dimethylaminomethyl)phenol, N - A mixture of 10 parts by weight of benzylethylenediamine was used.The base agent and the hardening agent were mixed in a ratio of 100 parts by weight and 150 parts by weight, and the bending adhesive strength to concrete and the bending strength of the cured product were determined in the same manner as in Example 9. The compressive strength was measured. The results are summarized in Table 3. As shown in Table 3, the adhesiveness was good and a strong cured product was obtained. However, a mercaptan odor due to the polysulfide polymer was generated during mixing.

Table 3 Example 11 The same formulation as in Example 10 was applied to the concrete surface and cured at 20° C. for 4 days.

2 kg/c++f from the back side of this concrete
water pressure was applied for a year. After − years, the surface condition of the concrete was observed. Water seeps from the concrete surface,
Further, there was no peeling of the paint film from the concrete, and it was confirmed that the civil engineering and construction material of the present invention has sufficient performance as a coating material for concrete floors.

〔Effect of the invention〕

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

(2) Since the civil engineering and construction material of the present invention does not contain any component having a mercaptan odor, the construction site is not limited by the odor.

(3) The civil engineering and construction materials of the present invention include adhesives for repairing cracks in concrete, coating agents for concrete floors, surface protection linings for concrete, adhesives for tiles, adhesives for pouring new and old concrete, and floor coatings. Suitable for material primer, seal coat pavement of road surfaces, etc.

Claims (1)

[Claims] 1. A civil engineering and construction material containing (A) a modified epoxy resin containing a bisphenol skeleton and a polysulfide skeleton and having both terminal groups as epoxy groups, and (B) an amine as a main component. 2. The civil engineering and construction material according to claim 1, wherein the weight ratio of the polysulfide skeleton in the modified epoxy resin as component (A) is 5% to 75%.